(en)The disclosure relates to compositions exhibiting a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol. The compositions can include at least 15 wt % of a polyetherimide; at least 35 wt % of a polycarbonate; a polyetherimide siloxane; and optionally, at least one UV stabilizer. The disclosure also relates to methods of shaping such compositions and articles produced from such compositions.

1.ApplicationNumber: US-201414216064-A
1.PublishNumber: US-9228082-B2
2.Date Publish: 20160105
3.Inventor: NARAYANAN ADITYA
CAO FENG

4.Inventor Harmonized: NARAYANAN ADITYA(US)
CAO FENG(US)

5.Country: US
6.Claims:
(en)The disclosure relates to compositions exhibiting a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol. The compositions can include at least 15 wt % of a polyetherimide; at least 35 wt % of a polycarbonate; a polyetherimide siloxane; and optionally, at least one UV stabilizer. The disclosure also relates to methods of shaping such compositions and articles produced from such compositions.

7.Description:
(en)BACKGROUND OF THE INVENTION
High heat thermoplastics such as polyetherimides are known as outstanding high performance materials. Polyetherimides can have a high glass transition temperature (Tg) of 217° C., high modulus, and strength at elevated temperatures and excellent chemical resistance, according to ASTM D543-06. Polyetherimide has an amber color with yellowness index greater than 50. This physical characteristic of polyetherimide limits its colorability to dark colors and fairly light colors, but not to very light colors such as certain white colors. Further, polyetherimide has low impact strength at room temperatures.
Lower heat materials such as polycarbonates and modified versions thereof (example, but not limited to polycarbonate esters) have excellent colorability, high impact strength and very good flow properties. However, these materials have poor resistance to harsh chemical reagents, susceptible to environmental stress cracking, poor UV resistance for light colors and relatively lower strength and modulus compared to polyetherimides.
Thus there exists a need to have a polymer system that can combine the above challenging, but desirable characteristics, all-in-one such as a chemically resistant, high flow, white-colorable, and good impact performance.
Blends of polyetherimide and PC have been evaluated for higher heat, improved ductility, and flame retardance. However, the specific combination of a polymer system that simultaneously imparts excellent chemical resistance, according to ASTM D543-06, to harsh chemical reagents (e.g., concentrated sulfuric acid, phosphoric acid etc.), high flow (thin wall less than 1 mm), colorable to certain ‘white’ colors (defined by L, a, b values), being UV resistant (color shift dE (DE* or ΔE) less than 6-7 units after 300 hrs exposure to ASTM D4459) with good notched impact strength (minimum 50 J/m at 23° C./2 lb hammer weight at greater than 15 wt % TiO 2 pigment loading levels) and environmental stress cracking resistance to many chemicals such as hand sanitizers, moisturizers, sunscreen, cooking oil, e.g., olive oils, hand creams, and the like.
Further, there is a clear need for plastic materials, in addition to possessing all of the above desired characteristics, to also be able to be metallized with a metal such as, but not limited to aluminum, preferably wherein the aluminum is deposited and anodized to provide desirable characteristics such as corrosion resistance and wear resistance, better adhesion to paints and dyes vs. bare metal.
However, most polymeric materials may not survive the various mechanical/chemical treatments (such as, but not limited to, pre-treatment, etching, milling, desmutting, anodizing, coloring, sealing) on the plastic material typically involved during the anodization process
For the foregoing reasons, there is a need for a plastic material that can possess the aforementioned desired characteristics as well as be able to endure the anodization process by maintaining it properties and structural integrity.
BRIEF SUMMARY OF THE INVENTION
An embodiment relates to a novel polymer system comprising PEI-PC-Siloxane-PEI with a unique combination of properties. The properties can include, but are not limited to, high flow (less than 1 mm), chemical resistance, according to ASTM D543-06, to harsh reagents, strength retention under ESCR conditions, UV resistance after 300 hr exposure to ASTM D4459, good strength, modulus and impact performance even at very high TiO 2 pigment loading levels, very good endurance to the anodization process after exposure to harsh chemicals (such as but not limited to sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid etc.), colorable to very light colors (white) to dark colors (jet black). The synergistic functioning of this polymer and additive system is important to realize the desired characteristics of good mechanical properties, UV resistance, chemical resistance, according to ASTM D543-06, high flow, colorability, ESCR in addition to enduring the anodization process that finds huge interest in the consumer electronics industry.
Various embodiments relate to compositions comprising: at least 15 wt % of at least one polyetherimide other than the polyetherimide siloxane; at least 35 wt % of at least one polycarbonate; at least one polyetherimide siloxane; at least one UV stabilizer; and at least one colorant. The composition can exhibit a UV resistance of change in color (ΔE) ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol.
The composition can have a color selected from gray, black, white, light gray, and combinations thereof. Both the gray color and the black color can exhibit an L* value of below 80. When the composition has either the gray color or the black color, the at least one colorant can comprises at least 0.001 parts per hundred (pph) of carbon black. Both the white color and the light gray color can exhibit an L* value greater than or equal to 80. When the composition has either the white color or the light gray color, the at least one colorant can comprise less than 50 pph of titanium dioxide.
The weight ratio of polycarbonate to polyetherimide can provide the composition with a melt index ranging from 1.5 to 6 g/min., at 295° C. and at a loading level of 6.7 kg. The melt index can be sufficient to enable the composition to be molded into a cavity having a dimension of greater than 0 and less than or equal to 3 mm.
An article, comprising the composition and shaped by one selected from molding, extruding, and combinations thereof, can exhibits a strength retention of at least 50% when immersed in an acid solution for a period of 2 to 24 hours at a temperature of about 23° C. and at a strain level selected from 0%, 0.5%, 1.0%, and combinations thereof. The acid solution can be selected from sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof, and wherein the acid solution has a concentration of at least 20%.
In another embodiment, an embodiment is a composition comprising:
at least 15 wt % of at least one polyetherimide; at least 35 wt % of at least one polycarbonate; at least one polyetherimide siloxane; at least one UV stabilizer; and at least one colorant,

wherein the composition exhibits a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol; wherein the composition has a color selected from gray, black, white, light gray, and combinations thereof, wherein both the gray color and the black color exhibit an L* value of below 80; wherein, when the composition has either the gray color or the black color, the at least one colorant comprises at least 0.001 pph of carbon black; wherein both the white color and the light gray color exhibit an L* value greater than or equal to 80; wherein, when the composition has either the white color or the light gray color, the at least one colorant comprises less than 50 pph of titanium dioxide; wherein the weight ratio of polycarbonate to polyetherimide provides the composition with a melt index ranging from 1.5 to 6 g/min., at 295° C. and at a loading level of 6.7 kg; wherein the melt index is sufficient to enable the composition to be molded into a cavity having a dimension of greater than 0 and less than or equal to 3 mm; wherein an article, comprising the composition and shaped by one selected from molding, extruding, and combinations thereof, exhibits a strength retention of at least 50% when immersed in an acid solution for a period of less than 1 up to 24 hours at a temperature of about 23° C. and at a strain level selected from 0%, 0.5%, 1.0%, and combinations thereof; wherein the acid solution is selected from sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof, and wherein the acid solution has a concentration of at least 20%.


Other embodiments relate to a process for shaping such compositions, and to articles comprising such compositions.
These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.


DETAILED DESCRIPTION OF THE INVENTION
Some embodiments are based on the remarkable discovery that by using a specific combination of polyetherimide, polycarbonate, and polyetherimide siloxane copolymer in specific conditions, it is possible to make a composition such that articles made from the composition exhibit UV resistance features that are suitable for several applications. Advantageously, the compositions can also be colored to certain colors while retaining the UV resistance features. Some embodiments relate to compositions (and articles made from the compositions) that can also exhibit a unique combination of flow properties, chemical resistance properties according to ASTM D543-06, and ultraviolet resistance properties that make them suitable for certain applications, e.g., consumer electronic applications.
The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention as well as to the examples included therein. All numeric values are herein assumed to be modified by the term “about,” whether or not explicitly indicated. The term “about” generally refers to a range of numbers that one of skill in the art would consider equivalent to the recited value (i.e., having the same function or result). In many instances, the term “about” may include numbers that are rounded to the nearest significant figure.
An embodiment relates to a composition that exhibits a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol. Generally, various embodiments relate to a composition comprising: (a) at least 15 wt % of a polyetherimide; (b) at least 35 wt % of a polycarbonate; and (c) a polyetherimide siloxane. The composition can have a variety of useful properties. Advantageously, in an embodiment, articles molded or extruded from our composition can exhibit a useful combination of UV resistance, colorability, and chemical resistance properties that are useful in consumer electronic applications.
The composition can have a tensile modulus of elasticity (MPa) per ASTM D638 protocol within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700 and 3800 MPa. For example, according to certain preferred embodiments, the composition can have a tensile modulus of elasticity (MPa) of from 2800 MPa to 3300 MPa.
The composition can have a tensile elongation at yield per ASTM D638 protocol within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20%. For example, according to certain preferred embodiments, the composition can have a tensile elongation at yield ranging from 4% to 10%.
The composition can have a tensile elongation at break per ASTM D638 protocol within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90%. For example, according to certain preferred embodiments, the composition can have a tensile elongation at break per ASTM D638 protocol of from 1-80%. The composition can have a tensile stress at yield per ASTM D638 protocol within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100 MPa. For example, according to certain preferred embodiments, the composition can have a tensile stress at yield ranging from 55 MPa to 80 MPa.
The tensile stress at break, per ASTM D638 protocol, of compositions according to various embodiments can be within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, and 125 MPa. For example, according to certain preferred embodiments, the tensile stress at break of compositions according to various embodiments can range from 10 to 100 MPa.
The heat deflection temperature (1.82 MPa load) per ASTM D648 protocol of compositions according to various embodiments can be within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, and 200 degrees Celsius. For example, according to certain preferred embodiments, the heat deflection temperature (1.82 MPa load) of compositions according to various embodiments can range from 120° C. to 160° C.
The mold shrinkage imparted by a molding composition can generally be within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95 and 2%. For example, according to certain preferred embodiments, the mold shrinkage imparted by a molding composition can generally be in a range of from 0.2 to 0.8%.
An article, shaped by molding or extruding the composition, can have a notched Izod impact strength per ASTM D256 protocol that is within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 and 500 J/m, as measured by a notched Izod (2 lb hammer, 23° C.). For example, according to certain preferred embodiments, an article, shaped by molding or extruding the composition, can have an impact strength that is at least 50 J/m, as measured by a notched Izod (2 lb hammer, 23° C.).
An article, shaped by molding or extruding the composition, can have a reverse-notched impact properties per ASTM D256 protocol 100 J/m (2 lb-ft/inch) to 2300 J/m (46 lb-ft/inch) (5 lb hammer, 23° C.) that is within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 200, 300, 400, 500, 600, 700, 800, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, J/m, as measured by a notched Izod (5 lb hammer, 23° C.). For example, according to certain preferred embodiments, an article, shaped by molding or extruding the composition, can have an impact strength that is at least 2000 J/m, as measured by Reverse Notched Izod with a 5 lb hammer at 23° C.
The composition can have a natural polymer color, having a chromaticity C* with low variation. The variation of the chromaticity C* can be within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5 and 20 units when a viewing angle changes from 15° to 110°, based on the angle of observation. For example, according to certain embodiments, the variation of the chromaticity C* can be less than 12 units when a viewing angle changes from 15° to 110°, based on the angle of observation.
The hue angle of the composition can vary within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10 degrees. For example, according to certain preferred embodiments, the hue angle of the composition can vary by less than 5° based on a viewing angle change in a range of from 15° to 110°, even when the composition does not contain a colorant.
The chromaticity C* and the hue angle can have the above-identified variation when the viewing angle changes by an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, and 110 degrees. For example, according to certain preferred embodiments, the chromaticity C* can have the above-identified variation when the viewing angle changes by an amount of from 15° to 110°, based on the angle of observation.
Upon molding, compositions according to various embodiments can impart notched impact resistance properties per ASTM D256 protocol, to molded articles generally within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.5, 1, 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 200, 300, 400, and 500 lb-ft/inch. For example, according to certain preferred embodiments, upon molding, compositions according to various embodiments can impart impact resistance properties generally at least 1 lb-ft/inch (50 J/m for notched Izod) at room temperature. In other embodiments, the lower limit and/or upper limit can be selected from 100, 200, 300, 400, 500, 600, 700, 800, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, J/m, as measured by a notched Izod (5 lb hammer, 23° C.). For example, according to certain preferred embodiments, an article, shaped by molding or extruding the composition, can have an impact strength that is at least 2000 J/m, as measured by Reverse Notched Izod with a 5 lb hammer at 23° C.
The composition can include one or more polyetherimides to provide high heat resistance, chemical resistance, according to ASTM D543-06, to multiple reagents, and initial polymer color light enough to make bright white, jet black and any other colored products.
The composition can include an amount of polyetherimide within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, and 50 wt %. For example, according to certain preferred embodiments, the composition can include an amount of polyetherimide of at least 15 wt %.
The polyetherimide can be a homopolymer or a copolymer. The polyetherimide can be selected from (i) polyetherimide homopolymers, e.g., polyetherimides, (ii) polyetherimide co-polymers, e.g., siloxane-polyetherimides, polyetherimide sulfones, and (iii) combinations thereof. Polyetherimides are known polymers and are sold by SABIC Innovative Plastics under the ULTEM*, EXTEM*, and SILTEM* brands.
In an embodiment, the polyetherimides are of formula (1):

wherein a is more than 1, for example 10 to 1,000 or more, or more specifically 10 to 500.

The group V in formula (1) is a tetravalent linker containing an ether group (a “polyetherimide” as used herein) or a combination of an ether groups and arylene sulfone groups (a “polyetherimide sulfone”). Such linkers include but are not limited to: (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, optionally substituted with ether groups, arylene sulfone groups, or a combination of ether groups and arylene sulfone groups; and (b) substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl groups having 1 to 30 carbon atoms and optionally substituted with ether groups or a combination of ether groups, arylene sulfone groups, and arylene sulfone groups; or combinations comprising at least one of the foregoing. Suitable additional substitutions include, but are not limited to, ethers, amides, esters, and combinations comprising at least one of the foregoing.
The R group in formula (1) includes but is not limited to substituted or unsubstituted divalent organic groups such as: (a) aromatic hydrocarbon groups having 6 to 20 carbon atoms and halogenated derivatives thereof; (b) straight or branched chain alkylene groups having 2 to 20 carbon atoms; (c) cycloalkylene groups having 3 to 20 carbon atoms, or (d) divalent groups of formula (2):

wherein Q 1 includes but is not limited to a divalent moiety such as —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups.

In an embodiment, linkers V include but are not limited to tetravalent aromatic groups of formula (3):

wherein W is a divalent moiety including —O—, —SO 2 —, or a group of the formula —O—Z—O— wherein the divalent bonds of the —O— or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, and wherein Z includes, but is not limited, to divalent groups of formulas (4):


wherein Q 1 includes, but is not limited to a divalent moiety including —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups.

In a specific embodiment, the polyetherimide comprise more than 1, specifically 10 to 1,000, or more specifically, 10 to 500 structural units, of formula (5):

wherein T is —O— or a group of the formula —O—Z—O— wherein the divalent bonds of the —O— or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions; Z is a divalent group of formula (3) as defined above; and R is a divalent group of formula (2) as defined above.

In another specific embodiment, the polyetherimide sulfones are polyetherimides comprising ether groups and sulfone groups wherein at least 50 mole % of the linkers V and the groups R in formula (1) comprise a divalent arylene sulfone group. For example, all linkers V, but no groups R, can contain an arylene sulfone group; or all groups R but no linkers V can contain an arylene sulfone group; or an arylene sulfone can be present in some fraction of the linkers V and R groups, provided that the total mole fraction of V and R groups containing an aryl sulfone group is greater than or equal to 50 mole %.
Even more specifically, polyetherimide sulfones can comprise more than 1, specifically 10 to 1,000, or more specifically, 10 to 500 structural units of formula (6):

wherein Y is —O—, —SO 2 —, or a group of the formula —O—Z—O— wherein the divalent bonds of the —O—, SO 2 —, or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, wherein Z is a divalent group of formula (3) as defined above and R is a divalent group of formula (2) as defined above, provided that greater than 50 mole % of the sum of moles Y+moles R in formula (2) contain —SO 2 — groups.

It is to be understood that the polyetherimides and polyetherimide sulfones can optionally comprise linkers V that do not contain ether or ether and sulfone groups, for example linkers of formula (7):









Imide units containing such linkers are generally be present in amounts ranging from 0 to 10 mole % of the total number of units, specifically 0 to 5 mole %. In an embodiment no additional linkers V are present in the polyetherimides and polyetherimide sulfones.
In another specific embodiment, the polyetherimide comprises 10 to 500 structural units of formula (5) and the polyetherimide sulfone contains 10 to 500 structural units of formula (6).
The polyetherimide and polyetherimide sulfones can be prepared by various methods, including, but not limited to, the reaction of a bis(phthalimide) for formula (8):

wherein R is as described above and X is a nitro group or a halogen. Bis-phthalimides (8) can be formed, for example, by the condensation of the corresponding anhydride of formula (9):


wherein X is a nitro group or halogen, with an organic diamine of the formula (10):

H 2 N—R—NH 2 (10),

wherein R is as described above.

Illustrative examples of amine compounds of formula (10) include: ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(b-amino-t-butyl) toluene, bis(p-b-amino-t-butylphenyl)ether, bis(p-b-methyl-o-aminophenyl)benzene, bis(p-b-methyl-o-aminopentyl) benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl)ether and 1,3-bis(3-aminopropyl) tetramethyldisiloxane. Mixtures of these amines can be used. Illustrative examples of amine compounds of formula (10) containing sulfone groups include but are not limited to, diamino diphenyl sulfone (DDS) and bis(aminophenoxy phenyl) sulfones (BAPS). Combinations comprising any of the foregoing amines can be used.
The polyetherimides can be synthesized by the reaction of the bis(phthalimide) (8) with an alkali metal salt of a dihydroxy substituted aromatic hydrocarbon of the formula HO—V—OH wherein V is as described above, in the presence or absence of phase transfer catalyst. Suitable phase transfer catalysts are disclosed in U.S. Pat. No. 5,229,482. Specifically, the dihydroxy substituted aromatic hydrocarbon a bisphenol such as bisphenol A, or a combination of an alkali metal salt of a bisphenol and an alkali metal salt of another dihydroxy substituted aromatic hydrocarbon can be used.
In an embodiment, the polyetherimide comprises structural units of formula (5) wherein each R is independently p-phenylene or m-phenylene or a mixture comprising at least one of the foregoing; and T is group of the formula —O—Z—O— wherein the divalent bonds of the —O—Z—O— group are in the 3,3′ positions, and Z is 2,2-diphenylenepropane group (a bisphenol A group). Further, the polyetherimide sulfone comprises structural units of formula (6) wherein at least 50 mole % of the R groups are of formula (4) wherein Q is —SO 2 — and the remaining R groups are independently p-phenylene or m-phenylene or a combination comprising at least one of the foregoing; and T is group of the formula —O—Z—O— wherein the divalent bonds of the —O—Z—O— group are in the 3,3′ positions, and Z is a 2,2-diphenylenepropane group.
The polyetherimide and polyetherimide sulfone can be used alone or in combination. In an embodiment, only the polyetherimide is used. In another embodiment, the weight ratio of polyetherimide: polyetherimide sulfone can be from 99:1 to 50:50.
The polyetherimides can have a weight average molecular weight (Mw) of 5,000 to 100,000 grams per mole (g/mole) as measured by gel permeation chromatography (GPC). In some embodiments the Mw can be 10,000 to 80,000. The molecular weights as used herein refer to the absolute weight averaged molecular weight (Mw).
The polyetherimides can have an intrinsic viscosity greater than or equal to 0.2 deciliters per gram (dl/g) as measured in m-cresol at 25° C. Within this range the intrinsic viscosity can be 0.35 to 1.0 dl/g, as measured in m-cresol at 25° C.
The polyetherimides can have a glass transition temperature of greater than 180° C., specifically of 200° C. to 500° C., as measured using differential scanning calorimetry (DSC) per ASTM test D3418. In some embodiments, the polyetherimide and, in particular, a polyetherimide has a glass transition temperature of 240 to 350° C.
The polyetherimides can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) DI 238 at 340 to 370° C., using a 6.7 kilogram (kg) weight.
One process for the preparation of polyetherimides having structure (1) is referred to as the nitro-displacement process (X is nitro in formula (8)). In one example of the nitro-displacement process, N-methyl phthalimide is nitrated with 99% nitric acid to yield a mixture of N-methyl-4-nitrophthalimide (4-NPI) and N-methyl-3-nitrophthalimide (3-NPI). After purification, the mixture, containing approximately 95 parts of 4-NPI and 5 parts of 3-NPI, is reacted in toluene with the disodium salt of bisphenol-A (BPA) in the presence of a phase transfer catalyst. This reaction yields BPA-bisimide and NaNO 2 in what is known as the nitro-displacement step. After purification, the BPA-bisimide is reacted with phthalic anhydride in an imide exchange reaction to afford BPA-dianhydride (BPADA), which in turn is reacted with meta-phenylene diamine (MPD) in ortho-dichlorobenzene in an imidization-polymerization step to afford the product polyetherimide.
An alternative chemical route to polyetherimides having structure (1) is a process referred to as the chloro-displacement process (X is Cl in formula (8)). The chloro-displacement process is illustrated as follows: 4-chloro phthalic anhydride and meta-phenylene diamine are reacted in the presence of a catalytic amount of sodium phenyl phosphinate catalyst to produce the bischlorophthalimide of meta-phenylene diamine (CAS No. 148935-94-8). The bischlorophthalimide is then subjected to polymerization by chloro-displacement reaction with the disodium salt of BPA in the presence of a catalyst in ortho-dichlorobenzene or anisole solvent. Alternatively, mixtures of 3-chloro- and 4-chlorophthalic anhydride may be employed to provide a mixture of isomeric bischlorophthalimides which may be polymerized by chloro-displacement with BPA disodium salt as described above.
Siloxane polyetherimides can include polysiloxane/polyetherimide block copolymers having a siloxane content of greater than 0 and less than 40 weight percent (wt %) based on the total weight of the block copolymer. The block copolymer comprises a siloxane block of Formula (I):

wherein R 1-6 are independently at each occurrence a substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted, saturated, unsaturated, or aromatic polycyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms or substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, V is a tetravalent linker selected from substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers, g is 1 to 30, and d is 2 to 20. Commercially available siloxane polyetherimides can be obtained from SABIC under the brand name SILTEM*.

The polyetherimide can have a weight average molecular weight (Mw) within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 73000, 74000, 75000, 76000, 77000, 78000, 79000, 80000, 81000, 82000, 83000, 84000, 85000, 86000, 87000, 88000, 89000, 90000, 91000, 92000, 93000, 94000, 95000, 96000, 97000, 98000, 99000, 100000, 101000, 102000, 103000, 104000, 105000, 106000, 107000, 108000, 109000, and 110000 Daltons. For example, the polyetherimide can have a weight average molecular weight (Mw) from 5,000 to 100,000 Daltons, from 5,000 to 80,000 Daltons, or from 5,000 to 70,000 Daltons. The primary alkyl amine modified polyetherimide will have lower molecular weight and higher melt flow than the starting, unmodified, polyetherimide.
The polyetherimide can be selected from a polyetherimide, for example as described in U.S. Pat. Nos. 3,875,116; 6,919,422 and 6,355,723, a silicone polyetherimide, for example as described in U.S. Pat. Nos. 4,690,997, 4,808,686, a polyetherimide sulfone, as described in U.S. Pat. No. 7,041,773, and combinations thereof, incorporated herein by reference their entirety.
The polyetherimide can be a silicone polyetherimide comprising a dimethyl silicone in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, and 60 weight percent. For example, the polyetherimide can be a silicone polyetherimide comprising from 1 to 40 weight percent of a dimethyl silicone block, or from 5 to 40 weight percent of a dimethyl silicone block. The polyetherimide can be a silicone polyetherimide comprising an amount of a dimethyl silicone, as described above, the dimethyl silicone can have a silicone block length within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, and 75 silicone repeat units. For example, the polyetherimide can be a silicone polyetherimide comprising from 5 to 40 repeat units of a dimethyl silicone, that is, having a silicone block length of 5 to 50 repeat units.
The polyetherimide can have a glass transition temperature within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, and 300 degrees Celsius. For example, the polyetherimide can have a glass transition temperature (Tg) greater than about 200 degrees Celsius.
The polyetherimide can be substantially free of benzylic protons. The polyetherimide can be free of benzylic protons. The polyetherimide can have an amount of benzylic protons below 100 ppm. In an embodiment, the amount of benzylic protons ranges from more than 0 to below 100 ppm. In another embodiment, the amount of benzylic protons is not detectable.
The polyetherimide can be substantially free of halogen atoms. The polyetherimide can be free of halogen atoms. The polyetherimide can have an amount of halogen atoms below 100 ppm. In an embodiment, the amount of halogen atoms ranges from more than 0 to below 100 ppm. In another embodiment, the amount of halogen atoms is not detectable.
The composition can include an amount of polycarbonate within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, and 70 wt %. For example, according to certain preferred embodiments, the composition can include an amount of polycarbonate of at least 35 wt %, or at least 50 wt % of polycarbonate.
The polycarbonate can be a homopolymer or a copolymer. The polycarbonate can be a copolymer of polycarbonate and siloxane or copolymer of polycarbonate and polycarbonate-ester or other polycarbonates copolymers. The polycarbonate can be a polycarbonate homopolymer or a polycarbonate copolymer as further described below. Polycarbonates are polymers having repeating structural carbonate units (1)

in which at least 60 percent of the total number of R 1 groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. In an embodiment, each R 1 is a C 6-30 aromatic group, that is, contains at least one aromatic moiety. R 1 can be derived from an aromatic dihydroxy compound of the formula HO—R 1 —OH, in particular (2)

HO-A 1 -Y 1 -A 2 -OH (2)

wherein each of A 1 and A 2 is a monocyclic divalent aromatic group and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 . In an exemplary embodiment, one atom separates A 1 from A 2 . Also included are bisphenol compounds (3)


wherein R a and R b are each independently a halogen atom or a monovalent hydrocarbon group and may be the same or different; p and q are each independently integers of 0 to 4; and X a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group. In an embodiment, the bridging group X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-18 organic group. The C 1-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as a halogen, oxygen, nitrogen, sulfur, silicon, or phosphorous. The C 1-18 organic group can be disposed such that the C 6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C 1-18 organic bridging group. In particular, X a is a C 1-18 alkylene group, a C 3-18 cycloalkylene group, a fused C 6-18 cycloalkylene group, or a group of the formula —B 1 —W—B 2 — wherein B 1 and B 2 are the same or different C 1-6 alkylene group and W is a C 3-12 cycloalkylidene group or a C 6-16 arylene group.

Exemplary C 1-18 organic bridging groups include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene and cycloalkylidenes such as cyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene. A specific example of bisphenol (3) wherein X a is a substituted cycloalkylidene is the cyclohexylidene-bridged, alkyl-substituted bisphenol (4)

wherein R a′ and R b′ are each independently C 1-12 alkyl, R g is C 1-12 alkyl or halogen, r and s are each independently 1 to 4, and t is 0 to 10. In a specific embodiment, at least one of each of R a′ and R b′ is disposed meta to the cyclohexylidene bridging group. The substituents R a′ , R b′ , and R g can, when comprising an appropriate number of carbon atoms, be straight chain, cyclic, bicyclic, branched, saturated, or unsaturated. In an embodiment, R a′ and R b′ are each independently C 1-4 alkyl, R g is C 1-4 alkyl, r and s are each 1, and t is 0 to 5. In another specific embodiment, R a′ , R b′ and R g are each methyl, r and s are each 1, and t is 0 or 3. In another exemplary embodiment, the cyclohexylidene-bridged bisphenol is the reaction product of two moles of a cresol with one mole of a hydrogenated isophorone (e.g., 1,1,3-trimethyl-3-cyclohexane-5-one).

X a in bisphenol (3) can also be a substituted C 3-18 cycloalkylidene (5)









wherein R r , R p , R q , and R t are independently hydrogen, halogen, oxygen, or C 1-12 organic groups; I is a direct bond, a carbon, or a divalent oxygen, sulfur, or —N(Z)— where Z is hydrogen, halogen, hydroxy, C 1-12 alkyl, C 1-12 alkoxy, or C 1-12 acyl; h is 0 to 2, j is 1 or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with the proviso that at least two of R r , R p , R q , and R t taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring. It will be understood that where the fused ring is aromatic, the ring as shown in formula (5) will have an unsaturated carbon-carbon linkage where the ring is fused. When k is one and i is 0, the ring as shown in formula (5) contains 4 carbon atoms, when k is 2, the ring as shown in formula (5) contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. In an embodiment, two adjacent groups (e.g., R q and R t taken together) form an aromatic group, and in another embodiment, R q and R t taken together form one aromatic group and R r and R p taken together form a second aromatic group. When R q and R t taken together form an aromatic group, R p can be a double-bonded oxygen atom, i.e., a ketone.
In another specific embodiment of the bisphenol compound (3), the C 1-18 organic bridging group includes groups —C(R c )(R d )— or —C(═R e )—, wherein R c and R d are each independently a hydrogen atom or a monovalent C 1-6 linear or cyclic hydrocarbon group and R e is a divalent hydrocarbon group, p and q is each 0 or 1, and R a and R b are each a C 1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.
Other useful aromatic dihydroxy compounds of the formula HO—R 1 —OH include aromatic dihydric compounds (6)

wherein each R h is independently a halogen atom, a C 1-10 hydrocarbyl such as a C 1-10 alkyl group, a halogen-substituted C 1-10 alkyl group, a C 6-10 aryl group, or a halogen-substituted C 6-10 aryl group, and n is 0 to 4. The halogen is usually bromine.

Some illustrative examples of specific aromatic dihydroxy compounds include the following: 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis (hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutene, 1,1-bis(4-hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)adamantane, alpha, alpha′-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindane bisphenol”), 3,3-bis(4-hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxybenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like, or combinations comprising at least one of the foregoing dihydroxy compounds.
Specific examples of bisphenol compounds (3) include 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) propane (also known as “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, 1,1-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations comprising at least one of the foregoing dihydroxy compounds can also be used. In one specific embodiment, the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene in formula (13).
“Polycarbonate” as used herein includes homopolycarbonates (wherein each R 1 in the polymer is the same), copolymers comprising different R 1 moieties in the carbonate units (referred to herein as “copolycarbonates”), copolymers comprising carbonate units and other types of polymer units (such as ester units, diorganosiloxane units, urethane units, arylene ether units, arylene sulfone units, arylene ketone units, and combinations thereof), and combinations of at least one homopolycarbonate and/or at least one copolycarbonate and/or at least one polycarbonate copolymer. As used herein, a “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.
A specific polycarbonate copolymer is a poly(carbonate-ester). Such copolymers further contain, in addition to repeating carbonate units (1), repeating ester units (7)

wherein J is a divalent group derived from a dihydroxy compound, and can be, for example, a C 2-10 alkylene group, a C 6-20 alicyclic group, a C 6-20 aromatic group or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and T divalent group derived from a dicarboxylic acid, and can be, for example, a C 2-10 alkylene group, a C 6-20 alicyclic group, a C 6-20 alkyl aromatic group, or a C 6-20 aromatic group. Poly(carbonate-ester)s containing a combination of different T and/or J groups can be used. The poly(carbonate-ester)s can be branched or linear.

In an embodiment, J is a C 2-30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure. In another embodiment, J is derived from an aromatic dihydroxy compound (3). In another embodiment, J is derived from an aromatic dihydroxy compound (4). In another embodiment, J is derived from an aromatic dihydroxy compound (6).
Exemplary aromatic dicarboxylic acids that can be used to prepare the polyester units include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether, 4,4′-bisbenzoic acid, or a combination comprising at least one of the foregoing acids. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids. A specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98. In another specific embodiment, J is a C 2-6 alkylene group and T is p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group, or a combination thereof.
The molar ratio of carbonate units to ester units in the copolymers can vary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10, more specifically 25:75 to 75:25, depending on the desired properties of the final composition.
A specific embodiment of a poly(carbonate-ester) (8) comprises repeating aromatic carbonate and aromatic ester units

wherein Ar is divalent aromatic residue of a dicarboxylic acid or combination of dicarboxylic acids, and Ar′ is a divalent aromatic residue of a bisphenol (3) or a dihydric compound (6). Ar is thus an aryl group, and is preferably the residue of isophthalic acid (9a), terephthalic acid (9b),


or a combination thereof. Ar′ may be polycyclic, e.g., a residue of biphenol or bisphenol A, or monocyclic, e.g., the residue of hydroquinone or resorcinol.

Further in the poly(carbonate-ester) (8), x and y represent the respective parts by weight of the aromatic ester units and the aromatic carbonate units based on 100 parts total weight of the copolymer. Specifically, x, the aromatic ester content, is 20 to less than 100 wt %, specifically 30 to 95 wt %, still more specifically 50 to 95 wt %, and y, the carbonate content, is from more than zero to 80 wt %, from 5 to 70 wt %, still more specifically from 5 to 50 wt %, each based on the total weight of units x+y. In general, any aromatic dicarboxylic acid conventionally used in the preparation of polyesters may be utilized in the preparation of poly(carbonate-ester)s (8) but terephthalic acid alone can be used, or mixtures thereof with isophthalic acid wherein the weight ratio of terephthalic acid to isophthalic acid is in the range of from 5:95 to 95:5. Poly(carbonate-ester)s (8) comprising 35 to 45 wt % of carbonate units and 55 to 65 wt % of ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of 45:55 to 55:45 are often referred to as poly(carbonate-ester)s (PCE) and copolymers comprising 15 to 25 wt % of carbonate units and 75 to 85 wt % of ester units having a molar ratio of isophthalate to terephthalate from 98:2 to 88:12 are often referred to as poly(phthalate-carbonate)s (PPC). In these embodiments the PCE or PPC (8) can be derived from reaction of bisphenol-A and phosgene with iso- and terephthaloyl chloride, and can have an intrinsic viscosity of 0.5 to 0.65 deciliters per gram (measured in methylene chloride at a temperature of 25° C.).
In another specific embodiment, a poly(carbonate-ester) comprises carbonate units (1) derived from a bisphenol compound (3), and ester units derived from an aromatic dicarboxylic acid and dihydroxy compound (6). Specifically, the ester units are arylate ester units (9)

wherein each R 4 is independently a halogen or a C 1-4 alkyl, and p is 0 to 3. The arylate ester units (9) can be derived from the reaction of a mixture of terephthalic acid and isophthalic acid or chemical equivalents thereof with compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 2,4,5-trifluoro resorcinol, 2,4,6-trifluoro resorcinol, 4,5,6-trifluoro resorcinol, 2,4,5-tribromo resorcinol, 2,4,6-tribromo resorcinol, 4,5,6-tribromo resorcinol, catechol, hydroquinone, 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2,3,5-trimethyl hydroquinone, 2,3,5-tri-t-butyl hydroquinone, 2,3,5-trifluoro hydroquinone, 2,3,5-tribromo hydroquinone, or a combination comprising at least one of the foregoing compounds. The arylate ester units (8) can be poly(isophthalate-terephthalate-resorcinol ester) units, also known as “ITR” esters.

The poly(carbonate-ester)s comprising arylate ester units (9) can comprise, based on the total weight of the copolymer, from 1 to less than 100 wt %, 10 to less than 100 wt %, 20 to less than 100 wt %, or 40 to less than 100 wt % of carbonate units (1) derived from a bisphenol compound (3), and from greater than 0 to 99 wt %, greater than 0 to 90 wt %, greater than 0 to 80 wt %, or greater than 0 to 60 wt % of ester units derived from an aromatic dicarboxylic acid and dihydroxy compound (6). A specific poly(carbonate-ester) comprising arylate ester units (9) is a poly(bisphenol-A carbonate)-co-poly(isophthalate-terephthalate-resorcinol ester).
In another specific embodiment, the poly(carbonate-ester) contains carbonate units (1) derived from a combination of a bisphenol (3) and an aromatic dihydric compound (6), and arylate ester units (9). The molar ratio of carbonate units derived from bisphenol (3) to carbonate units derived from aromatic dihydric compound (6) can be 1:99 to 99:1. A specific poly(carbonate-ester) of this type is a poly(bisphenol-A carbonate)-co-(resorcinol carbonate)-co(isophthalate-terephthalate-resorcinol ester).
The polycarbonates can further comprise siloxane units, for example a poly(carbonate-siloxane) or a poly(carbonate-ester-siloxane). The siloxane units are present in the copolymer in polysiloxane blocks, which comprise repeating siloxane units (10)

wherein each R is independently the same or different C 1-13 monovalent organic group. For example, R can be a C 1 -C 13 alkyl, C 1 -C 13 alkoxy, C 2 -C 13 alkenyl group, C 2 -C 13 alkenyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, C 6 -C 14 aryl, C 6 -C 10 aryloxy, C 7 -C 13 arylalkyl, C 7 -C 13 aralkoxy, C 7 -C 13 alkylaryl, or C 7 -C 13 alkylaryloxy. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an embodiment, where a transparent polysiloxane-polycarbonate is desired, R is unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.

The value of E in formula (10) can vary depending on the type and relative amount of each component in the composition, the desired properties of the, and like considerations. Generally, E has an average value of 5 to 50, specifically 5 to about 40, more specifically 10 to 30. A combination of a first and a second (or more) copolymers can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.
In an embodiment, the polysiloxane blocks are of formula (11) or (12)

wherein E is as defined in siloxane (10) and each R can be the same or different, and is as defined in siloxane (1). Each Ar in blocks (11) and (12) can be the same or different, and is a substituted or unsubstituted C 6 -C 30 arylene group, wherein the bonds are directly connected to an aromatic moiety. The Ar groups in (11) can be derived from a bisphenol (3), for example 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and 1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising at least one of the foregoing compounds can also be used. Each R 5 in formula (12) is independently a divalent C 1 -C 30 organic group, for example a divalent C 2 -C 8 aliphatic group.

In a specific embodiment, the polysiloxane blocks are of formula (13):

wherein R and E are as defined in formula (10); R 6 is a divalent C 2 -C 8 aliphatic group; each M is independently a halogen, cyano, nitro, C 1 -C 8 alkylthio, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 2 -C 8 alkenyl, C 2 -C 8 alkenyloxy group, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkoxy, C 6 -C 10 aryl, C 6 -C 10 aryloxy, C 7 -C 12 aralkyl, C 7 -C 12 aralkoxy, C 7 -C 12 alkylaryl, or C 7 -C 12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4. In an embodiment, M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl; R 2 is a dimethylene, trimethylene or tetramethylene group; and R is a C 1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or C 6-8 aryl such as phenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another embodiment, M is methoxy, n is one, R 2 is a divalent C 1 -C 3 aliphatic group, and R is methyl.

In an embodiment, the polycarbonate is a poly(carbonate-siloxane) which comprises carbonate units (1) derived from a bisphenol (3), specifically bisphenol A, and siloxane units (13) wherein M is methoxy, n is one, R 2 is a divalent C 1 -C 3 aliphatic group, and R is methyl. The poly(carbonate-siloxane)s can comprise 50 to 99 wt % of carbonate units and 1 to 50 wt % siloxane units. Within this range, the poly(carbonate-siloxane)s can comprise 70 to 98 wt %, more specifically 75 to 97 wt % of carbonate units and 2 to 30 wt %, more specifically 3 to 25 wt % siloxane units.
In another embodiment, the polycarbonate is a poly(carbonate-ester-siloxane) which comprises carbonate units (1) derived from a bisphenol (3), specifically bisphenol A; siloxane units (13) wherein M is methoxy, n is one, R 2 is a divalent C 1 -C 3 aliphatic group, and R is methyl and ester units (9), specifically (isophthalate-terephthalate-resorcinol) ester units.
Polycarbonates can be manufactured by processes such as interfacial polymerization and melt polymerization. Although the reaction conditions for interfacial polymerization can vary, an exemplary process generally involves dissolving or dispersing a dihydric phenol reactant in aqueous caustic soda or potash, adding the resulting mixture to a water-immiscible solvent medium, and contacting the reactants with a carbonate precursor in the presence of a catalyst such as triethylamine and/or a phase transfer catalyst, under controlled pH conditions, e.g., 8 to 12. The most commonly used water immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, and the like.
Exemplary carbonate precursors include a carbonyl halide such as carbonyl bromide or carbonyl chloride, or a haloformate such as a bishaloformates of a dihydric phenol (e.g., the bischloroformates of bisphenol A, hydroquinone, or the like) or a glycol (e.g., the bishaloformate of ethylene glycol, neopentyl glycol, polyethylene glycol, or the like). Combinations comprising at least one of the foregoing types of carbonate precursors can also be used. In an exemplary embodiment, an interfacial polymerization reaction to form carbonate linkages uses phosgene as a carbonate precursor, and is referred to as a phosgenation reaction.
Among the phase transfer catalysts that can be used are catalysts of the formula (R 3 ) 4 Q + X, wherein each R 3 is the same or different, and is a C 1-10 alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a C 1-8 alkoxy group or C 6-18 aryloxy group. Exemplary phase transfer catalysts include, for example, [CH 3 (CH 2 ) 3 ] 4 NX, [CH 3 (CH 2 ) 3 ] 4 PX, [CH 3 (CH 2 ) 5 ] 4 NX, [CH 3 (CH 2 ) 6 ] 4 NX, [CH 3 (CH 2 ) 4 ] 4 NX, CH 3 [CH 3 (CH 2 ) 3 ] 3 NX, and CH 3 [CH 3 (CH 2 ) 2 ] 3 NX, wherein X is Cl − , Br − , a C 1-8 alkoxy group or a C 6-18 aryloxy group. An effective amount of a phase transfer catalyst can be 0.1 to 10 wt % based on the weight of bisphenol in the phosgenation mixture. In another embodiment an effective amount of phase transfer catalyst can be 0.5 to 2 wt % based on the weight of bisphenol in the phosgenation mixture.
All types of polycarbonate end groups are contemplated as being useful in the polycarbonate composition, provided that such end groups do not significantly adversely affect desired properties of the compositions.
Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. The branching agents can be added at a level of 0.05 to 2.0 wt %. Mixtures comprising linear polycarbonates and branched polycarbonates can be used.
A chain stopper (also referred to as a capping agent) can be included during polymerization. The chain stopper limits molecular weight growth rate, and so controls molecular weight in the polycarbonate. Exemplary chain stoppers include certain mono-phenolic compounds, mono-carboxylic acid chlorides, and/or mono-chloroformates. Mono-phenolic chain stoppers are exemplified by monocyclic phenols such as phenol and C 1 -C 22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol; and monoethers of diphenols, such as p-methoxyphenol. Alkyl-substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atom can be specifically mentioned. Certain mono-phenolic UV absorbers can also be used as a capping agent, for example 4-substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and the like.
Mono-carboxylic acid chlorides can also be used as chain stoppers. These include monocyclic, mono-carboxylic acid chlorides such as benzoyl chloride, C 1 -C 22 alkyl-substituted benzoyl chloride, toluoyl chloride, halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoyl chloride, 4-nadimidobenzoyl chloride, and combinations thereof; polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydride chloride, and naphthoyl chloride; and combinations of monocyclic and polycyclic mono-carboxylic acid chlorides. Chlorides of aliphatic monocarboxylic acids with less than or equal to 22 carbon atoms are useful. Functionalized chlorides of aliphatic monocarboxylic acids, such as acryloyl chloride and methacryoyl chloride, are also useful. Also useful are mono-chloroformates including monocyclic, mono-chloroformates, such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumyl phenyl chloroformate, toluene chloroformate, and combinations thereof.
Alternatively, melt processes can be used to make the polycarbonates. Generally, in the melt polymerization process, polycarbonates can be prepared by co-reacting, in a molten state, the dihydroxy reactant(s) and a diaryl carbonate ester, such as diphenyl carbonate, in the presence of a transesterification catalyst in a Banbury® mixer, twin screw extruder, or the like to form a uniform dispersion. Volatile monohydric phenol is removed from the molten reactants by distillation and the polymer is isolated as a molten residue. A specifically useful melt process for making polycarbonates uses a diaryl carbonate ester having electron-withdrawing substituents on the aryls. Examples of specifically useful diaryl carbonate esters with electron withdrawing substituents include bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or a combination comprising at least one of the foregoing esters. In addition, useful transesterification catalysts can include phase transfer catalysts of formula (R 3 ) 4 Q + X, wherein each R 3 , Q, and X are as defined above. Exemplary transesterification catalysts include tetrabutylammonium hydroxide, methyltributylammonium hydroxide, tetrabutylammonium acetate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium phenolate, or a combination comprising at least one of the foregoing.
The polyester-polycarbonates in particular can also be prepared by interfacial polymerization as described above with respect to polycarbonates generally. Rather than utilizing the dicarboxylic acid or diol per se, the reactive derivatives of the acid or diol, such as the corresponding acid halides, in particular the acid dichlorides and the acid dibromides can be used. Thus, for example instead of using isophthalic acid, terephthalic acid, or a combination comprising at least one of the foregoing acids, isophthaloyl dichloride, terephthaloyl dichloride, or a combination comprising at least one of the foregoing dichlorides can be used.
The polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25° C., of 0.3 to 1.5 deciliters per gram (dl/gm), specifically 0.45 to 1.0 dl/gm. The polycarbonates can have a weight average molecular weight of 10,000 to 200,000 Daltons, specifically 20,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to polycarbonate references. GPC samples are prepared at a concentration of 1 mg per ml, and are eluted at a flow rate of 1.5 ml per minute. Combinations of polycarbonates of different flow properties can be used to achieve the overall desired flow property. In an embodiment polycarbonates are based on bisphenol A, in which each of A 3 and A 4 is p-phenylene and Y 2 is isopropylidene. The weight average molecular weight of the polycarbonate can be 5,000 to 100,000 Daltons, or, more specifically 10,000 to 65,000 Daltons, or, even more specifically, 15,000 to 35,000 Daltons as determined by GPC as described above.
The polyester-polycarbonates in particular are generally of high molecular weight and have an intrinsic viscosity, as determined in chloroform at 25° C. of 0.3 to 1.5 dl/gm, and preferably from 0.45 to 1.0 dl/gm. These polyester-polycarbonates may be branched or unbranched and generally will have a weight average molecular weight of from 10,000 to 200,000, preferably from 20,000 to 100,000 as measured by GPC as described above.
The poly(carbonate-siloxane)s can have a weight average molecular weight of 2,000 to 100,000 Daltons, specifically 5,000 to 50,000 Daltons as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards. The poly(carbonate-siloxane) can have a melt volume flow rate, measured at 300° C./1.2 kg, of 1 to 50 cubic centimeters per 10 minutes (cc/10 min), specifically 2 to 30 cc/10 min. Mixtures of polyorganosiloxane-polycarbonates of different flow properties can be used to achieve the overall desired flow property.
The foregoing polycarbonates can be used alone or in combination, for example a combination of a homopolycarbonate and one or more poly(carbonate-ester)s, or a combination of two or more poly(carbonate-ester)s. Blends of different polycarbonate-esters may be used in these compositions.
The polycarbonate component can contribute to high flow for thin-wall geometry (greater than 0 and less than or equal to 3 or less than or equal 2 or less than or equal 1 mm), can contribute to high impact strength (greater than 50 J/m), can reduce polymer YI, and can improve colorability/uniform color of the blend to provide uniformity of colored products.
In order for the composition to have very good flow to fill thin walls, it can be useful for the composition to have a melt index (MI) at 295° C., 6.7 kg of greater than or equal to 1.5 g/min. For purposes of the present invention thin walls can include thicknesses within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 and 4 mm. For example, according to certain preferred embodiments, thin walls can include thicknesses of greater than 0 to 3 mm, or from greater than 0 to less than or equal to 2 mm, or from greater than 0 to less than or equal to 1 mm.
Various embodiments can provide valuable flow features. When the composition has the polyetherimide component and the polycarbonate component in sufficient amounts, the composition can exhibit a melt index within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 20, 25, 30, 35, and 40 g/min. For example, according to certain preferred embodiments, when the composition has the polyetherimide component and the polycarbonate component in sufficient amounts, the composition can exhibit a melt index ranging from 1.5 to 3 g/min, at 295° C. and a loading level of 6.7 kg. According to some preferred embodiments, the weight ratio of polycarbonate to polyetherimide can be selected to provide the composition with a melt index ranging from 1.5 to 6 g/min., at 295° C. and at a loading level of 6.7 kg. These flow features can be sufficient to enable the composition to be molded into a cavity having a dimension that is within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 and 4 mm. For example, according to certain preferred embodiments, thin walls can include thicknesses of greater than 0 to 3 mm, or from greater than 0 to less than or equal to 2 mm, or from greater than 0 to less than or equal to 1 mm.
Beneficially, the melt index can be sufficient to enable the composition to be molded into a cavity having a dimension greater than 0 and less than or equal to 3 mm. Preferably, the melt index can be sufficient to enable the composition to be molded into a cavity having a dimension greater than 0 and less than or equal to 1 mm.
In addition to having the desirable melt index, the composition can also exhibit high notched and unnotched impact strength. An article molded or extruded from the composition can have an impact strength within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 200, 300, 400, and 500 J/m. For example, according to certain preferred embodiments, an article molded or extruded from the composition can have an impact strength that is more than or equal to 50 J/m.
The weight ratio of polycarbonate to polyetherimide used to impart the desirable melt index and the desirable impact strength within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 1:5, 2:5, 3:5, 4:5, and 5:5. For example, according to certain preferred embodiments, the weight ratio of polycarbonate to polyetherimide used to impart the desirable melt index and the desirable impact strength can be from 2:5 to 4:5.
The composition can have excellent melt-processability to be molded into complex article shapes with ability to fill wall thicknesses within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, and 3 mm. For example, according to certain preferred embodiments, the composition can have excellent melt-processability to be molded into complex article shapes with ability to fill wall thicknesses less than 1 mm.
The composition can be melt-processed, using, but not limited to, the following methods injection molding, extrusion, and combinations thereof. The composition can contain polyetherimide to impart good melt stability and a melt viscosity of up to 30 minutes, which constitutes an improvement compared to polycarbonates. The composition can be melt-processed at a minimum process temperature of 490° F. (254° C.).
The composition can include one or more polyetherimide siloxanes copolymers. As indicated above, siloxane polyetherimides can include polysiloxane/polyetherimide block copolymers having a siloxane content of greater than 0 and less than 40 weight percent (wt %) based on the total weight of the block copolymer. The block copolymer comprises a siloxane block of Formula (I):

wherein R 1-6 are independently at each occurrence selected from substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted, saturated, unsaturated, or aromatic polycyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms and substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, V is a tetravalent linker selected from substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers, g equals 1 to 30, and d is 2 to 20. Commercially available siloxane polyetherimides can be obtained from SABIC Innovative Plastics under the brand name SILTEM*.

Various embodiments can provide valuable UV resistance. For example, as described above, an article molded or extruded from the composition exhibits a resistance to ultraviolet light exposure of ΔE ranging from 4 to 10 units, per ASTM D-4459 protocol after the article is exposed to ultraviolet light for 300 hours. According to various embodiments, the composition can further comprise an ultraviolet stabilizer.
Suitable ultraviolet (UV) stabilizers can include any stabilizer, which when used in accordance to our invention, enables our composition (or an article derived from the composition) to exhibit a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol. Examples of suitable UV stabilizers can include benzophenones, triazines, benzoxazinones, benzotriazoles, benzoates, formamidines, cinnamates/propenoates, aromatic propanediones, benzimidazoles, cycloaliphatic ketones, formanilides, cyanoacrylates, benzopyranones, salicylates, and combinations thereof.
UV absorbing additives include hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones; aryl salicylates; monoesters of diphenols such as resorcinol monobenzoate; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB™ 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB™ 531); 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol (CYASORB™ 1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (CYASORB™ UV-3638); poly[(6-morphilino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino], 2-hydroxy-4-octyloxybenzophenone (UVINUL™ 3008), 6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenyl (UVINUL™ 3026), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol(UVINUL™ 3027), 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol (UVINUL™ 3028), 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (UVINUL™ 3029), 1,3-bis[(2′ cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis-{[(2′-cyano-3′,3′-diphenylacryloyl)oxy]methyl}-propane (UVINUL™ 3030), 2-(2H-benzotriazole-2-yl)-4-methylphenol (UVINUL™ 3033), 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenyethyl)phenol (UVINUL™ 3034), ethyl-2-cyano-3,3-diphenylacrylate (UVINUL™ 3035), (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL™ 3039), N,N′-bisformyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylendiamine (UVINUL™ 4050H), bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate (UVINUL™ 4077H), bis-(1,2,2,6,6-pentamethyl-4-piperdiyl)-sebacate+methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate (UVINUL™ 4092H) 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane (UVINUL™ 3030); 2,2′-(1,4-phenylene) bis(4H-3,1-benzoxazin-4-one); 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane; TINUVIN™ 234; nano-size inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, all with particle size less than or equal to 100 nanometers; or the like, or combinations comprising at least one of the foregoing UV absorbers. UV absorbers can be used in amounts of 0.01 to 1 part by weight, based on 100 parts by weight of polycarbonate and impact modifier. UV absorbers that can be particularly useful with the polycarbonate compositions disclosed herein include 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (e.g., CYASORB™ 5411 commercially available from Cytec Industries, Inc., Woodland Park, N.J.) and 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (e.g., CYASORB™ UV-3638, commercially available from Cytec Industries, Inc., Woodland Park, N.J.), and combinations comprising at least one of the foregoing.
Specific examples of UV stabilizers include and are not limited to 2,2″-methylenebis(6-(2H-benzotriazol-2-yl)-4-4(1,1,3,3,-tetramethylbutyl)phenol, available as LA-31RG having CAS 103597-45-1; 2,2′-(p-phenylene) bis-4H-3,1-benzoxazin-4-one, available as Cyasorb UV-3638, and having CAS:18600-59-4.
Suitable UV stabilizers are ordinarily such that when a composition of our invention is subjected to extrusion conditions, at least 70% of the stabilizer is retained in the composition. In some embodiments, the extrusion conditions involve extruding the composition into pellets at a die temperature ranging from 600° F. to 620° F. The composition can include a phosphorus stabilizer in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 wt %. The phosphorous stabilizer can be mixed together with the other components of the composition. Alternatively, the phosphorous stabilizer can be introduced as a component of a polyetherimide thermoplastic resin composition comprising (a) a polyetherimide resin, and, (b) a phosphorous-containing stabilizer. A preferred phosphorous-containing stabilizer for the polyetherimide resin is described in U.S. Pat. No. 6,001,957, the entire disclosure of which is herein incorporated by reference. The phosphorous-containing stabilizer is present in an amount effective to increase the melt stability of the polyetherimide resin, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by gravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10% by weight of the initial amount of the sample remains unevaporated upon heating the sample from room temperature to 300° C. at a heating rate of 20° C. per minute under an inert atmosphere, wherein the phosphorous-containing compound is a compound according to the structural formula P—R 1 a , wherein each R 1 is independently H, alkyl, alkoxyl, aryl, aryloxy or oxo, and a is 3 or 4. For example, according to certain preferred embodiments, the composition can include a phosphorus stabilizer in an amount of between 0.01 to 10 wt %, from 0.05 to 10 wt %, or from 5 to 10 wt %.
UV additive loading levels can be selected to ensure that the said colored products have dE* (color change) against its original color, after 300 hrs UV exposure per ASTM D4459 protocol within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, and 12 units. The lower limit and/or upper limit of the UV additive can be selected from 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 wt %. For example, according to certain preferred embodiments, UV additive loading levels can be selected to ensure that the said colored products have dE* (color change) against its original color, after 300 hrs UV exposure per ASTM D4459 protocol of smaller that 5-6 units.
A light colored product can be produced. The light colored product can be a white or light gray color exhibiting an L* value greater than or equal to 80. The light colored product can be made with an amount of UV additive within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 100, 150, 200, 250, 300, 350, 400, 450 and 500 pph. For example, according to certain preferred embodiments, the light colored product can be made with an amount of UV additive greater than 2 pph.
The composition and color package, according to various embodiments can have tolerance to chemical attacks. The colored products can also exhibit limited color change during parts fabrication processes.
Various embodiments can provide valuable chemical resistance, according to ASTM D543-06, to various reagents. The composition, according to various embodiments can contain a combination of polyetherimide and polyetherimide siloxane to impart excellent environmental stress crack resistance (ESCR) to upon exposure to various chemical reagents. An article molded or extruded from the composition can exhibits a strength retention within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and 100% when the article is immersed in a chemical selected from the group of an acid solution having an acid concentration ranging from 20 to 70%, the acid solution selected from the group of sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof, at a temperature of 23 C. and strain level selected from the group of 0%, 0.5%, 1%, and combinations thereof, for a period ranging from 1 minute to less than 1 hr or up to 24 hours. For example, according to certain preferred embodiments, an article molded or extruded from the composition can exhibits a strength retention of at least 50% when the article is immersed in a chemical selected from the group of an acid solution having an acid concentration ranging from 20 to 70%, the acid solution selected from the group of sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof, at a temperature of 23 C. and strain level selected from the group of 0%, 0.5%, 1%, and combinations thereof, for a period ranging from 1 minute to less than 1 hr or up to 24 hours. In another embodiment, an article molded or extruded from the composition can exhibit a strength retention of at least 50%; when the article is immersed in a chemical reagent selected from the group consisting of olive oil, banana boat sunscreen SPF-30, Purell® Hand Sanitizer, sebum (naturally secreted oil by the skin), and combinations thereof at a temperature of 23° C. and strain level selected from the group of 0%, 0.5%, 1%, and combinations thereof, for a period ranging from 1 minute to less than 1 hour or up to 24 hours. Advantageously, as such, articles molded or extruded from our composition can exhibit a useful combination of UV resistance, colorability, and chemical resistance properties that are useful in consumer electronic applications.
The composition can contain a combination of polyetherimide and polyetherimide siloxane to provide excellent chemical resistance, according to ASTM D543-06, to secondary chemical exposures seen by the molded article. Examples of chemical exposures include but are not limited to, sulfuric acid, nitric acid, formic acid, phosphoric acid, acetic acid at a minimum 20% concentration and at 20° C. or higher temperature conditions.
Typical polycarbonates cannot perform to the level of performance as the compositions according to various embodiments after exposure to cooking oils, hand sanitizers, moisturizers, sunscreen, hand cream etc. Polycarbonates can provide a minimum of 30% strength retention after exposure. More specifically, the polymer system, after exposure (from less than 1 hr. up to 24 hrs) to various environmental chemical reagents (23° C.) can retain min. 30% retention.
Various embodiments can provide valuable color features. The composition can also include a colorant. The colorant can be any suitable colorant, including a pigment, a dye, and/or combinations thereof. The colorant can be an organic colorant, an inorganic colorant, and/or combinations thereof. Useful colorants can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines, phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or combinations comprising at least one of the foregoing pigments. Dyes are generally organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C 2-8 ) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 7-amino-4-methylcoumarin; 3-(2′-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2′-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3″″,5″″-tetra-t-butyl-p-quinquephenyl; 2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4′-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; 1,1′-diethyl-2,2′-carbocyanine iodide; 3,3′-diethyl-4,4′,5,5′-dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylen-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or combinations comprising at least one of the foregoing dyes. In a specific embodiment the colorant can be titanium dioxide, carbon black, and/or combinations thereof.
The composition can include an amount of the colorant within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, and 75 wt %. For example, according to certain preferred embodiments, The composition can include an amount of the colorant greater than 0 to 50% by weight or from more than 0 to 25 wt %.
The composition can have any suitable color including white, light gray, and/or combinations thereof. The white or light gray color can exhibit an L* value greater than or equal to 80. A composition having a white or light gray color can comprise an amount of titanium dioxide within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, and 70 pph. For example, according to certain preferred embodiments, a composition having a white or light gray color can comprise an amount of titanium dioxide of less than 50 pph.
The composition can have any suitable color including gray, black, and/or combinations thereof. The gray or black color can exhibit an L* value of below 80. A composition having a gray or black color can comprise an amount of carbon black within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900 and 1000 pph. For example, according to certain preferred embodiments, a composition having a gray or black color can comprise an amount of carbon black of at least 0.001 pph.
In addition, the composition can include various other additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the composition, in particular colorability and UV resistance. Combinations of additives can be used. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Exemplary additives include antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, surface effect additives, radiation stabilizers, fillers, reinforcing agents, flame retardants, and anti-drip agents. A combination of additives can be used. In general, the additives are used in the amounts generally known to be effective. The total amount of additives (other than any filler or reinforcing agents) is generally 0.01 to 25 parts per hundred parts by the total weight of the polymers in the composition (phr).
Antioxidants include organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, or the like; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or the like; amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, or combinations comprising at least one of the foregoing antioxidants. Antioxidants are generally used in amounts of 0.01 to 25 parts by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent.
Heat stabilizers include organophosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like; phosphonates such as dimethylbenzene phosphonate or the like, phosphates such as trimethyl phosphate, or the like, or combinations comprising at least one of the foregoing heat stabilizers. Heat stabilizers are generally used in amounts of 0.1 to 25 parts by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent. Light stabilizers include benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxy benzophenone, or the like, or combinations comprising at least one of the foregoing light stabilizers. The light stabilizers can be present in an amount of 0.01 to 1 wt %, specifically, 0.1 to 0.5 wt %, and more specifically, 0.15 to 0.4 wt %, based upon the total weight of the polymer composition, excluding any filler or reinforcing agent.
Plasticizers, lubricants, and/or mold release agents can also be used. There is considerable overlap among these types of materials, which include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A; poly-alpha-olefins; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate, stearyl stearate, pentaerythritol tetrastearate, and the like; combinations of methyl stearate and hydrophilic and hydrophobic nonionic surfactants comprising polyethylene glycol polymers, polypropylene glycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers, or a combination comprising at least one of the foregoing glycol polymers, e.g., methyl stearate and polyethylene-polypropylene glycol copolymer in a suitable solvent; waxes such as beeswax, montan wax, paraffin wax, or the like. Such materials are generally used in amounts of 0.1 to 1 part by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent.
The term “antistatic agent” refers to monomeric, oligomeric, or polymeric materials that can be processed into polymers and/or sprayed onto materials or articles to improve conductive properties and overall physical performance. Examples of monomeric antistatic agents include glycerol monostearate, glycerol distearate, glycerol tristearate, ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylarylsulfates, alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such as sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, quaternary ammonium salts, quaternary ammonium polymers, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, or the like, or combinations comprising at least one of the foregoing monomeric antistatic agents.
Polymeric antistatic agents include certain polyesteramides polyether-polyamide (polyetheramide) block copolymers, polyetheresteramide block copolymers, polyetheresters, or polyurethanes, each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Such polymeric antistatic agents are commercially available, for example PELESTAT® 6321 (Sanyo) or PEBAX® MH1657 (Atofina), IRGASTAT® P18 and P22 (Ciba-Geigy). Other polymeric materials that can be used as antistatic agents are inherently conducting polymers such as polyaniline (commercially available as PANIPOL® EB from Panipol), polypyrrole and polythiophene (commercially available from Bayer), which retain some of their intrinsic conductivity after melt processing at elevated temperatures. In an embodiment, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or a combination comprising at least one of the foregoing can be used in a polymer composition containing chemical antistatic agents to render the composition electrostatically dissipative. Antistatic agents are generally used in amounts of 0.1 to 25 parts by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent.
Possible fillers and reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripoli, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonates (such as chalk, limestone, marble, and synthetic precipitated calcium carbonates) talc (including fibrous, modular, needle shaped, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicate or (armospheres), kaolin, whiskers of silicon carbide, alumina, boron carbide, iron, nickel, or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, heavy spar, TiO 2 , aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, ground nut shells, or rice grain husks, and reinforcing organic polymer fibrous fillers, as well combinations comprising at least one of the foregoing fillers or reinforcing agents. Also mentioned are metals and metal oxides such as particulate, fibrous, or flake aluminum, bronze, zinc, copper, nickel, steel, or the like. The fillers and reinforcing agents can be surface treated with silanes to improve adhesion and dispersion within the polymer matrix. Fillers and reinforcing agents can be used in amounts of 1 to 200 parts by weight, based on 100 parts by weight of the polymers in the composition.
In a specific embodiment a reinforcing agent is used. The reinforcing agent can be a natural material such as described above (e.g., fibrous cellulose, cotton, sisal, jute, starch, or lignin), or a fibrous organic polymer such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, poly(vinyl alcohol), or a combination comprising at least one of the foregoing.
Surface effect additives include mineral flakes or metallic pigment that can be in the form of flakes of regular or irregular shape. The metallic pigment can have a mean particle size of 1 to 3500 micrometers, or 1 to 500 micrometers, 10 to 300 micrometers, 10 to 100 micrometers. Preferred metallic pigments are based on metals of Groups 4, 6, 8, 9, 10, 11, 13, and 14 of the periodic table of the elements. Examples of metallic pigments, which can be colored, include aluminum, bronze, brass, chromium, copper, gold, iron, molybdenum, nickel, tin, titanium, zinc, and the like. Glitter, which is a special type of aluminum pigment produced from foil, can also be used. The foil, typically rolled to gauges of less than 0.025 mm, can be cut into square, rectangular, or hexagonal shapes in sizes from 0.2 to 3 mm, and optionally coated with a transparent epoxy lacquer to halt oxidative dulling of the foil. The metallic pigment can optionally be coated, for example, with rosin or fatty acids, such as oleic or linoleic acid. Optionally, the metallic pigment can be initially in granular form comprising a carrier material, which may comprise at least one polymer. Suitable carrier materials comprise mineral oil, wax, polyethylene, oxidized polyethylene, poly(methyl methacrylate), or the like. In granular form the metallic pigment can represent 70-80% of the granule with the remainder being the carrier. The pigments can be used to produce or enhance bright sparkle as well as hammer and leafing finishes in multilayer composites of the invention. Suitable special visual effect additives can also comprise a plurality of microsphere beads having a of 1 to 1300 micrometers, 1 to 850 micrometers, or 10 to 200 micrometers. In a particular embodiment the beads comprise glass and have a diameter of 50 micrometers. In another particular embodiment the beads comprise barium titanate.
Additives which provide special visual effects can be present in an amount of 0.005 phr to 25 phr, depending upon such factors as whether the composition is substantially clear or opaque. For example, when the composition is clear, less additive providing a special visual effect is used than when the composition is opaque. As little as 0.005 phr mica or 0.01 phr metallic pigment such as aluminum may be employed in clear compositions. In some embodiments a metallic pigment such as aluminum may be used in an amount of 0.01 phr and 10 phr, and in other embodiments in an amount of 0.05 phr and 8 phr, with 1 to 4 phr being preferred. In other embodiment's mineral flake such as mica may be used in an amount of 0.005 phr to 25 phr, or 0.01 phr to phr, or 4 to 10 phr.
The reinforcing agents can be provided in the form of monofilament or multifilament fibers and can be used individually or in combination with other types of fiber, through, for example, co-weaving or core/sheath, side-by-side, orange-type or matrix and fibril constructions, or the like. Exemplary co-woven structures include glass fiber-carbon fiber structures, carbon fiber-aromatic polyimide (aramid) fiber structures, and aromatic polyimide-fiberglass, or the like. Fibrous fillers can be supplied in the form of, for example, rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements, such as preforms or braids. The fibrous, reinforcing fillers can have filament diameters of 1.0 to 35.0 micrometers, and lengths of 0.5 millimeter to 2 centimeters or longer.
In an exemplary embodiment, glass fibers are used as the reinforcing agent. Useful glass fibers can be formed from any type of fiberizable glass composition including those prepared from fiberizable glass compositions known as “E-glass,” “A-glass,” “C-glass,” “D-glass,” “R-glass,” and “S-glass,” as well as E-glass derivatives that are fluorine-free and/or boron-free. ECR-glass and NE glass can be used as well. Most reinforcement mats include glass fibers formed from E-glass.
Commercially produced glass fibers generally having filament diameters of 4.0 to 35.0 micrometers may be included in the compositions. The fibers can have a round or flat cross-section. The filaments may be made by standard processes, e.g., by steam or air blowing, flame blowing, and mechanical pulling. Exemplary filaments for polymer reinforcement are often made by mechanical pulling. The glass fibers may be sized or unsized. Sized glass fibers are generally coated on at least a portion of their surfaces with a sizing composition selected for compatibility with the polymer matrix material. The sizing composition facilitates wet-out and wet-through of the organic polymer upon the fiber strands and assists in attaining selected physical properties in the composition.
The glass fibers are beneficially glass strands that have been sized. In preparing the glass fibers, a number of filaments can be formed simultaneously, sized with the coating agent and then bundled into what is called a strand. Alternatively the strand itself can be first formed of filaments and then sized. The glass fibers can be used in any suitable length, for example lengths of 0.5 millimeter to 2 centimeters. In an embodiment, the glass fiber reinforcing agents can be used in lengths of 1 millimeter to 1 centimeter.
The reinforcing agents, specifically the glass fibers, are used in effective amounts, for example 1 to 200 parts by weight, based on 100 parts by weight of the polymers in the composition, more specifically 30 to 150 parts by weight, based on 100 parts by weight of the polymers in the composition.
Useful flame retardants include organic compounds that include phosphorus, bromine, and/or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants can be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus-nitrogen bonds.
One type of organic phosphate is an aromatic phosphate of the formula (GO) 3 P═O, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl group, provided that at least one G is an aromatic group. Two of the G groups can be joined together to provide a cyclic group, for example, diphenyl pentaerythritol diphosphate. aromatic phosphates include, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5′-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5′-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, or the like. A specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.
Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of the formulas below:

wherein each G 1 is independently a hydrocarbon having 1 to 30 carbon atoms; each G 2 is independently a hydrocarbon or hydrocarbonoxy having 1 to 30 carbon atoms; each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30. Di- or polyfunctional aromatic phosphorus-containing compounds of this type include resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, respectively, their oligomeric and polymeric counterparts, and the like.

Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl) phosphine oxide. Specific examples include phosphoramides of the formula

wherein each A moiety is a 2,6-dimethylphenyl moiety or a 2,4,6-trimethylphenyl moiety. These phosphoramides are piperazine-type phosphoramides.

When present, phosphorus-containing flame retardants are generally present in amounts of 0.1 to 25 parts by weight, more specifically 1 to 10 parts by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent.
Halogenated materials can also be used as flame retardants, for example bisphenols of which the following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)ethane; 1,1-bis-(2-chloro-4-methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; 2,2-bis-(2,6-dichlorophenyl)-pentane; 2,2-bis-(3,5-dibromophenyl)-hexane; bis-(4-chlorophenyl)-phenyl-methane; bis-(3,5-dichlorophenyl)-cyclohexylmethane; bis-(3-nitro-4-bromophenyl)-methane; bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)-methane; and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2 bis-(3-bromo-4-hydroxyphenyl)-propane. Also included are 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2′-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4′-dibromobiphenyl, and 2,4′-dichlorobiphenyl as well as decabromo diphenyl oxide, and the like. Also useful are oligomeric and polymeric halogenated aromatic compounds, such as a copolycarbonate of bisphenol A and tetrabromobisphenol A and a carbonate precursor, e.g., phosgene.
Metal synergists, e.g., antimony oxide, can also be used with the flame retardant. When present, halogen containing flame retardants are generally present in amounts of 0.1 to 25 parts by weight, more specifically 1 to 10 parts by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent. Anti-drip agents can also be used in the composition, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. An exemplary TSAN comprises 50 wt % PTFE and 50 wt % SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt % styrene and 25 wt % acrylonitrile based on the total weight of the copolymer. Antidrip agents can be used in amounts of 0.1 to 10 parts by weight, based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent.
Radiation stabilizers can also be present, specifically gamma-radiation stabilizers. gamma-radiation stabilizers include alkylene polyols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexandiol, and the like; cycloalkylene polyols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol, and the like; branched alkylenepolyols such as 2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well as alkoxy-substituted cyclic or acyclic alkanes. Unsaturated alkenols are also useful, examples of which include 4-methyl-4-penten-2-ol, 3-methyl-pentene-3-ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl-4-pene-2-ol, and 9-decen-1-ol, as well as tertiary alcohols that have at least one hydroxy substituted tertiary carbon, for example 2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone, 2-phenyl-2-butanol, and the like, and cyclic tertiary alcohols such as 1-hydroxy-1-methyl-cyclohexane. Certain hydroxymethyl aromatic compounds that have hydroxy substitution on a saturated carbon attached to an unsaturated carbon in an aromatic ring can also be used. The hydroxy-substituted saturated carbon can be a methylol group (—CH 2 OH) or it can be a member of a more complex hydrocarbon group such as —CR 4 HOH or —CR 2 4 OH wherein R 4 is a complex or a simple hydrocarbon. Specific hydroxy methyl aromatic compounds include benzhydrol, 1,3-benzenedimethanol, benzyl alcohol, 4-benzyloxy benzyl alcohol and benzyl benzyl alcohol. 2-Methyl-2,4-pentanediol, polyethylene glycol, and polypropylene glycol are often used for gamma-radiation stabilization. Gamma-radiation stabilizing compounds are typically used in amounts of 0.1 to 25 parts by weight based on 100 parts by weight of the polymer composition, excluding any filler or reinforcing agent.
Other embodiments relate to articles comprising the composition. An article molded from the composition can have a yellowness index that is less than 120 when a colorant is not present and less than 100 when a colorant is present. An article molded from the composition can have a yellowness index that is less than 65. An article molded from the composition can have L* value greater than 85 without using titanium dioxide in an amount greater than 25 pph. The improved colorability and uniform color of blend comprising the composition can ensure uniformity of colored products.
The composition can have a white or light gray color, exhibiting an L* value greater than 85 without using titanium dioxide in an amount greater than 25 pph. The polycarbonate components can help to provide an initial color of the polymer system having color value of YI, L*, a* and b*.
By employing a minimal loading level of SILTEM, a polyetherimide siloxane, and by carefully selecting the type of polycarbonate, the light colored products of the polymer system, for example a white color, can provide a color change (dE*-CIE 94) not exceeding 10-11 units upon UV exposure per ASTM D4459 protocol without UV additives.
The composition can be made into light colored products, such as white or light gray, having L* value greater than 85 without using TiO 2 greater than 25 pph. The TiO 2 loading and the additive colors in the polymer formulation can be controlled. The light colors can be reached within dE* smaller than 0.5 unit at TiO 2 loading below 50 pph (part-per-hundred) against the predetermined design targets. The polymer system can be made into jet black that has no whitish pearlescent effect on the surface. The light colored products can have L* values greater than 85.
The initial polymer color and color imparted by additives can control the colorability of the polymer system. The polymer system that can provide a white color that has smaller that 0.3-0.5 unit of dL*, da*, db* and dE* per CIE 94 standard against predetermined color targets. The initial polymer can have a uniform color that is not viewing angle dependent, or that has a pearlescent effect. Component blendability can be measured by a multiple viewing angle spectrophotometer to ensure that the uniform color is achievable. According to various embodiments, the color of the composition exhibits low variation, based on the angle of observation. The colored products can maintain their properties after fabrication.
Another embodiment relates to an article comprising a composition according to various other embodiments. For example a composition comprising at least 15 wt % of a polyetherimide; at least 35 wt % of a polycarbonate; a polyetherimide siloxane; and optionally, at least one UV stabilizer, wherein the composition exhibits a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol. The article can be a molded article. The article can be machined. The article can be selected from films, fibers, foams, and combinations thereof.
Still other embodiments relate to metalized articles comprising the composition. For example, according to some embodiments, the article can further comprise a metal substrate. The metal can be any metal allowing for good adhesion to the metal layer and imparting good cosmetic appearance. The polymer system can retain its properties and structural integrity after being exposed to various metallization processes to be coated, for example, with Aluminum or other metals providing good adhesion to the metal layer and impart good cosmetic appearance.
As described above, an article, comprising the composition and shaped by one selected from molding, extruding, and combinations thereof, can exhibit a strength retention of at least 50% when immersed in an acid solution for a period of ranging from 1 minute to less than 1 hr or up to 24 hours at a temperature of about 23° C. and at a strain level selected from 0%, 0.5%, 1.0%, and combinations thereof. The acid solution can be selected from sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof. The acid solution can have a concentration within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90%. For example, according to certain preferred embodiments, the acid solution can have a concentration of at least 20% or less than 70%.
An embodiment relates to a method for making an article comprising extruding, injection molding, compressing molding, machining, film pressing, one or more compositions according to other embodiments. The method can further comprise applying a metal substrate to the article.
According to various embodiments, a polymer system comprising a blend of PEI, polycarbonate and SILTEM can be molded to a final article in variety of colors, ranging from a natural color, a very light, or white color to a very dark or black color. The colors can be provided within a specific dE* limit. Multiple properties, indicative of the colors can be maintained after the final article is exposed to several environmental conditions such as but not limited to UV, ESCR, and mechanical contact. The mechanical contact can include, but is not limited to grinding/bead-blasting.
Another embodiment relates to a process of shaping the compositions described according to other embodiments. The process can comprise shaping the composition by at least one selected from injection molding, compression molding, extrusion, film shaping, machining, and combinations thereof. The process can further comprise placing a substrate into the cavity before the composition is injection molded into the cavity and the composition adheres to the substrate. The substrate can be a metal. The metal can be aluminum. The process can further comprise extruding the composition and recovering a shaped article.
The composition can be injection molded into a cavity having a dimension within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, and 3.0 mm. For example, according to certain preferred embodiments, the composition can be injection molded into a cavity having a dimension greater than 0 and less than 1 mm.
Another embodiment relates to a process for producing a shaped article, the process comprising shaping a composition according to various other embodiments. For example a composition comprising at least 15 wt % of a polyetherimide; at least 35 wt % of a polycarbonate; a polyetherimide siloxane; and optionally, at least one UV stabilizer, wherein the composition exhibits a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol.
The shaping can be injection molding, compression molding, extrusion, film shaping, machining, and/or combinations thereof. The process can include extruding the composition and recovering a shaped article. The process can include injection molding the composition into a cavity having a dimension greater than 0 and less than or equal to 3 mm. The cavity can have a dimension of greater than 0 and less than 1 mm.
A substrate can be placed into the cavity before the composition is injection molded into the cavity and the composition can adhere to the substrate. The substrate can be any suitable material, such as a metal. The metal can be any suitable metal, preferably aluminum, copper, steel, and/or combinations thereof.
Another embodiment relates to a shaped article produced by the processes according to various other embodiments. The article can be a component of an electronic device. The electronic device can be a personal computer, a telephone (mobile as well as landline), a digital camera, a Global Positioning System (GPS) device, a music player, a video player, a video display, hand held devices, e.g., touch screen devices such as computer laptops, tablet computers, smart phones, and/or combinations thereof.
Various embodiments relate to compositions comprising: at least 15 wt % of at least one polyetherimide; at least 35 wt % of at least one polycarbonate; at least one polyetherimide siloxane; at least one UV stabilizer; and at least one colorant.
The composition can exhibit a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol.
The composition can have a color selected from gray, black, white, light gray, and combinations thereof. Both the gray color and the black color can exhibit an L* value of below 80. When the composition has either the gray color or the black color, the at least one colorant can comprises at least 0.001 pph of carbon black. Both the white color and the light gray color can exhibit an L* value greater than or equal to 80. When the composition has either the white color or the light gray color, the at least one colorant can comprise less than 50 pph of titanium dioxide.
The weight ratio of polycarbonate to polyetherimide can provide the composition with a melt index ranging from 1.5 to 6 g/min., at 295° C. and at a loading level of 6.7 kg. The melt index can be sufficient to enable the composition to be molded into a cavity having a dimension of greater than 0 and less than or equal to 3 mm.
In another embodiment, the volume ratio of polycarbonate to polyetherimide can also provide the composition with a melt index ranging from 1.5 to 6 g/min., at 295° C. and at a loading level of 6.7 kg. The melt index can be sufficient to enable the composition to be molded into a cavity having a dimension of greater than 0 and less than or equal to 3 mm.
An article, comprising the composition and shaped by one selected from molding, extruding, and combinations thereof, can exhibits a strength retention of at least 50% when immersed in an acid solution for a period of less than 1 hr up to 24 hours at a temperature of about 23° C. and at a strain level selected from 0%, 0.5%, 1.0%, and combinations thereof.
The acid solution can be selected from sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof, and wherein the acid solution has a concentration of at least 20%.
In any of the foregoing embodiments, he polyetherimide is a composition comprising: (a) a polyetherimide resin; and, (b) a phosphorous-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide resin, wherein the phosphorous-containing stabilizer exhibits a low volatility, such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300° C. at a heating rate of 20° C. per minute under an inert atmosphere.
Other embodiments relate to shaping such compositions, and to articles comprising such compositions.
EXAMPLES
The following is a list of materials used in the polymer formulations.
Material Description Source Polycarbonate A Polycarbonate endcapped homopolymer sold under the trade name SABIC LEXAN 100 Polycarbonate B Polycarbonate endcapped homopolymer SABIC Polyetherimide A Polyetherimide sold under the trade name ULTEM 1010 SABIC Polyetherimide B Polyetherimide sold under the trade name ULTEM 1000 SABIC Polycarbonate C Lexan PCE, copolymer of polycarbonate and polyesters SABIC Polycarbonate D Lexan EXL*, copolymer of polycarbonate and siloxane SABIC Siloxane Copolymer of siloxane and polyetherimide SABIC polyetherimide (ULTEM 9000) UV Stabilizer A 2-(2′-HYDROXY-5-T-OCTYLPHENYL)-BENZOTRIAZOLE, Weihai Trade name UV5411 UV Stabilizer B 2,2′-Methylene bis-[4-(1,1,3,3-tetramethylbutyl)-6-(2H- ADK benzotriazole-2-yl)phenol], Trade name LA-31RG UV Stabilizer C 4H-3,1-Benzoxazin-4-one, 2,2′-(1,4-phenylene)bis- Cytec UV Stabilizer D 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol BASF UV Stabilizer F 2,4-Bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)- Cytec 1,3,5-triazine. Acts as a UV light stabilizer UV Stabilizer G Triazine derivative BASF TiO2 Titanium dioxide Millenium Carbon black Carbon black Cabot S.R.52 Macrolex Red 5B Farbtex/Lanxess P.B.28 Sicopal Blue K6310 BASF
Methods for Making Articles for Mechanical Properties Evaluation

Injection Molding

Injection molding of ASTM parts was done on a 180-Ton DEMAG machine. The pellets were dried at 250° F. for a minimum of 8 hours prior to molding. The oil-heated mold was set at 200° F. A flat barrel temperature profile was set between 550° F.-570° F. Injection speed was set at about 1 inch/sec and screw speed at 75 RPM. The residence times were calculated from Equation 1.








Residence
⁢



⁢
Time
⁢



⁢
Calculation
⁢

:


⁢




⁢

t
=






(

Barrel
⁢



⁢
size
⁢



⁢

(
oz
)


)

⁢

(


Sp
.
Gr
.

/
1.05

)








(

28.35
⁢



⁢
g
⁢

/

⁢
oz

)

⁢

(

Cycle
⁢



⁢
time
⁢



⁢

(
secs
)


)






Part
⁢



⁢
Weight
⁢



⁢

(
g
)








Equation
⁢



⁢
1







From the equation above, a cycle time of 30 seconds was used (residence time 2.5 min) to mold the ASTM parts.
Test Procedures for Color and Mechanical Properties Evaluation
Melt Flow Rate (MFR) on pellets (dried for 4 hours at 125° C. prior to measurement) was measured according to ASTM D1238 method at dwelling time of 360 seconds and a load of 6.6 kgf and temperature of 295° C.
Capillary viscosity, which is another indicator of melt-flow was measured by ASTM D3835 or ISO D11433. Dried pellets were extruded through a capillary Rheometer and the force at varied shear rates was determined to estimate the shear viscosity.
Tensile properties were tested according to ASTM D638 method using injection molded bars at 23° C. with a crosshead speed of 5 mm/min.
Izod notched and reverse notched impact was measured at 23° C. with a pendulum of 2 lbf/ft and 5 lbf/ft pendulum energy respectively according to ASTM D256 method.
Flexural properties or three point bending were measured at 23° C. on a crosshead speed of 1.3 mm/min according to ASTM D790 method.
Heat Deflection Temperature was tested on five bars having the dimensions 5×0.5×0.125 inches (127×12.7×3.2 mm) using ASTM method D648.
Chemical resistance tests were performed by soaking the color plaques into specified chemical concentrations and exposure conditions. Color differences dE* was measured by spectrophotometer on difference between before and after chemical exposure. Similarly, the ASTM Tensile bars were immersed in the same chemical for predefined exposure conditions and the parts were tested for strength retention before and after chemical exposure using the same ASTM D638 method described above.
Color measurements were performed on injection molded 2-inch×3-inch color plaque at 0.1-inch thickness using i7 spectrophotometer made by X-Rite under measurement conditions of CWF lighting, 10 degree observer CIE 94 standard, both UV and specular component included (SCI) mode.
UV test was performed according to ASTM D4459 and the color shift of DE* was the difference of between color plaques before and after exposure and measured by i7 spectrophotometer.
Methods for Making Composition for Color Match and UV Stabilization Evaluation
The polymer and colorants components were dry blended. The blend was extruded into pellets using Prizm 25 mm twin screw extruder Model TSE24 HC at 600E-620° F. die temperature.
Methods for Molding Articles for Color Match and UV Stabilization Evaluation
The extruded pellets were molded into 2-inch×3-inch color plaques using a Nissei 85 Ton molder Model FN1000 at barrel temperature of 600° F.-620° F. and mold face temperature of 200° F.-225° F. Normal injection speed and standard cycle times were used.
Examples 1-4 and Comparative Example 1
The purpose of these examples was to make compositions in accordance with our invention and to demonstrate that the inventive compositions have balance properties in terms of polymer colorability, improved UV performance and well maintained physical properties.
Compositions were made in accordance to the procedure mentioned above in which all components in Table 1 were dry blended, extruded and molded into color plaques according to the procedure. Each example in Table 1 represents a super-white color of polyetherimide/polycarbonate blend. Inventive Example 1 through 4 includes UV stabilizer B whereas Comparative Example 1 excludes UV stabilizer B for direct comparison on an equal base formula.





TABLE 1



Compositions Used in Inventive Examples 1-4 and Comparative Example 1













Comparative


Example 1
Example 2
Example 3
Example 4
Example 1










Polyetherimide A
33.900
33.900
33.900
33.900
33.900

Siloxane
6.000
6.000
6.000
6.000
6.000

Polyetherimide






Polycarbonate A
56.8800
56.8800
56.8800
56.8800
56.8800

Polycarbonate B
3.0000
3.0000
3.0000
3.0000
3.0000

UV Stabilizer A
0.1200
0.1200
0.1200
0.1200
0.1200

TiO 2
18.660
18.6600
18.6600
18.6600
18.6600

S.R.52
0.00166
0.00166
0.00166
0.00166
0.00166

S.V.13
0.00084
0.00084
0.00084
0.00084
0.00084

P.B.28
0.0720
0.0720
0.0720
0.0720
0.0720

UV Stabilizer B
2.0000
4.0000
6.0000
8.0000
0



































Our results show that the examples of our invention, articles made from our composition exhibited a UV resistance of ΔE* ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol. Our results also show that when an article was not made from a composition in accordance to our invention, the article did not exhibit a UV resistance of DE* (ΔE*) ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol.





TABLE 2



Initial Color Data for Inventive Example 1-4

and Comparative Example 1













Comparative


Example 1
Example 2
Example 3
Example 4
Example 1










L*
91.29
91.05
90.67
90.14
91.32

a*
−0.56
−0.64
−0.67
−0.76
−0.66

b*
0.21
0.79
1.27
1.76
−0.2




























Table 2 shows initial color data of inventive Example 1 through 4 and Comparative Example 1 before UV exposure. Since UV stabilizer itself usually has yellow color, its addition into the white base formula will affect object color, usually making a white less white and reducing L* value. As seen in Table 1 and 2, UV stabilizer B, as an ideal on in Example 1 through 4, does not substantially reduce L* value versus the Comparative Example 1, even at loading as high as 8 pph (parts-per-hundred). This is critical especially when a target color in real application, such as hand held consumer electronic devices, is a super white having L* value above 90 units and UV stability is essential at the same time as the color is directly seen by devices' users every day. Generally, when L* value is lowered by addition of a colored material, such as yellowish UV stabilizer, increasing loading of a white pigment, such as TiO 2 is the only way to boost L* value. However, higher TiO 2 loading is undesired as it often reduces resin physical properties, such as high melt flow and lower impact strength. Initial color data in Table 2 demonstrate that the inventive compositions with UV stabilizer B included are able to achieve white colors having L* value exceeding 90 without a need to increase TiO 2 loading. At the same time, the 300 hours of UV exposure data per ASTM D4459 in Table 3 show that the inventive Example 1 through 4 have reduced DE* (dE), compared against the Comparative Example 1, with improved UV stability over 20 to 54% depending on the loading of UV stabilizer B.
Data demonstrate the inventive compositions were able to achieve a white color that has L* value exceeding 90 without need to increase TiO2 loading, compared to the Comparative Example 1, even when yellowish UV stabilizer is at high loadings. The significance of this is that improvements in UV performance (See Table 3) by inclusion of a yellowish UV stabilizer are not made at expenses of polymer colorability to achieve a desired white color having high L* value without significant increase in TiO2 loading.





TABLE 3



UV Exposure Data for Example 1-4 and Comparative Example 1















Com-







parative



Example
Example
Example
Example
Example



1
2
3
4
1











DE*
Initial
0.00
0.00
0.00
0.00
0.00


100 Hrs
4.77
3.66
2.73
2.38
6.43


200 Hrs
5.84
4.66
3.61
3.22
7.68


300 Hrs
7.46
6.08
5.04
4.38
9.59








UV stability
22.2%
36.6%
42.2%
54.3%
0

improvements













































TABLE 4



Physical Properties for Inventive Example 1-4 and Comparative Example 1

















Comparative

TEST
ASTM
Unit
Example 1
Example 2
Example 3
Example 4
Example 1












Flexural Modulus
D790
MPa
2813
NA
NA
3192
2861

Flexural Strength
D790
MPa
109
NA
NA
117
107

Tensile Modulus
D638
MPa
2882
NA
NA
3054
2841

Tensile Strength
D638
MPa
68
NA
NA
71
67

Impact Strength (N)
D256
J/m
112
NA
NA
341
166

Impact Strength (RN)
D256
J/m
2120
NA
NA
1576
2121

HDT (0.45 MPa)
D648
° C.

NA
NA



HDT (1.82 MPa)
D648
° C.
135
NA
NA
130.4
136

MI (295° C., 6.7 kg)
D1238
° C.
1.77
NA
NA
3.21
1.29

Sp. Gr.
D792
—
1.36
NA
NA
1.36
1.37


































Mechanical property such as tensile, flexural, HDT and Izod impact are listed in Table 4 for Invention examples 1 to 4 and Comparative Example 1. Invention examples 1, 4 and Comparative Example 1 maintain good mechanical properties such as tensile and flexural properties, HDT properties that are comparable with one another. It must be mentioned here that the Invention example 4 displayed the best impact and flow properties. The results demonstrate that inclusion of UV stabilizer B has no obvious adverse effect on targeted physical properties, even at loading as high as 8 pph (parts per hundred of resin). Thus, the invention has made resin compositions that achieve a balance of colorability and enhanced UV performance while maintaining good mechanical properties. The resin compositions of the invention, such as the compositions of Examples 1 to 4, can further be formulated with one or more additives as described above, in particular reinforcing agents such as glass fibers.
Example 5-7 and Comparative Example 2
The purpose of Example 5-7 was to show the inventive compositions have improved initial color uniformity as a result of properly selected polymer components over the Comparative Example 2. Polyetherimide usually does not blend well with other resins, such as polycarbonate. When the two are blended together, they are immiscible with each other, forming an opaque resin system that has two morphological phases, which interact with incident light in such a way that they render the blend a non-uniform color appearance. Such non-uniform natural resin color will then results in surface color variation when a colored article is made out of the resin blend. Table 5 shows the composition of each example, which was blended, extruded, and molded according to the procedure mentioned above.





TABLE 5



Composition Used in Example 5-7 and Comparative Example 2








Exam-
Exam-
Exam-
Comparative


ple 5
ple 6
ple 7
Example 2









Polyetherimide A
33.900
33.900
33.900
33.9000

Siloxane
6.000
6.000
6.000
6.000

Polyetherimide





Polycarbonate A
56.8800
56.8800
56.8800
0

Polycarbonate B
3.0000
3.0000
3.0000
0

UV Stabilizer A
0.1200
0.1200
0.1200
0

UV Stabilizer B
4.000
6.000
8.000
0

Polycarbonate C
0
0
0
60.000





































TABLE 6



Surface Color Data for Inventive Example 5-7 and Comparative Example 2













Com-






parative


°
Example 5
Example 6
Example 7
Example 2










C*
15°
17.388
18.541
19.292
1.052


45°
25.717
26.885
27.524
16.218


75°
26.721
28.043
28.52
24.947


110°
26.701
28.162
28.653
27.173

h°
15°
94.7
92.7
93.5
168.0


45°
93.6
92.1
92.8
92.7


75°
93.3
91.7
92.4
91.3


110°
93.3
91.9
92.5
92.0

Delta C*
15° ---> 110°
9.3
9.6
9.3
27.4

Delta h°
15° ---> 110°
1.4°
0.8°
1.1°
76°



































Table 6 shows color data measured on 2-inch×3-inch color plaques using Gonio spectrophotometer that measures color property at multiple viewing angles from 15° to 110°. Color parameter C* is chromaticity, which represents degree of color saturation. The higher the value, the more saturated the color, which is then perceived more intense. Color parameter h° is hue angle and each angle represents a particular color. Comparative Example 2 in Table 6 represents a typical polyetherimide/polycarbonate blend and inventive example 5, 6 & 7 are new blends replacing Polycarbonate C with Polycarbonate A and B. Data in Table 6 suggest when a viewing angle changes from 15° to 110°, color of natural polymer changes as both C* and h° have different numbers. However, chromaticity C* of the inventive Example 5 through 7 have delta ranges of 9.3, 9.6 and 9.3 respectively, all of which are much smaller than 27.4 of the Comparative Example 2. Visually, the Comparative Example is perceived much more color intensity difference than that of the inventive examples when viewing angle is changed. In similar fashion, delta ranges of hue angle h°, when a viewing angle changes from 15° to 110°, the inventive Example 5 through 7 are 1.4°, 0.8° and 1.1° respectively as oppose to 76° for the Comparative Example 2. Both smaller delta ranges of C* and h° suggest that the inventive compositions have more uniform color on the surfaces of molded plaques than that of Comparative Example 2 when POLYCARBONATE C is replaced by polycarbonate A and B.
Example 8-14, Example 1 and Comparative Example 3
Examples in Table 7A and 7B are to demonstrate another aspect of the invention, that is the new blends of polyetherimide/polycarbonate have improved UV performance without use of UV stabilizer by replacing polycarbonate C in typical polyetherimide/polycarbonate blend as shown in Comparative Example 3 with single polycarbonate A or in combination with polycarbonate B, or even by single polycarbonate D. When additional UV stability is required, proper UV stabilizer can be used without significant adverse effect on blends colorability.
Table 7A and 7B is compositions of inventive Example 8 through 14, Example 1 and Comparative Example 3. They were extruded and molded into 2-inch×3-inch color plaques for UV testing. The purpose of these examples was to demonstrate inventive compositions' UV performance improvement when polycarbonate C is replaced either by polycarbonate A only or in combination with polycarbonate B at different levels or completely by polycarbonate D. Each composition represented a white color and comparisons are made on same white color package that includes TiO2, carbon black, S.R.52 and P.B.28.
Tables 7A and 7B: Compositions in Example 8-11, Example 1, and Comparative Example 3











TABLE 7A









Comparative

Name
Example 8
Example 1
Example 9
Example 10
Example 11
Example 3













Polyetherimide
33.900
33.900
53.900
53.900
33.900
33.900

B







Siloxane
6.0000
6.000
6.0000
6.0000
6.00
6.0000

polyetherimide







Polycarbonate A
56.8800
56.8800
36.8800
36.8800
0
0

Polycarbonate B
3.0000
3.000
3.0000
3.0000
0
0

Polycarbonate C
0
0
0
0
0
60.0000

Polycarbonate D
0
0
0
0
59.802
0

UV Stabilizer A
0.1200
0.1200
0.1200
0.1200
0.1200
0

TiO2
16.7580
18.660
16.7580
16.7580
16.7580
16.7580

Carbon black
0.0006
0.00166
0.0006
0.0006
0.0006
0.0006

S.R.52
0.00170
0.00084
0.00170
0.00170
0.00170
0.00170

P.B.28
0.0900
0.0720
0.0900
0.0900
0.0900
0.0900

UV stabilizer B
0
2.000
0
2.000
0
0



































TABLE 7B Com- Example Example Example parative Name 12 13 14 Example 3 Polyetherimide B 33.900 53.900 53.900 33.900 Siloxane 6.00 6.00 6.00 6.0000 polyetherimide Polycarbonate A 0 0 0 0 Polycarbonate B 0 0 0 0 Polycarbonate C 0 0 0 60.0000 Polycarbonate D 59.802 39.802 39.802 0 UV Stabilizer A 0.1200 0.1200 0.1200 0 TiO2 16.7580 16.7580 16.7580 16.7580 Carbon black 0.0006 0.0006 0.0006 0.0006 S.R.52 0.00170 0.00170 0.00170 0.00170 P.B.28 0.0900 0.0900 0.0900 0.0900 UV stabilizer B 2.000 0 2.000 0
Tables 8A and 8B: Initial Color Data for Examples 8-14, Example 1, and Comparative Example 3












TABLE 8A




Example 8
Example 1
Example 9
Example 10
Example 11
Comparative Example 3













L*
88.13
91.29
88.87
89.36
88.69
91.32

a*
−0.59
−0.56
−0.72
−0.81
−0.11
−0.66

b*
0.02
0.21
0.61
1.17
1.90
−0.20
































TABLE 8B







Comparative


Example 12
Example 13
Example 14
Example 3











L*
88.85
88.26
88.50
91.32

a*
−0.20
−0.32
−0.38
−0.66

b*
2.18
2.33
2.72
−0.20
























Table 8 shows initial color data before UV exposure. Comparative Example 3 represented good colorability of a typical polyetherimide/polycarbonate blend achieved as it can make a super white having L* value over 90. However, its UV performance shows 14 units of DE* after 300 hours exposure (Table 9A).
Example 8 represents inventive formulation, in which Polycarbonate C was replaced by Polycarbonate A and B. The formulation was also made polycarbonate rich as the Comparative Example 3. The new blend has DE* of 10.0 after 300 hours exposure, representing a 30.3% improvement (Table 9A). With additional UV stabilizer B as seen in Example 1 (Table 7A), UV performance is further improved to DE* of 7.46, representing a 47.8% improvement (Table 9A). At the same time, the Example 1 can achieve the same L* value as the Comparative Example 3 by slightly adjustment in TiO 2 loading.
Example 9 represented another inventive formulation in which the Polycarbonate C was replaced by Polycarbonate A and Polycarbonate B. But unlike the Example 8, the formulation is made into Polyetherimide rich (Table 7A). Its UV performance was also enhanced as shown smaller DE* of 11.03 after 300 hrs exposure vs the 14 units of the Comparative Example 3, representing a 22.9% improvement. With additional UV stabilizer as shown in Example 10, UV performance was further improved by an even smaller DE* of 9.14, representing a 36.04% improvement (Table 9A).
Example 10 represents another inventive formulation in which the Polycarbonate C is replaced by Polycarbonate D (Table 7A) and the formulation was made into polycarbonate rich like the Comparative Example 3. Without UV stabilizer, the formulation exhibited excellent UV performance of much smaller DE* of 3.78 as oppose to DE* of 14 units in the Comparative Example 3 after 300 hrs exposure, representing a 73.54% improvement (Table 9A). With additional UV stabilizer as shown in Example 12 (Table 7B), DE*was even further reduced to 2.01, representing an 85.93% improvement (Table 9B).
Example 13 represents another inventive formulation in which the Polycarbonate C was replaced by Polycarbonate D. But different from Example 11, the formulation was made into Polyetherimide rich (Table 7B). Its UV performance is improved with a smaller DE* of 7.76 versus DE* of 14 for the Comparative Example 3 after 300 hrs exposure, representing a 45.70% improvement. By additional UV stabilizer, the UV performance was further improved as seen DE* is further reduced to 6.30 as shown in Example 14, representing a 55.91% improvement (Table 9B).
Data suggest when polycarbonate C was replaced by polycarbonate A/polycarbonate B or polycarbonate D, polymer compositions of the inventive Example 8 through 14 are still able to make a bright white color that has L* value greater than 85 with reasonable TiO 2 loading. When a white color has L* over 90 as Comparative Example 3, the polymer composition, such as Example 8, is able to match its L*, a* and b* values, as shown in Example 1, by slightly adjust components of color package, especially TiO 2 loading. When additional UV stabilizer B was included, the UV performance of Example 8 was further improved (see Example 8 vs Example 1 in Tables 9 A and 9B).
Tables 9A and 9B: UV Data after 300 Hours Exposure for Example 8-14, Example 1, and Comparative Example 3











TABLE 9 A









Comparative


Example 8
Example 1
Example 9
Example 10
Example 11
Example 3














DE*
Initial
0.00
0.00
0.00
0.00
0.00
0.00


100 Hrs
5.95
4.77
6.65
5.03
1.41
11.12


200 Hrs
8.64
5.84
9.82
7.99
2.92
13.41


300 Hrs
10.00
7.46
11.02
9.14
3.78
14.29









UV Stability
30.0%
47.8%
22.9%
36.0%
73.5%
0

Improvement








































TABLE 9 B





Example
Example
Example
Comparative



12
13
14
Example 3












DE*
Initial
0.00
0.00
0.00
0.00


100 Hrs
1.38
3.99
2.67
11.12


200 Hrs
1.43
6.82
5.23
13.41


300 Hrs
2.01
7.76
6.30
14.29







UV Stability
85.9%
45.7%
55.9%
0

Improvement






























Tables 9A and 9B shows UV exposure data per ASTM D4459 for inventive Example 8-14, 1 and Comparative Example 3. Data demonstrate that when POLYCARBONATE C was replaced by polycarbonate A and polycarbonate B or polycarbonate D, UV performance was significantly improved as shown DE* reduced from 14.29 of the Comparative Example 3 to 10.00 of Example 8, 11.02 of Example 9, 3.78 of Example 11 and 7.76 of Example 13. When UV stabilizer B was used as shown in Example 1, UV performance is further improved as DE* further drops from 10.00 of Example 8 to 7.46 in Example 1, from 11.02 of Example of 9 to 9.14 in Example 10, from 3, 78 of Example of 11 to 2.01 in Example 12 and from 7.76 of Example of 13 to 6.30 in Example 14.
Tables 10A and 10B: Physical Properties in Example 8-11, 1, and Comparative Example 3












TABLE 10A










Comparative

TEST
ASTM
Unit
Example 8
Example 1
Example 9
Example 10
Example 3














Flexural Modulus
D790
MPa
2861
2813
2992
2744
2551

Flexural Strength
D790
MPa
107
109
120
115
112

Tensile Modulus
D638
MPa
2841
2882
2972
3151
2372

Tensile Strength
D638
MPa
67
68
73
76
81

Impact Strength (N)
D256
J/m
166
112
119
151
315

Impact Strength (RN)
D256
J/m
2121
2120
2073
2130
2143

HDT (0.45 MPa)
D648
° C.






HDT (1.82 MPa)
D648
° C.
136
135
143
156
161

MI (295° C., 6.7 kg)
D1238
° C.
1.29
1.77
1.4

2.45*

Sp. Gr.
D792
—
1.37
1.36
1.37
1.37
1.36











































TABLE 10B










Comparative

TEST
ASTM
Unit
Example 11
Example 12
Example 13
Example 14
Example 3














Flexural Modulus
D790
MPa
2558
2703
2834
3006
2551

Flexural Strength
D790
MPa
74
78
107
112
112

Tensile Modulus
D638
MPa
2668
2779
2813
3833
2372

Tensile Strength
D638
MPa
55
51
69
70
81

Impact Strength (N)
D256
J/m
91
77
94
64
315

Impact Strength (RN)
D256
J/m
862
361
1794
1053
2143

HDT (0.45 MPa)
D648
° C.






HDT (1.82 MPa)
D648
° C.
127
121
142
145
161

MI (295° C., 6.7 kg)
D1238
° C.
1.78
—
1.8
—
2.45*

Sp. Gr.
D792
—
1.35
1.32
1.37
1.38
1.36



*Melt Index of Comparative Example 3 was done at the test conditions (337° C., 6.7 kg)






























Mechanical property such as tensile, flexural, HDT and Izod impact are listed in Tables 10 A and 10B. Comparative Example 3 represents some properties the indicated polyetherimide/polycarbonate blend can achieve. Although the polyetherimide/polycarbonate blend of Comparative Example 3 achieved some useful properties, it did not exhibit the UV resistance that articles molded from our composition exhibited (it did not exhibit a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol.)
The composition Example 8 containing Polycarbonate A/B and PEI, maintained good mechanical properties such as tensile, flexural, good Izod impact and flow properties as shown in Table. Mechanical properties of Example 1 were already described previously. Example 1 which contains UV stabilizer compares well in properties Vs. Example 8 (no UV stabilizer). Notched Impact strength was about 30% lower for Example 1 Vs. 8. One possible reason for this might be due to the higher loading levels of TiO2 pigment for Example 1 Vs. 8. In the case of composition example 9—upon increasing the ULTEM polyetherimide component and consequently lowering the polycarbonate A/B component, the notched impact properties were reduced by approximately 30%.
Similarly Example 10 is the UV stabilized version of Example 9 and here one can see similar mechanical properties to Example 9. In Examples 11, the Polycarbonate C was replaced by Polycarbonate D and the mechanical properties are shown in Table. Mechanical properties were comparable to Examples 8-10 however impact properties are lower down to 91 MPa (Notched-Izod). Example 12 is the UV stabilized version of Example 11 and the mechanical properties are comparable and similar to Example 11. One can also notice lower HDT for Examples 11 and 12 due to the Polycarbonate D which contains siloxane copolymer. In the case of composition example 13—upon increasing the ULTEM polyetherimide component and consequently lowering the polycarbonate D component, the mechanical properties are similar to Examples 11 and 12, but the HDT increases. This can be due to the higher PEI content which gives rise to higher HDT. All other properties are comparable. Finally Example 14 is the UV stabilized version of Example 13 and here the properties are similar to Example 13 as expected. Comparative Example 3 is shown for comparing mechanical properties with the invention examples 1, 8-14. Comparative Example 3 has good mechanical properties including tensile, flexural, impact, HDT and flow properties.
The composition used in Comparative Example 3 also maintained good mechanical properties such as tensile, flexural, very good Izod impact and flow properties as shown below in Table. I This polymer composition yielded very high impact properties, similar to the composition used in invention Example 4 and also had good flow properties.
The overall good colorability, significantly improved UV performance and well maintained physical properties at the same time, not achievable by good polyetherimide/polycarbonate blend as Comparative Example 3, offers the inventive blends great advantages to applications where color aesthetics and UV stability are most critical parameters to product designers, especially in consumer electronic market, since color is the first to see by consumers every day. The broader resin blend flexibility along with different levels of UV stability improvements of the invention offers electronic product designers wide choices when cost and benefits becomes a factor in material selection. Though inventive examples show drops in HDT versus Comparative Example 3, they are well above the acceptable range for consumer electronics' applications, especially hand held devices since heat generation by battery operated hand held device is much limited.
Example 2 and Comparative Example 4-5
Table 11 is compositions of inventive Example 2 and Comparative Example Examples 3, 4, and 5. The compositions were extruded and molded ASTM parts for physical properties testing and comparison. The purpose of these examples were to demonstrate inventive compositions outstanding performance as a combination of Mechanical properties such as Tensile properties, flexural properties, impact properties and flow properties as well as UV exposure resistance and chemical resistance to a wide range of chemicals, upon comparison with Comparative Example 4 (100% Polycarbonate A), Comparative Example 5 (100% Polyetherimide) and Comparative Example 3 (Polycarbonate C—Polyetherimide A blend) Each composition represents a white color and comparisons are made on white color packages that includes TiO2, carbon black, S.R.52 and P.B.28.
TABLE 11 Composition for Example 2 and Comparative Example 4-5 Compar- Comparative Comparative ative Name Example 2 Example 4 Example 5 Example 3 Polyetherimide A 33.900 — 100.000 33.900 Siloxane 6.000 — — 6.0000 Polyetherimide Polycarbonate A 56.8800 97.000 — — Polycarbonate B 3.0000 3.000 — — Polycarbonate C — — — 60.000 UV Stabilizer A 0.1200 — — — TiO 2 18.6600 2.000 — 16.7580 S.R.52 0.00166 — — 0.0006 S.V.13 0.00084 — — 0.00170 P.B.28 0.0720 — — 0.0900 UV Stabilizer B 4.0000 — — —
Table 12A shows the summary of desired properties listed in the claims of this patent for compositions listed in Table 11.












TABLE 12A







Comparative
Comparative
Comparative

TEST
ASTM
Unit
Example 2
Example 4
Example 5
Example 3













—
—
—





Flexural Modulus
D790
MPa
3192
2340
3510
2510

Flexural Strength
D790
MPa
117
93
165
112

Tensile Modulus
D638
MPa
3054
2380
3580
2580

Tensile Strength
D638
MPa
71
62
110
74

Impact Strength (N)
D256
J/m
341
907
53
315

Impact Strength (RN)
D256
J/m
1576
—
1335
2143

HDT (0.45 MPa)
D648
° C.
—
137
210
—

HDT (1.82 MPa)
D648
° C.
130
132
201
160

Chemical Resistance
—
—
V.Good
Poor
Excellent
V.Good

Flow properties
—
—
V.Good
Excellent
Fair
V.Good

Colorability
—
—
V.Good
Excellent
Poor
V.Good

UV stability
—
—
V.Good
Fair
V.Good
Poor


































In Table 12A, it can be seen that Comparative Example 4 shows good mechanical properties such as tensile and flexural properties and outstanding impact properties, has good colorability to light colors but has poor UV stability as per predefined exposure conditions and poor chemical resistance to some of the chemicals listed in this patent as shown in Table 12B.
Comparative Example 5 shows very good mechanical properties such as tensile and flexural properties, reasonable impact, outstanding chemical resistance to the chemicals listed. However, the composition of Comparative Example 5 exhibited poor flow properties, and very poor colorability to light color, which means that the article of Comparative Example 5 could not even be colored to the desired white color that can be achieved by our composition.
Comparative Example 3 shows good mechanical properties such as tensile, flexural properties, excellent impact properties and flow properties, very good chemical resistance to the chemicals listed. However, the article and compositions used in Comparative Example 3 had poor UV stability(did not exhibit a UV resistance of ΔE ranging from more than 0 to less than or equal to 10 units after exposure to ultraviolet light for 300 hours, per ASTM D-4459 protocol).
Therefore, the compositions used in comparative Example 3, 4, and 5 have some good properties and some poor properties but none have a combination of all the desired properties.
Invention Example 12 has an excellent combination of the above properties, i.e., good mechanical properties such as tensile, flexural properties, excellent impact and flow properties, very good chemical resistance to the chemicals listed and very good UV stability. Such an invention example exhibits a rare and extraordinary combination of properties as shown in Table 12A.
A Summary of our results as discussed in this application is summarized Table 12B and in the description following Table 12B.
TABLE 12B Chemical Resistance to Listed Chemical Agents. Example 2 Comparative Example 4 Comparative Example 5 Comparative Example 3 Grade Duration Strain Yield Nominal Strain Yield Nominal Strain Yield Nominal Strain Yield Nominal Strain Chemicals of Exposure level (%) Strength at Break Strength at Break Strength at Break Strength at Break Olive Oil 1 day 0 100% 100% — — 101% 97% 102% 96% 1 day 0.5 101% 89% — — 105% 105% 101% 110% 1 day 1 100% 98% 101% 85% 112% 100% 99% 111% Banana Boat 1 day 0 100% 100% 100% 96% 103% 101% 102% 103% Sunscreen SPF- 1 day 0.5 100% 135% 100% 87% 99% 90% 101% 80% 30 1 day 1 100% 97% 0% 0% 98% 99% 100% 100% Purell Hand 1 day 0 100% 100% — — 99% 99% 100% 99% Sanitizer 1 day 0.5 101% 82% — — 115% 105% 101% 80% Sebum 1 day 0 100% 100% — — 95% 102% 100% 100% 1 day 0.5 102% 84% 101% 82% 106% 98% 101% 89% 1 day 1 101% 84% 98% 6% 111% 100% 101% 97% 70% Sulfuric 120 0 100% 86% 52% 49% 108% 114% 100% 119% Acid minutes
Table 12B shows the Examples according to the invention and Comparative Examples that use various chemicals for compositions listed in Table 11.

Our results show that articles made from our composition had polyetherimide component and the polycarbonate component in sufficient amount for the composition to exhibit a combination of flow properties, chemical resistance properties, and ultraviolet resistance properties commensurate with our invention. More particularly, articles from our invention exhibited a melt index ranging from 2 to 4 g/min, at a temperature of 295° C. and a load of 6.7 kg, sufficient to enable the composition to be molded into a cavity having a dimension that is more than 0 and less than less than 1 mm. The article had an impact strength that is more than or equal to 30 J/m. With respect to chemical resistance, articles made from our composition exhibited a strength retention of at least 50% when the article is immersed in a chemical selected from the group of an acid solution having an acid concentration ranging from 20 to 70%, the acid solution selected from the group of sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, and combinations thereof, at a temperature of 23° C. and strain level selected from the group of 0%, 0.5%, 1%, and combinations thereof, for a period of 2 or 24 hours. With respect to the ultraviolet resistance, articles made from our composition exhibited a resistance to ultraviolet light exposure of delta E ranging from 4 to 10 units, per ASTM D-4459 protocol after the article is exposed to ultraviolet light for 300 hours.
Comparison in Table 12 is made to polycarbonate A, legacy polyetherimide B, and a failure example of the blend of polycarbonate-ester copolymer-polyetherimide and lastly the invention example of our new polycarbonate homopolymer-polyetherimide blend Example 4 that has a rare unique combination of good mechanical properties, processability (at polycarbonate conditions), chemical resistance, flow properties, colorability and UV stability. This combination of stringent properties is rare and we do not know of other materials that can perform all of the above requirements commensurate with the scope of our invention.
Example 15-19 and Comparative Example 1
The purpose of Examples 2 and 15-19 in Table 13 was to demonstrate suitable UV stabilizers. Comparisons were made on the same base white color formulation. UV exposures were tested per ASTM D4459 on 2″×3″ color plaques made according to the extrusion and molding procedures set forth before. Initial UV stabilizers were loaded at 4 pph (parts-per-hundred). After extrusion, UV stabilizer retained in each formulation were analyzed by GC and reported as weight percentage for retention calculated based on initial loading. Example 17 containing UV stabilizer E (dimethyl succinate polymer with 4-hydroxy-2,2,6,6,-tetramethyl-1-piperidineethanol) was not extrudable because the UV Stabilizer E, was decomposed under extrusion temperature causing foaming strand. Example 2, 15, 16, 18 & 19 show above 84% retention, suggesting that UV stabilizer B, C, D, F & G are heat stable under resin processing temperature. As results, each Example shows reduced DE* versus the Comparative Example 1 after 300 hrs exposure, representing UV stability improvement of 35.35%, 30.16%, 25.96%, 33.26% and 38.47% respectively after 300 hours exposure.
The impact of yellow nature of UV stabilizers on initial white color war evaluated and the results are shown in Table 13. Although they did not affect L* values much, b* values of each initial white color were affected, making the whites yellower at various degree versus the Comparative Example 1 as b* values increase. UV stabilizer B, C, D as shown in Example 2, 15, and 16 are much more preferred, as they have negligible initial color change, than UV stabilizer G and F as they significantly altered initial color, although they are all heat stable under high processing temperature, have excellent retention and improve UV stability of resin-color compositions.












TABLE 13




Comp.








Ex. 1
Ex. 2
Ex. 15
Ex. 16
Ex. 18
Ex. 19
















Formulation
Polyetherimide A
33.900
33.900
33.900
33.900
33.900
33.900



Siloxane
6.0000
6.0000
6.0000
6.0000
6.0000
6.0000



Polyetherimide









Polycarbonate A
56.8800
56.8800
56.8800
56.8800
56.8800
56.8800



Polycarbonate B
3.0000
3.0000
3.0000
3.0000
3.0000
3.0000



UV Stabilizer A
0.1200
0.1200
0.1200
0.1200
0.1200
0.1200



TiO 2
18.6600
18.6600
18.6600
18.6600
18.6600
18.6600



S.R.52
0.00166
0.00166
0.00166
0.00166
0.00166
0.00166



S.V.13
0.00084
0.00084
0.00084
0.00084
0.00084
0.00084



P.B.28
0.0720
0.0720
0.0720
0.0720
0.0720
0.0720



UV Stabilizer B

4.0000







UV Stabilizer C


4.0000






UV Stabilizer D



4.0000





UV Stabilizer F





4.0000



UV Stabilizer G






4.0000

Analytical
Initial loading (%)

3.37
3.37
3.37
3.37
3.37
3.37

Data
Analytical (%)
0
2.95
3.08
3.23
NA
2.84
3.02


Retention after

87.54%
91.43%
95.88%
NA
84.30%
89.64%


extrusion (%)








UV Exposure
300 Hrs
9.59
6.20
6.70
7.10
NA
6.40
5.90

(DE*)









UV Stability
300 hrs

35.35%
30.16%
25.96%
NA
33.26%
38.47%

Improvement









Initial Color
L*
92.19
91.21
91.97
91.76
NA
90.67
91.70


a*
−0.99
−1.21
−0.92
−1.27
NA
−0.69
−2.00


b*
−0.69
0.42
−0.71
0.29
NA
3.83
1.51















































The following patent references are hereby incorporated by reference in their entireties: U.S. Pat. Nos. 4,629,759; 4,816,527; 5,051,483; 5,106,915; 5,387,639; 7,452,944; 4,548,997; 4,673,708; 4,816,527; 6,011,122; 6,310,145; 3,405,042; 3,616,310; and 5,229,482. The following non-patent references are hereby incorporated by reference in their entireties: http://www.aacoa.com/anodizing/process.htm; http://www.anodizing.org/Anodizing/processes.html; and http://en.wikipedia.org/wiki/Anodizing.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein.
All the features disclosed in this specification (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.