(en)There is described a block copolymer comprising at least a block [A] and a block [B], where: (a) (i) block [A] comprises from 5 to 95 mole-% per mole-% of the block [A] of itaconate functional moieties; (b) (i) block [B] is substantially free of itaconate functional moieties. Preferably the block copolymer is made by a controlled radical polymerisation (CRP) such as reversible addition-fragmentation chain transfer (RAFT).

1.ApplicationNumber: US-201314375879-A
1.PublishNumber: US-2015024227-A1
2.Date Publish: 20150122
3.Inventor: NABUURS TIJS
SCHELLEKENS MICHAEL ARNOLDUS JACOBUS
OVERBEEK GERARDUS CORNELIS

4.Inventor Harmonized: NABUURS TIJS(NL)
SCHELLEKENS MICHAEL ARNOLDUS JACOBUS(NL)
OVERBEEK GERARDUS CORNELIS(NL)

5.Country: US
6.Claims:
(en)There is described a block copolymer comprising at least a block [A] and a block [B], where: (a) (i) block [A] comprises from 5 to 95 mole-% per mole-% of the block [A] of itaconate functional moieties; (b) (i) block [B] is substantially free of itaconate functional moieties. Preferably the block copolymer is made by a controlled radical polymerisation (CRP) such as reversible addition-fragmentation chain transfer (RAFT).

7.Description:
(en)The present invention relates to block copolymers and polymeric materials obtained and/or obtainable from monomers such as 2-methylidenebutanedioates (also referred to herein as itaconates) and/or from monomers related to itaconates. The invention also relates to a process for making such block copolymers and their use for example to prepare for example coatings, inks and/or adhesives. It is preferred that the block copolymers of the invention, and/or the itaconate functional monomers used to prepare them are obtained from bio-renewable sources.
The term itaconate functional monomers is defined further herein and for example includes itaconic acid and its isomers and derivatives; such as itaconate esters (including di and mono esters), itaconic amides (including di and mono amides), itaconate amic acids, itaconic imide, itaconate anhydride and itaconate salts.
It is one object of the present invention to provide block polymers from itaconate functional monomers, using techniques such as controlled radical polymerisation (CRP), preferably so the block copolymers have improved properties.
A further object of the invention provides sequential polymers prepared from a sequential polymerization of an itaconate block copolymer of the invention, where optionally the block copolymer is used as stabilizer or seed in the sequential polymerization.
Itaconate monomers have been described for very many years. However they have not been widely used to make commercial vinyl polymers because they are expensive and difficult to process. They also have been rarely used to make block copolymers.
WO11/073417 (DSM) discloses an aqueous emulsion comprising at least a vinyl polymer, said vinyl polymer comprising: a) 45 to 99 wt-% of itaconate ester monomers having formula (I), wherein R and R′ are independently an alkyl or an aryl group; b) 0.1 to 15 wt-% of ionic or potentially ionic unsaturated monomers; c) 0 to 54 wt-% of unsaturated monomers, different from a) and b); and 0.9 to 54.9 wt-% by weight of total monomers of a chaser monomer composition added subsequently and polymerised after the polymerisation of monomers a), b) and c); wherein a)+b)+c) and the chaser monomer composition add up to 100 wt-%; and wherein the aqueous emulsion contains less than 0.5 wt-% free itaconate ester monomers of formula I based on the total weight of the aqueous emulsion. Although it is a stated object of the invention to provide a vinyl polymer with a high total concentration of itaconate ester monomers (see page 2, lines 14 to 17) in practise the larger proportion of such itaconate esters are lower itaconate esters (i.e. esters of small alkyl groups such as DMI). This document does not describe block co-polymers nor does it teach that it would be desirable to use a high concentration of higher itaconate esters (i.e. esters of large alkyl groups such as DBI). Indeed '417 states that itaonate esters are difficult to process (see page 2, lines 23 to 25) which combined with the teaching of the examples demotivates a reader to incorporated large amounts of hydrophobic higher itaconate esters like DBI in a copolymer. The only examples in '417 that describe use of a DBI monomer are Examples 2, 4, 5 and 6. It can be seen that DBI is used as co-monomer only at a low concentrations in the final copolymer prepared in these Examples (at a maximum of 22.7 wt-%) which are each also prepared with significant amounts of another hydrophobic monomer butyl acrylate (BA). A styrene chaser monomer is always present in the final product (at least 1.5 wt-%). These examples teach away from using DBI or other higher itaconate esters to replace common hydrophobic monomers such as BA, EHA and/or styrene. No significant improvement is seen in film properties such as hardness and water sensitivity of the copolymers prepared in this document.
U.S. Pat. No. 5,431,846 (Lever Bros.) describes block copolymers derived from itaconic acid and a vinyl alcohol or ester. The copolymers are used to bind multivalent metals and are used to prepare biodegradable detergents.
WO 2008-079055 (Arkema) describes copolymers with a backbone obtained from a RAFT polymerisation of methacrylate monomers and an acrylate and/or styrene co-monomer.
JP 2000-086951 (Dainichiseika) describes water resistant inks which can still be recycled where the ink contains a random, block or graft copolymer that contains from 35 to 95% of a monomer of a lower alkyl ester of a unsaturated carboxylic acid one of which may be itaconic acid. These polymers are sufficiently functional so the ink has been printed it may later be saponified by an acid or alkali (preferable alkali) to make the ink sufficiently soluble or swellable so it can be released and the printed substrate can be recycled.
JP 55-012727 (Ashai) describes composite articles made from aromatic copolymers of a monovinyl substituted aromatic compound, a conjugated diene and an ethylene vinyl acetate copolymers. An unsaturated carboxylic acid or anhydride (one of which may be itaconic acid) is grafted onto to one of these copolymers. Such groups would be pendent from the main polymer chain.
GB 1053649 (Rohm & Haas) describes oil soluble graft copolymers having pendent units derived from maleic and/or itaconic anhydride grafted thereon.
CN101979417 (University of Beijing) discloses a method for preparing an itaconic anhydride-styrene monomer alternating copolymer by reacting itaconic anhydride, styrene monomers, a conventional thermal decomposed initiator in a reaction medium such as an alkyl ester of an organic acid, optionally dissolved in acetone or cyclohexane. The resultant copolymers have an average particle size of 350 to 1,000 nm. Microspheres with the particle sizes of more than 800 nm can be synthesized by adding a crosslinker, and the gel content can reach 75 percent. Although this method controls the morphology of the polymer chains it is different from controlled radical polymerization (CRP) and it does not produce block copolymers.
A paper by G E Roberts, T P Davis, and J P A Heuts, in Macromolecules 35, 9954 (2002) describes Catalytic Chain Transfer Polymerization (CCTP) of dimethyl itaconate to produce a low molecular weight homopolymer. Copolymers are not described.
It would be advantageous to use itaconate functional monomers to prepare block copolymers as for example itaconate monomers may be obtainable from a renewable source and block copolymers may be prepared with useful properties that may be tailored as desired based on the type and size of the constituent blocks:
It is an object of the invention to solve some or all of the problems identified herein.
Therefore broadly in accordance with one aspect of the invention there is provided a block copolymer comprising at least a block [A] and a block [B], where:
(a) (i) block [A] comprises from 5 to 100 mole-%, preferably from 5 to 95 mole-%, of itaconate functional moieties based on block [A]. (b) (i) block [B] is substantially free of itaconate functional moieties.

In one optional proviso the block copolymer of the invention is other than a graft copolymer.
In another optional proviso the block copolymer of the invention is substantially free of itaconate functional moieties which are pendent from the main polymer chain. Thus in one embodiment of the invention block [A] forms part of the polymer backbone.
In still other optional proviso the block copolymer of the invention is substantially free of reactive groups that may be saponified with alkali or acid (e.g. free acid groups).
Copolymers of the invention may also be independently limited by one or more of the following optional provisos:
(I) when component (a) consists of DBI in an amount of less than 30% by weight of the total monomers then the copolymer is substantially free of any chloro groups; and (II) when component (a) consists of DBI in an amount of less than 23% by weight of the total monomers then the copolymer is prepared by other than an emulsion polymerisation method in which a chaser monomer is used; and (III) when component (a) consists of DBI in an amount of less than 23% by weight of the total monomers then if component (d) is present, component (d) is other than styrene or a mixture consisting of butyl acrylate (60 wt-% of mixture) and styrene (40 wt-% of mixture) (IV) the copolymer is substantially free of styrene (preferably styrene free), more preferably component (d) if present is other than styrene or a mixture consisting of butyl acrylate (60 wt-% of mixture) and styrene (40 wt-% of mixture), more preferably component (d) if present is other than styrene (STY), butyl acrylate (BA), 2-ethyl hexyl; acrylate (EHA) or mixtures thereof. (V) is prepared by other than an emulsion polymerisation method in which a chaser monomer is used; and (VI) the copolymer is prepared by other than an emulsion polymerisation method in which a chaser monomer is used optionally this proviso applying only when component (a) consists of DBI preferably in an amount of from 8.5 to 15% by weight of the total monomers (a)+(b)+(c)+(d). (VII) when component (a) consists of DBI then component (a) is present in an amount other than 8.5 wt-%, 21.8 wt-%, 22.5 wt-% or 22.7 wt % of the total monomer composition, preferably other than from 8 wt-% to 23 wt %, (VIII) when component (a) consists of DBI then component (a) is present in an amount other than 4.7 wt-%, 5.0 wt-%, 8.5 wt-%, 21.8 wt-%, 22.5 wt-%, 22.7 wt %, 25.0 wt-%, 28.7 wt-%, 30.0 wt-% or 41.2 wt-% of the total monomer composition, preferably other than from 4 wt-% to 42 wt %, (IX) the copolymer is obtained other than from a polymerisation of a dimethyl itaconate (DMI) and dibutyl itaconate (DBI) in the respective weight ratio of 15 to 85 in the presence of poly diethyl itaconate seed polymer; more preferably the copolymer is obtained other than from polymerisation of dialkyl itaconate(s) in the presence of a poly diethyl itaconate seed polymer; most preferably the copolymer is obtained other than from polymerisation in the presence of a poly dialkyl itaconate seed polymer; (X) if polymerisation of the copolymer occurs in the presence of an initiator system comprising organoborane amine complex and an activator then component (a) is present in an amount greater than 20 wt-%, preferably at least 24 wt-% of total monomers (a)+(b)+(c)+(d).

In one embodiment of the invention the itaconate functional moieties in block [A] consist only of moieties obtained and/or obtainable from itaconate anhydride monomer, and preferably such moieties consist of 100 mole-% of block [A].
As used herein in relation to the copolymers and blocks [A] and [B] herein the term ‘itaconate functional moiety’ denotes any (optionally divalent) monomer units in the copolymer and/or block that may be obtained and/or obtainable from any itaconic functional monomer as defined herein.
It will be appreciated the blocks [A] and [B] may be prepared in any order [A] before [B] or vice versa or they may be prepared at the same time in the same vessel. Block copolymers of the invention can also comprise the blocks [A] and [B] in any sequence in the polymer chains for example polymer chains may be the same or different and comprise or consist of any suitable sequences such as AB, BA, ABA or BAB blocks. Other additional blocks (denoted by C D etc.) may also be included in the block copolymers of the invention for example to form polymer chains with these blocks in any sequence such as ABC, BAC, ABCD etc.
Usefully block [A] comprises at least 5 mole-%, more usefully at least 20 mole-%, most usefully at least 30 mole-%, for example at least 40 mole-% of itaconate functional moieties based on the monomers in block [A] especially where the itaconate functional moiety is other than itaconic anhydride and/or itaconic imide and amides thereof:
Conveniently block [A] comprises no more than 95 mole-%, more usefully no more than 90 mole-%, even more usefully no more than 85 mole-%, most usefully no more than 80 mole-%, for example no more than 75 mole-% of itaconate functional moieties based on the monomers in block [A].
Preferably block [A] comprises from 20 to 95 mole-%, more preferably from 30 to 95 mole-%, most preferably from 40 to 95 mole-% of itaconate functional moieties based on the monomers in block [A] especially where the itaconate functional moiety is other than those obtained and/or obtainable from itaconic anhydride, itaconic imide and/or amides thereof:
Where the itaconate functional moiety is obtained and/or obtainable from itaconic anhydride, itaconic imide and/or amides thereof block [A] may comprise from 10 to 95 mole-%, advantageously from 20 to 95 mole-%, more advantageously from 35 to 95 mole-% of such itaconate functional moieties based on the monomers in block [A].
The same Block [A] may comprise one or a mixture of two or more different itaconate functional moieties, however in one embodiment of the invention moieties obtained and/or obtainable from itaconic anhydride, itaconic imide and/or amides thereof are not mixed in the same block with other it itaconate functional moieties.
In preferred block copolymers of the invention block [B] comprises less than 95 mole-% of the block [B] of one or more ethylenically unsaturated monomers other than itaconate functional moieties.
Preferably, block [B] comprises at least 5 mole-% of (meth)acrylate or styrene monomers, more preferred at least 15 mole-% of the block [B]. In a most preferred case block [B] comprises at least 15 mole-% of (meth)acrylate monomers of the block [B].
More preferred block copolymers of the invention are prepared by a controlled radical polymerisation using a control agent where:
(a) (ii) block [A] has an average degree of polymerization x, where x is an integer greater than 5; (b) (ii) block [B] has an average degree of polymerization y, where y is an integer greater than 5.

The average degree of polymerisation x (or y) may be determined by the total molar amount of monomers in block [A] (or [B]) divided by the total molar amount of control agent—such as a RAFT agent or a nitroxide control agent.
Usefully the degree of polymerisation in the invention herein is for integer x in blocks A is from 5 to 80, more usefully from 5 to 50, most usefully from 5 to 40 and/or integer y in blocks B is from 10 to 400, more usefully from 10 to 200, most usefully from 10 to 150.
In accordance with another aspect of the invention there is provided a process for preparing a block copolymer where the process comprises at least the step of:
(I) performing a controlled radical polymerisation of at least one itaconate functional monomer in the presence of a control agent and optionally a source of free radicals to form the copolymer; where the copolymer comprises at least a block [A] and a block [B], where:
(a) (i) block [A] comprises from 5 to 95 mole-% of itaconate functional moieties based on the monomers in block [A]; and
(ii) optionally block [A] has an average degree of polymerization x, where x is an integer greater than 5;
(b) (i) block [B] is substantially free of itaconic functional moieties; and
(ii) optionally block [B] has an average degree of polymerization y, where y is an integer greater than 5.


Usefully in this aspect of the invention both x and y are independently integers >5.
Preferably in the process of the invention step (I) comprises a reversible addition-fragmentation chain transfer mechanism (RAFT) optionally in solution, in the presence of a RAFT control agent and a source of free radicals.
Itaconate Functional Monomers
The term itaconate functional monomers is defined further herein and for example includes itaconic acid and its isomers and derivatives; such as itaconate esters (including di and mono esters), itaconic amides (including di and mono amides), itaconate amic acids, itaconic imides, itaconic anhydride and itaconate salts.
Itaconate functional monomers comprise derivatives of itaconic acid









and/or derivatives of isomers of itaconic acid. Isomers of itaconic acid comprises the isomers: citraconic acid









glutaconic acid









and/or mesaconic acid









Itaconate functional monomers that are suitable for use in the present invention may also be represented generally by Formula 1:









where Ra and Rb independently represent H and/or any optionally substituted hydrocarbo moiety (such as any aliphatic, cycloaliphatic or aromatic moieties); and

X and Y independently represent —O— and/or —NRc-, where Rc independently in each case represents H and/or any optionally substituted hydrocarbo moiety (such as any aliphatic, cycloaliphatic or aromatic moieties);

X and Y can independently be —O— —NH— or —NR 3 where R3 is C1-4 alkyl

Ra and Rb independently may comprise: optionally substituted C 1-20 alkyl, C 3-20 aryl and/or C ′-20 alkaryl; more preferably C 1-6 alkyl, C 3-8 aryl and/or C 4-10 alkaryl, and most preferably C 1-4 alkyl, C 3-6 aryl and/or C 4-7 alkaryl

Ra and Rb can be different, but preferably are the same.

When X and Y are both O, Formula 1 represents 2-methylidenebutanedioate diesters (also referred to herein as itaconate diesters). X and Y are both NRc, Formula 1 represents itaconate diamides.
When one or X or Y is O and the other is NRc Formula 1 represents a compound having one ester and one amide group.
In Formula 1 where X and Y represent the same moiety the formulae comprise a cyclic moiety and substituents Ra and Rb are superfluous. Thus in Formula 1 when X and Y are the same moiety Formula can be represented as Formula 1A









where Y represents —O— or —NRc and Rc is H or C1-20 hydrocarbo (e.g. alkyl, aryl, cycloalkyl, or alkylaryl groups having up to 20 carbon atoms).
Formula 1A may also represent compounds when Y is a NRc moiety i:e itaconic imides comprising a five membered ring as represented by Formula 1B:









such as N-ethyl itaconic imide when Rc is ethyl.
It will be appreciated that the term itaconate functional monomer(s) as used herein denotes any compound of Formulae 1, 1A; and/or 1B herein.
Conveniently Formula 1 may represent dialkyl or aryl esters of itaconic acid, dialkyl or aryl amides of itaconic acid. More conveniently Ra and Rb may be independently selected from the group consisting of: methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, 2-ethylhexyl, decyl, dodecyl, phenyl, 2-phenylethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and 4-hydroxybutyl. More conveniently Ra and Rb are selected from: methyl, ethyl, n-butyl and 2-ethylhexyl. Most conveniently Ra and Rb are selected from methyl and ethyl for example methyl.
Usefully the itaconate functional monomers may be present in the compositions and/or copolymers of the invention in an amount of at least 10 wt-%, more usefully at least 20 wt-%, even more usefully at least 25 wt-% and most usefully at least 30 wt-%, based on the total weight of the copolymer being 100%.
Conveniently the itaconate functional component (a) may be present in the compositions and/or copolymers of the invention in an amount of less than 80 wt-%, more conveniently less than 75 wt-%, even more conveniently less than 70 wt-%, most conveniently less than 65 wt-%, and for example less than 60 wt-%; based on the total weight of the copolymer being 100%.
Preferably the itaconate functional component (a) may be present in the compositions and/or copolymers of the invention in an amount of from 10 to 80 wt-%, more preferably from 20 to 75 wt-%, even more preferably from 25 to 70 wt-%, most preferably from 30 to 65 wt-% based on the total weight of the copolymer being 100%.
Itaconate functional monomers such as those represented by Formula 1 may also be broadly divided into two types higher itaconate esters which are generally hydrophobic and lower itaconate esters which are generally hydrophilic
In one embodiment of the invention the itaconate functional monomer may be an itaconate diester of Formula 1 where Ra and Rb are independently optionally substituted C 1-3 hydrocarbo groups, such as C 1-3 alkyl, an example of which is dimethyl itaconate (DMI).
In another embodiment of the invention the itaconate functional monomer may be an itaconate diester of Formula 2 where Ra and Rb are independently optionally substituted C 4-8 hydrocarbo groups, such as C 4-6 alkyl, an example of which is dibutyl itaconate (DBI).
Preferred block copolymer of the invention comprises at least blocks [A]×[B]y, wherein block [A] further comprises less than 95 mole-% of block [A] of moieties (monomer units) obtained and/or obtainable from one or more ethylenically unsaturated monomers other than itaconic functional monomers.
Another aspect of the present invention provides an aqueous coating composition comprising a block copolymer of the invention.
More preferred block copolymers of the invention are prepared using a controlled radical polymerization (CRP) process, most preferably selected from CCTP; RAFT polymerization, Nitroxide Mediated Polymerisation (NMP), (Reversed) Iodine Transfer Polymerisation ((R)ITP) and/or Atom Transfer radical Polymerisation (ATRP).
Controlled Radical Polymerisations are known in the art and include processes such as RAFT, RITP, NMP, ATRP, and CCTP. These processes are described in papers such as: M. Destarac (Macromol. React. Eng. 2010, 4, 165-179); J. P. A. Heuts (Polym. Chem., 2011, 2, 2407); G. Moad, E. Rizzardo, S. H. Tang (Aust. J. Chem., 2010, 63, 1) and also in patents such as EP2003152B1 (Rohm and Haas) (e.g. see page 3 line 39 to page 4 line 4) and the contents of these documents are incorporated herein by reference and described in more detail below.
Preferred block copolymers of the invention (which may also be represented generally as [A]×[B]y) are prepared via controlled radical polymerization. The term “controlled radical polymerization” can be understood as a specific radical polymerization process, also denoted by the term of “living radical polymerization”, in which use is made of control agents, such that the polymer chains being formed are functionalized by end groups capable of being reactivated in the form of free radicals by virtue of reversible transfer or reversible termination reactions. Further features are described in WO2009/121911 the contents of which are incorporated herein by references. Preferred controlled radical polymerization mechanisms are NMP, RAFT, ATRP, RITP and CCTP. More preferred modes of polymerization are RAFT, NMP, RITP and CCTP. For monomers according to Formula 1, the most preferred controlled polymerization mechanisms are RAFT and NMP. For monomers according to Formula 2 the most preferred controlled polymerization mechanisms are RAFT, NMP and CCTP.
Especially preferred CRP techniques are CCTP and RAFT polymerization.
Suitable control agents for RAFT polymerization include thiocarbonylthio compounds such as dithioesters, trithiocarbonates, xanthates and dithiocarbamates. Preferably, the control agent is selected from the group of xanthates or trithiocarbonates. Preferred xanthates include O-ethyl-S-(1-methoxycarbonyl)ethyl dithiocarbonate (Rhodixan A1, available from Rhodia). Preferred trithiocarbonates include dibenzyltrithiocarbonate (BlocBuilder DB, available from Arkema), and dodecyl-derived trithiocarbonates including for example 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]butyl propionate and S-1-dodecyl-S′-(α,α′-dimethyl-α′-acetic acid)trithiocarbonate.
Suitable control agents for NMP include nitroxides such as 2,2,6,6-tetramethylpiperidin-1-oxyl also known as TEMPO, and 1-(diethoxyphosphinyI)-2,2-dimethylpropyl 1,1-dimethylethyl also known as SG1 nitroxide (BlocBuilder RC-50, available from Arkema), and alkoxyamines such as MONAMS, DIAMS and BlocBuilder MA (all available from Arkema).
Suitable control agents for ATRP include copper-based ATRP catalysts. Preferred ATRP processes include those where reduced levels of copper-based catalyst can be applied at levels below 0.1 wt % or more preferred below 0.01 wt %, such as ICAR ATRP, ARGET ATRP, electrochemically mediated ATRP, and SET-LRP as disclosed in open literature and known to those skilled in the art.
Suitable control agents for RITP and RITP include molecular iodine. RITP is described in more detail in WO2008155324 the contents of which are incorporated herein by reference.
CCTP is typically employed using cobalt (II) chelate complexes. CCTP is described in more detail in EP788518, EP1769031, and WO2007147561 the contents of which are incorporated herein by reference.
Other suitable RAFT and NMP control agents are described in the literature: for example M. Destarac (Macromol. React. Eng. 2010, 4, 165-179) the contents of which are incorporated herein by reference.
In a special embodiment according to the invention is provided an aqueous coating composition comprising a block copolymer; wherein the block copolymer comprises at least blocks [A]×[B]y, wherein block [A] comprises:
i) between 5 and 95 mole-% of ethylenically unsaturated monomer unit according to Formula 1 or 2, ii) less than 95 mole-% of other ethylenically unsaturated monomer units where i), and ii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5; wherein block [B] comprises: iii) at least 5 mole-% of (meth)acrylate or styrene monomer(s), more preferred at least 15 mole-% iv) no more than 95 mole-%, more preferred no more than 85 mole-% of other monomer(s) and where block [B] has an average degree of polymerization y, where y is an integer >5

Optionally, the block copolymer of the invention is partly or completely grafted onto one or more Polymer(s) P. Preferably the block copolymer is grafted onto Polymer P via an emulsion polymerisation or a solution-dispersion polymerisation process, more preferably via emulsion polymerization.
Preferably, Polymer P:
has a Tg of more than −15° C., more preferred in the range of from 0 to 100° C., most preferred in the range of from 20 to 60° C. contains more than 10 wt-%, more preferred more than 30 wt-%, most preferred more than 50 wt-% of (meth)acrylate monomers has a weight average molecular weight higher than 20 kg/mole, more preferably higher than 50 kg/mole, and most preferably higher than 70 kg/mole

In the case where the block copolymer is grafted onto a Polymer P, the ratio of block copolymer to Polymer P is preferably ranging between 1:99 and 70:30, more preferably between 5:95 and 60:40, most preferably between 10:90 and 50:50.
In a special embodiment is provided an aqueous coating composition comprising a block copolymer according to the invention, further comprising a Polymer P as described above, in a phase ratio of block copolymer to Polymer P of between 1:99 and 70:30, more preferably between 5:95 and 60:40, most preferably between 10:90 and 50:50.
The block copolymer according to the invention may comprise acid functional monomer(s) independently either block [A] or block [B] or both. Typical acid monomers that can independently comprise either or both these blocks may be selected from: acrylic acid, methacrylic acid, crotonic acid, b-CEA, itaconic acid, half esters of itaconic acid, half amides of itaconic acid, maleic anhydride, itaconic anhydride, fumaric acid, methylidene malonic acid, half esters of methylidene malonic acid, phosphate functional acid monomers, such as hydroxyethyl(meth)acrylate phosphate, or hydroxybutyl(meth)acrylate phosphate, and sulphonate functional monomers, such as AMPS and sodium styrene sulphonate.
Where acid monomers are copolymerized in blocks [A] and/or [B], the preferred concentration of acid monomer(s) is less than 60 mole-%, more preferably from 5 to 50 mole-%, and most preferably from 15 to 40 mole-% based on the block to which they are added.
In a special case it is possible that blocks [A] and/or [B] may comprise high amounts of acid, usefully higher than 85 mole-%, more usefully 100 mole-% as this can impart advantageous surface active properties to the block copolymer.
The acid value (AV) of block [A] and/or block [B] is preferably at least 5 mg KOH/g of solid material, more preferred between 5 and 400, most preferred between 10 and 200, even most preferred between 20 and 100 mg KOH/g of solid material.
In a special embodiment is provided an aqueous coating composition comprising a block copolymer; wherein the block copolymer comprises at least blocks [A]×[B]y, wherein block [A] comprises:
i) between 5 and 95 mole-% of itaconate functional moiety of Formula 1 and/or 3, ii) less than 95 mole-% of other ethylenically unsaturated monomer units where i), and ii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5; wherein block [B] comprises at least 85 mole-%, more preferably 100 mole-% of (potentially) acid monomer, and has an average degree of polymerization y, where y is an integer >5

When acid monomers are copolymerized in Polymer P, the concentration of non itaconate functional acid monomers is preferably below 20 wt-%, more preferably below 10 wt-%, most preferably between 1 and 7.5 wt-%, and even most preferred between 1.5 and 5 wt-%, based on total dry weight of Polymer P.
Preferably, acid monomers are copolymerized only in block [A] or Polymer P, more preferably, acid monomers are copolymerized only in block [A].
Block [A], block [B] and/or Polymer P may contain crosslinking monomers. Suitable crosslinking monomers are known in the art and may comprise any of the following. Crosslinking can also be achieved using one component crosslinkers, two component crosslinkers, by high temperature cure and/or radiation cure.
Monomers that can undergo crosslinking (such monomers are referred to as ‘cross-linking monomers’) may also improve adhesion of the coating to various substrates, enhance the colloidal stability of the polymer emulsion, and/or be used to affect Tg, or polymer polarity
Cross-linking monomers can induce crosslinking of the copolymer composition. Crosslinking can occur at ambient temperatures (using for instance diacetone acryl amide combined with adipic dihydrazide), at elevated temperatures (stoving conditions in which for instance copolymerized hydroxyethyl(meth)acrylate reacts with hexamethoxy methyl melamines), as 2C composition (copolymerized hydroxyethyl(meth)acrylate reacting with polyisocyanates, such as Bayhydur 3100), or as UV coating (when polymers or oligomers having multiple unsaturated groups are admixed. Typical examples include di- or tri-functional multifunctional acrylates such as trimethylol propane triacrylate or ethoxylated or propoxylated versions thereof). Other examples of crosslinking monomers include hydroxypropyl(meth)acrylate, silane functional monomers, such as 3-methacryloxypropyl trimethoxysilane (Geniosil GF31, ex Wacker).
Preferably such cross-linking monomers are present in an amount of not more than 15 wt-%, more preferably not more than 10 wt-%, most preferably from 1 to 8 wt-% of their respective monomer compositions
Some other preferred crosslinking monomers are listed below: diacetone acrylamide (in combination with polyhydrazides, polyhydrazines, polysemi-carbazides), acetoacetoxy ethyl methacrylate (in combination with polyamines, or polyhydrazides), glycidyl(meth)acrylates (in combination with polyamines), and hydroxyalkyl(meth)acrylate (such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, or 4-hydroxybutyl(meth)acrylate (in combination with polyisocyanates). fatty acid functional monomers, such as Visiomer MUMA (ex. Evonik) or Dapro Serad 521 and 522 (ex. Elementis)
other oxidatively curing monomers such as esters of geranic acid and hydroxyl functional (meth)acrylates.

silane functional crosslinking monomers such as those having an unsaturated (meth)acrylate or vinyl group and an alkoxy silane group, examples of which are: 3-methacryloxypropyltrimethoxysilane [CAS #: 2530-85-0], Methacryloxytrimethoxysilane [CAS #: 13688-56-7], Methacryloxypropyltris(trimethylsiloxy)silane [CAS #: 17096-07-0], 3-methacryloxypropyltriethoxysilane [CAS #: 21142-29-0], 3-methacryloxypropylmethyldimethoxysilane [CAS #: 14513-34-9], 3-methacryloxypropylmethyldiethoxysilane [CAS #: 65100-04-1], Methacryloxymethyltrimethoxysilane [CAS #: 54586-78-6], Methacryloxymethyltriethoxysilane [CAS #: 5577-72-0], Methacryloxymethyl(methyl)dimethoxysilane [CAS #: 121177-93-3], Methacryloxymethyl(methyl)diethoxysilane [CAS #: 3978-58-3], 3-Acryloxypropyltrimethoxysilane [CAS #: 4369-14-6].

In block [A] and/or block [B] the crosslinking monomer(s) are preferably present at a concentration of less than 40 mole-%, more preferably less than 30 mole-%, most preferably between 2.5 and 25 mole-% by mole of the respective block.
For Polymer P, possible crosslinking monomer(s) is preferably present at a concentration of less than 15 wt-%, more preferably less than 12.5 wt-%, and most preferably less than 10 wt-% based on the weight of the total monomer composition used to prepare Polymer P being 100%.
In a special embodiment is provided a block copolymer according to the invention, wherein the block copolymer comprises at least blocks [A]×[B]y; wherein block [A] comprises:
i) between 5 and 95 mole-% of ethylenically unsaturated monomer unit according to Formula 1, ii) less than 95 mole-% of other ethylenically unsaturated monomer units iii) from 2.5 to 25 mole-% of ethylenically unsaturated monomer bearing crosslinkable functional groups

where i), ii) and iii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5; wherein block [B] has an average degree of polymerization y, where y is an integer >5


Both block [A], block [B], and/or Polymer P may contain monomer(s) bearing adhesion promoting functionality such as comprising groups that promote adhesion especially to wet surfaces (adhesion promoting monomers). Suitable adhesion promoting monomers are known in the art and may comprise any of those listed herein.
Preferably such adhesion promoting monomers are present in an amount of not more than 10 wt-%, more preferably not more than 6 wt-%, most preferably from 0.5 to 5 wt-% of the respective monomer compositions.
Typical adhesion promoting monomers include ureido functional monomers, such as Plex 6852-O (ex. Evonik), i-bornyl(meth)acrylate, polyethylene(meth)acrylate, polypropylene(meth)acrylate and/or HPCA (available from BASF).
Convenient adhesion promoting monomer comprise olefinically unsaturated monomer with a wet-adhesion promoting functionality group thereon, such as acetoacetoxy groups and optionally substituted amine or urea groups, for example cyclic ureido groups, imidazole groups, pyridine groups, hydrazine or semicarbazide groups.
Optionally the adhesion promoting monomer may comprise those of Formula 3









where Y denotes an electronegative group,

R 6 is H, OH or an optionally hydroxy substituted C 1-10 hydrocarbo

R 7 is H or a C 1-10 hydrocarbo;

R 8 is a C 1-10 hydrocarbo group substituted by at least one activated unsaturated moiety; and; either:

A represents a divalent organo moiety attached to both the —HN— and —Y— moieties so the -A-, —NH—, —C(═O)— and —Y— moieties together represent a ring of 4 to 8 ring atoms, and R 7 and R 8 are attached to any suitable point on the ring; or

A is not present (and Formula 2 represents a linear and/or branched moiety that does not comprise a heterocyclic ring) in which case R 7 and R 8 are attached to R 6 ; and m is an integer from 1 to 4.

The ring moiet(ies) of Formula 2 are each attached to R 8 and in Formula 3 when m is 2, 3 or 4 then R 8 is multi-valent (depending on the value of m). If m is not 1 R 7 and —Y— may respectively denote the same or different moieties in each ring, preferably the same respective moieties in each ring. R 7 and R 8 may be attached at any suitable position on the ring.
Preferred monomers of Formula 2 comprise, conveniently consist essentially of, those where: A represents a optional substituted divalent
C 1-5 hydrocarbylene; and

—Y— is divalent —NR 9 — (where R 9 is H, OH, optionally hydroxy substituted

C 1-10 hydrocarbo or R 8 ) or divalent O,

More preferred monomers of Formula 2 comprise those where: m is 1 or 2
—Y— is —NR 8 — (i.e. where Formula 2 is attached to R 8 via a ring nitrogen), A represents a divalent C 1-3 hydrocarbylene; R 6 is H, R 7 is a C 1-10 hydrocarbo; and

R 8 comprises a (meth)acryloxyhydrocarbo group or derivative thereof (e.g. maleic anhydride).

Monomers represented by Formula 2 include some monomers informally referred to as ureido monomers. Further suitable ureido monomers of Formula 3 are described in “Novel wet adhesion monomers for use in latex paints” Singh et al, Progress in Organic Coatings, 34 (1998), 214-219, (see especially sections 2.2 & 2.3) and EP 0629672 (National Starch) both of which are hereby incorporated by reference. Conveniently the monomers of Formula 2 may be used as a substantially pure compound (or mixture of compounds) or may be dissolved in a suitable solvent such as a suitable (meth)acrylate or acrylic derivative for example methyl methacrylate.
Another suitable adhesion promoting monomer is hydroxypropylcarbamatacrylate (HPCA) which for example is available commercially from BASF as a 70% solution in ethanol (HPCA 70% EtOH)
HPCA has the structure









and is useful as a (wet) adhesion promoter and/or crosslinker and may be biobased and/or produced by enzymes.
Some monomers herein may perform more than one function (e.g. as a cross-linker and/or adhesion promoter).
Adhesion promoting functionalities that may improve adhesion may be matched to the different substrate to which the coating composition of which they are a part is to be applied. Thus monomers particular suited to adhere to old (aged) alkyd surfaces include ureido, DMAEMA and/or AAEM/amine), to plastic surfaces include iBOA, iBOMA and/or similar monomers and to metal surfaces include beta-CEA, phosphate, GA, GMA and/or silanes. Typical concentrations of adhesion promoting monomers in blocks [A] and/or [B] are less than 40 mole-%, more preferably less than 30 mole-%, most preferably from 5 to 25 mole-% by mole of the respective block.
For polymers of the invention especially those to be used in coating compositions, providing amino functional groups thereon may also be useful as such groups provide enhanced adhesion to certain substrates, such as wood and alkyd resins. Amino groups may be incorporated into a polymer by using a carboxyl functional precursor for example prepared by employing ethylenically unsaturated acid functional monomer(s) such as acrylic acid or methacrylic acid. At least some of the carboxy-functional groups may be converted to amino groups (as part of amino ester groups) by reaction with one or more iminating reagents. Useful iminating reagents may be selected from hydrocarbo imine, preferably C 1-8 hydrocarbyleneimine, more preferably C 1-4 alkyleneimine, most preferably ethylene imine, propylene imine or butylene imine. Such a reaction is well established in the art, being known as an imination reaction and the details of this are for example taught in U.S. Pat. No. 7,049,352 the contents of which are hereby incorporated herein by reference. Therefore a further aspect of the invention comprises iminated versions of the all the copolymers of the present invention as described herein. Polymers to be iminated usefully comprises reactive groups that are reactive with imines, preferred reactive groups being selected from aceto, carboxy and/or keto groups, for example acetocarboxy groups. Such imine-reactive groups may conveniently be introduced into the polymer by use of one or more of the following monomers: diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate (AAEM)
In another special embodiment is provided a block copolymer according to the invention, wherein the block copolymer comprises at least blocks [A]×[B]y; wherein block [A] comprises:
i) between 5 and 95 mole-% of ethylenically unsaturated monomer unit according to Formula 1 or 2, ii) less than 95 mole-% of other ethylenically unsaturated monomer units iii) from 0.5 to 15 mole-% of ethylenically unsaturated monomer bearing adhesion promoting functionality

where i), ii), and iii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5;

wherein block [B] has an average degree of polymerization y, where y is an integer >5 block [B] comprising between 1 and 20 mole-%, more preferably between 2.5 and 10 mole-% of crosslinking monomer(s).


In yet another special embodiment is provided a block copolymer according to the invention, wherein the block copolymer comprises at least blocks [A]×[B]y; wherein block [A] comprises:
i) between 5 and 95 mole-% of ethylenically unsaturated monomer unit according to Formula 1 or 2, ii) less than 95 mole-% of other ethylenically unsaturated monomer units

where i), and ii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5;

wherein block [B] consists essentially of a monomer selected from the group of isobornyl acrylate and isobornyl methacrylate, and has an average degree of polymerization y, where y is an integer >5

block [B] comprising up to 20 mole-%, preferably from 1 to 20 mole-%, more preferably between 2.5 and 10 mole-% of crosslinking monomer(s).


In a special embodiment of the invention is described a block copolymer, or the combination of block copolymer and Polymer P according to the invention, where the acid groups of the block copolymer or of Polymer P are reacted with an alkylene imine, preferably propylene imine. Preferably at least 30 mole-% of the acid groups are reacted with alkylene imine, more preferably at least 40 mole-%, most preferably between 45 and 90 mole-% of the acid groups in the block copolymer and/or Polymer P.
Preferably, the theoretical Tg values for blocks A and B, as calculated with the Fox equation, differ from each other by at least 5° C., more preferably by at least 10° C., most preferably by at least 20° C.
Preferably the number average molecular weight of block [A] and of block [B] are independently in the range of from 500 to 75,000 g/mol, more preferably 1,000 to 50,000 g/mol, most preferably 2,000 to 25,000 g/mol.
Preferably block copolymer [A]×[B]y has a weight average molecular weight <100,000 g/mol, more preferably <75,000 g/mol and especially <50,000 g/mol.
Preferably block [A] has an average degree of polymerization x from 5 to 500, more preferred from 10 to 300, most preferred from 15 to 200.
Preferably block [B] has an average degree of polymerization y from 5 to 500, more preferred from 10 to 300, most preferred from 15 to 200.
Preferably either block [A] or block [B] has a Hansch parameter less than 1.5, preferably <1.0, more preferably <0.8
Preferably polymer P has a Hansch parameter greater than 1.5, more preferably >2.0 and most preferred >2.5
In yet another special embodiment according to the invention Polymer P is obtained via an emulsion polymerization process in the presence of the block copolymer according to the invention, where Polymer P comprises: i) 0 to 15 wt % of ethylenically unsaturated monomer unit bearing adhesion promoting functional groups; ii) 0 to 15 wt % of ethylenically unsaturated monomer unit bearing water-dispersing functional groups; iii) 50 to 100 mol % of ethylenically unsaturated monomer selected from: C1-18 hydrocarbo(meth)acrylate(s) and/or styrenic monomer(s); iv) 0 to 35 wt % of ethylenically unsaturated monomer unit different from those from i), ii)+iii); where i), ii), iii)+iv) add up to 100%.
The block copolymers according to the invention can be made using solution polymerization, solution-dispersion polymerization, bulk polymerization and/or emulsion polymerization. For RAFT, the preferred processes are described in for example WO2009/121911 (e.g. see page 16 line 27 to page 17 line 29) the contents of which are incorporated herein by reference. The most preferred RAFT process is solution dispersion polymerisation, where the polymerisation is done in solution and the resulting polymer is dispersed after neutralizing (part of) the acid groups. The preferred solvents and solvent mixtures are described on page 17 line 4 of WO2009/121911. Polymer P is preferably prepared via emulsion polymerization also using the preferred process conditions described in WO2009/121911.
For CCTP, the preferred processes are described in EP1769031 the contents of which are incorporated herein by reference. For CCTP, the preferred polymerization process is solution polymerization, or emulsion polymerization e.g. as described in EP1769031.
Amphiphilic block copolymers are advantageously prepared using a solution dispersion polymerization process, or using an aqueous emulsion polymerization process. In an aqueous emulsion polymerization process a first block composition is prepared in aqueous solution, followed by the polymerization of a second block composition via an emulsion polymerization process (e.g. as disclosed in Chaduc et al. Macromol. Rapid Commun. 2011, 32, 1270-1276). These processes are particularly preferred for amphiphilic block copolymers prepared via the RAFT process.
In case itaconic anhydride is copolymerized in the block copolymer, preferred solvents are non-protic. Also water as reaction medium is not preferred during the polymerization of the block copolymer in cases where the block copolymer contains itaconic anhydride.
Preferred initiator type and concentration, preferred surfactant type and concentration, as well as stabilizing colloid for emulsion polymerisation, preferred polymerisation temperatures for bulk, solution, solution-dispersion and/or emulsion polymerisation, as well as preferred solvents and neutralizing amines for these processes are well known to those skilled in the art and for example are described in WO2009/121911 (see page 20 line 23 to page 21 line 26), EP788518, EP1769031, and WO2007147561 the contents of which are incorporated herein by reference.
The residual monomer level is preferably less than 3000 ppm, more preferably less than 2000 ppm, and most preferred less than 1000 ppm. In order to obtain such low free monomer levels, Polymer P can comprise a so called chaser monomer as described in WO2011073417 the contents of which are incorporated by reference.
In one embodiment according to the invention Polymer P is obtained by an emulsion polymerization process in the presence of the block copolymer according to the invention, where Polymer P comprises: i) at least 20 wt-% of dialkyl itaconate, more preferably at least 30 wt-%, ii) 0 to 15 wt % of ethylenically unsaturated monomer unit bearing water-dispersing functional groups, more preferably between 2.5 and 10 wt-%; and iii) not more than 80 wt-% of other ethylenically unsaturated monomer selected from: C1-18 hydrocarbo(meth)acrylate(s) and/or styrenic monomer(s) other than monomers i) and ii); where i), ii),+iii) add up to 100%, further characterized in that the polymerization is followed by a chaser monomer composition preferably comprising acrylic monomer(s) and/or styrene, further characterized in that the ratio of dry weight of chaser monomer composition compared to the dry polymer weight of Polymer P is between 2.5:97.5 and 30:70, more preferably between 5:95 and 20:80.
In yet another special embodiment according to the invention Polymer P is obtained by an emulsion polymerization process in the presence of the block copolymer according to the invention, where Polymer P comprises: i) at least 20 wt-% of dialkyl itaconate, more preferably at least 30 wt-%, ii) 0 to 15 wt % of ethylenically unsaturated monomer unit bearing water-dispersing functional groups, more preferably between 2.5 and 10 wt-%; and iii) not more than 80 wt-% of other ethylenically unsaturated monomer selected from: C1-18 hydrocarbo(meth)acrylate(s) and/or styrenic monomer(s) other than monomers i) and ii); where i), ii), +iii) add up to 100%, further characterized in that the dialkyl itaconate monomer(s) comprise at least 50 mole-% of higher itaconate(s) based on total weight of monomer i).
In the case of RAFT polymerization, the control agent functional group which is typically located at one of the chain ends of the prepared block copolymer can be deactivated or removed using any suitable method or process as disclosed in the open literature. The RAFT group can be deactivated or removed via for example oxidation reactions, radical induced reactions, hydrolysis, thermolysis, or aminolysis. In the case that the control agent functional group is not removed or only partially removed prior to the preparation of polymer P at least part of the polymer P chains will grow onto or become covalently attached to at least part of the block copolymer chains. Preferably, the RAFT group is preferably removed from the block copolymer prior to use as is or prior to using it as seed in the polymerization of Polymer P. Preferred ways of removing the RAFT agent are via aminolysis, or by oxidative removal. Removal of RAFT agents is further described in the review paper from Moad (Polym. Int. 2010, 60, p 9-25).
The block copolymer can be dissolved or emulsified in aqueous media. Preferably, the block copolymer is dispersed in water. The particle size of the block copolymer emulsion as measured by Dynamic Light Scattering is preferably in the range of 10 to 1000 nm, more preferably between 25 and 500 nm, even more preferably between 40 and 300 nm, and most preferred between 50 and 200 nm.
In the case of the combination of block copolymer(s) according to the invention with Polymer P, the preferred particle sizes are in the same ranges.
Preferably, the biorenewability content of the block copolymer according to the invention, that of Polymer P, as well as that of the total polymer composition is at least 15 wt-%, more preferred more than 25 wt-%, even more preferred at least 35 wt-%, and most preferred at least 45 wt-%. This can be achieved by copolymerization of (partially) biorenewable monomers. Typical examples of (partially) biobased monomers include:
Acrylic acid and esters thereof, where the acrylic acid can for instance be obtained from glycerol or lactic acid. The alkanol groups making the ester can also be obtained from biorenewable sources. Methacrylic acid and esters thereof, where the methacrylic acid can for instance be obtained from syn gas (Lucite technology). The alkanol groups making the ester can also be obtained from biorenewable sources. Itaconates; including itaconic acid, esters, half esters, amides, half amides, and imides made thereof. Again, the alkanol or alkyl amine groups can also be obtained from biorenewable resources. α-methylene butyrolactones, α-methylene valerolactones, α-methylene butyrolactams, α-methylene valerolactams, where the alkyl amine groups can also be obtained from biorenewable resources. Methylidene malonic acid and its mono and diesters, where the alkanol groups making the ester can also be obtained from biorenewable sources.

In a further embodiment there is provided an aqueous coating composition comprising a block copolymer; wherein the block copolymer comprises at least blocks [A]×[B]y, wherein block [A] comprises:
i) between 5 and 95 mole-% of ethylenically unsaturated monomer unit according to Formula 1 or 2, ii) at least 10 mole-% of a monomer unit according to Formula 3 (e.g. a ureido monomer), more preferred at least 20 mole-%, most preferred at least 30 mole-% iii) less than 85 mole-% of other ethylenically unsaturated monomer units where i), ii), and iii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5;

wherein block [B] has an average degree of polymerization y, where y is an integer >5


As well as block [A] comprising compounds of Formula 1, 1A and/or 1B it may comprise compounds of Formula 3









where R 5 is H, or a C1-5alkyl.
In the cases where itaconic anhydride is copolymerized in the block copolymer according to the invention, the anhydride can be post modified with a nucleophile to introduce further functional groups into the resultant polymer.
A yet other embodiment according to the invention provides a block copolymer wherein the block copolymer comprises at least blocks [A]×[B]y; wherein block [A] comprises:
i) between 5 and 95 mole-% of ethylenically unsaturated monomer unit according to Formula 2, ii) less than 95 mole-% of other ethylenically unsaturated monomer units

where i), and ii) add up to 100%; and block [A] has an average degree of polymerization x, where x is an integer >5;

wherein block [B] has an average degree of polymerization y, where y is an integer >5 and preferably block [A] comprises monomers of Formula 2A











where Y is —O—,
Polymers of this embodiment made be obtained and/or obtainable by emulsion polymerisation characterized by a further step in that before emulsification of the block copolymer at least 10 mole-% of the anhydride is converted to the amic acid by reaction between the anhydride and a primary or secondary amine. More preferably, at least 20 mole-% of the anhydride groups are converted to the amic acid, even more preferably at least 35 mole-%.
Where the block copolymer of the invention comprises dialkyl itaconates, in one embodiment the alkanols from which the ester groups of the itaconates are derived may be C 1-4 alkanols (preferably ethanol and/or methanol most preferably methanol) and these polymers may be post modified by transamidation of the ester groups. For example to prepare this embodiment alkyl amines may be reacted with the dialkyl itaconate containing polymer to form an amide and a volatile alcohol, which is removed by evaporation. It is preferred to replace at least 5 mole-% of the ester groups with an alkyl, aryl, cyclo alkyl or alkylaryl amine having up to 20 carbon atoms, more preferably up to 8 carbon atoms. It is more preferred to replace at least 10 mole-%, more preferably at least 25 mole-%, of the alkanol groups.
The block copolymer according to the invention is preferably used emulsified or dissolved in water. As mentioned above, the block copolymer can also be obtained in combination with a Polymer P. It is envisaged that the aqueous block copolymer emulsion or solution and the combination of block copolymer and Polymer P, can advantageously be blended with a second polymer emulsion to improve film properties. Typical examples of second polymer emulsions are sequential polymers, oligomer-polymer emulsions and/or urethane-acrylate emulsions, powerfeed emulsions, polymer emulsions comprising polymer particles with an average particle size of less than 120 nm, more preferably less than 90 nm, and a theoretical Tg of at least 60° C., more preferred at least 80° C., alkyd emulsions, polyester emulsions, and polyurethane emulsions. It is envisaged that the block copolymer according to the invention, as well as the combination of the block copolymer with Polymer P, can advantageously be admixed with multifunctional acrylic monomers making the combination radiation curable.
The second emulsion preferably comprises at least 10 wt-% of monomers obtained from biorenewable sources, more preferably, at least 30 wt-%, most preferably at least 40 wt-%.
The phase ratio of the block copolymer according to the invention, or in combination with Polymer P, to second emulsions is preferably between 95:5 and 10:90, more preferably between 90:10 and 30:70, and most preferably between 85:15 and 50:50, dry weight by dry weight. In the case the block copolymer according to the invention, either as produced or in combination with Polymer P, is admixed with multifunctional acrylic monomer, the preferred phase ratio is between 95:5 and 10:90, more preferably between 90:10 and 30:70, and most preferably between 85:15 and 50:50, dry weight by dry weight.
In a special embodiment of the invention is provided an aqueous polymer emulsion comprising a block copolymer according to the invention, wherein the block copolymer comprises at least blocks [A]×[B]y, which is blended with a second emulsion, which in turn is preferably a sequential emulsion, an oligomer supported emulsion, a so called powerfeed emulsion, an alkyd emulsion, a polyester emulsion, a polyurethane emulsion, a urethane-acrylate emulsion or a polyvinyl emulsion having a particle size of not more than 125 nm and a Tg of at least 80° C., in a phase ratio of between 95:5 and 10:90, more preferably between 90:10 and 30:70, and most preferably between 85:15 and 50:50, of dry weight of block copolymer by dry weight of second emulsion.
In a yet another special embodiment of the invention is provided an aqueous polymer emulsion comprising a block copolymer, wherein the block copolymer comprises at least blocks [A]×[B]y, which is blended with a multi-functional acrylic monomer, in a phase ratio of between 95:5 and 10:90, more preferably between 90:10 and 30:70, and most preferably between 85:15 and 50:50, of dry weight of block copolymer by dry weight of multi-functional acrylic monomer.
In yet another special embodiment of the invention is provided an aqueous polymer emulsion comprising a block copolymer and a sequentially polymerized Polymer P according to the invention, wherein the block copolymer comprises at least blocks [A]×[B]y, which aqueous polymer emulsion is blended with a second emulsion, which in turn is preferably a sequential emulsion, an oligomer supported emulsion, a so called power feed emulsion, an alkyd emulsion, a polyester emulsion, a polyurethane emulsion, a urethane-acrylate emulsion or a polyvinyl emulsion having a particle size of not more than 125 nm and a Tg of at least 80° C., in a phase ratio of between 95:5 and 10:90, more preferably between 90:10 and 30:70, and most preferably between 85:15 and 50:50, of dry weight of block copolymer and Polymer P by dry weight of second emulsion.
In yet another special embodiment of the invention is provided an aqueous polymer emulsion comprising a block copolymer and a sequentially polymerized Polymer P according to the invention, wherein the block copolymer comprises at least blocks [A]×[B]y, which aqueous polymer emulsion is blended with a multi-functional acrylic monomer, in a phase ratio of between 95:5 and 10:90, more preferably between 90:10 and 30:70, and most preferably between 85:15 and 50:50, of dry weight of block copolymer and Polymer P by dry weight of multi-functional acrylic monomer.
It is envisioned that the emulsion polymers of this invention can be used to prepare an aqueous coating composition which contains one or more inorganic pigments. These pigments are typically materials such as silicates, alumino silicates, alkali earth carbonates such as CaCO 3 , clays, metal oxides such as Al 2 O 3 , TiO 2 , Fe x O y , and ZnO, Phosphates, natural and synthetic zeolites, and organic opacifying materials such as Opaque Polymer (Ropaque™ Ultra). The PVC of the aqueous coating composition is defined as the fractional volume of pigment including opaque polymer based on the total volume of pigment and polymer in the coating composition. It is envisioned that aqueous coating composition prepared using the emulsion polymers of this invention will have a PVC of less than 90%. For interior and exterior decorative paints the PVC will be less than 60%, and more preferably less than 50%. For paints with 60 degree gloss values above 10 the PVC is preferably less than 40% and more preferably less than 30%. Barrier types of primers, direct to metal coatings, and decorative top coats preferably have a PVC of less than 30%. In certain embodiments the coatings may have a 60 degree gloss value less than 10, and be transparent. In these cases PVC levels below 5% are preferred.
The aqueous compositions of the invention may be used in various applications and for such purposes may be optionally further combined or formulated with other additives or components, such as defoamers, rheology control agents, thickeners, dispersing and stabilizing agents (usually surfactants), wetting agents, fillers, extenders, fungicides, bactericides, coalescing and wetting solvents (although solvents may not normally be required), plasticizers, anti-freeze agents, waxes and pigments.
The aqueous compositions may e.g. be used, appropriately formulated if necessary, for the provision of films, polishes, varnishes, lacquers, paints, inks and adhesives. However, they are particularly useful and suitable for providing the basis of protective coatings for interior and exterior decorative coatings for wood, metal, plastic, masonry, concrete, and wood composites including plastic wood and cement wood composite materials, clear and semi transparent stains and top coats for wood and wood composites including plastic wood and cement wood composite materials, clear and pigmented primers and top coats for wood furniture and flooring, road marking paints, coatings to protect and preserve structural metal against corrosion, such as bridges, water towers and tank farms, coatings for flooring including wood, wood composite and concrete flooring, barrier primers for wall board, wood and masonry to block migration of water soluble materials such as nicotine, inorganic salts, and tannins, coatings for paper, primers, colored base coats and clear top coats for automotive parts including plastics and metals, temporary coatings designed to temporarily protect a substrate, and then be easily removed at a later time, temporary coatings designed to be thermally decomposed after manufacture such as those used in the manufacture of cathode ray tubes or fluorescent lights, sound deading coatings such as those used on the underside of a car, inks, and overprint varnishes, and adhesive primers and structural adhesives.
Preferably the compositions of the invention have VOC levels of less than 100 g/L and more preferably less than 80 g/L, most preferably less than 50 g/L and especially less than 20 g/L of volatile organic components such as coalescing solvents.
In a preferred embodiment of the invention is provided a coating composition comprising an aqueous binder composition according to the invention.
In a preferred embodiment of the invention is provided a coating composition comprising an aqueous binder composition according to the invention having a PVC of less than 50%, more preferably of less than 25%. Preferably, stains would have a PVC of less than 10%, top coats would have a PVC of between 15 and 25%, and primer would have a PVC of between 25 and 50%.
In a preferred embodiment of the invention is provided a coating composition comprising an aqueous binder according to the invention, where the coating composition comprises hollow sphere pigment particles, such as for instance ROPAQUE™ DUAL, ROPAQUE™ ULTRA, ROPAQUE™ ULTRA E, and ROPAQUE™ Ultra EF (ex. DOW).
Silylation
The process of the present invention may optionally comprises a further silylation reaction to form a silylated block copolymer of the invention in which case one or more silylating reagents may be used during the process. Useful silylating reagents may be selected from at least one alkoxysilyl compound and/or alkyliminosilyl compound having a reactive hydrogen: for example aminosilanes
Suitable examples of aminosilanes include, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltributoxysilane, 3-aminopropylphenyldiethoxysilane, 3-aminopropylphenyldimethoxysilane, 3-aminopropyltris(methoxyethoxyethoxy)silane, 2-aminoisopropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutylethyldimethoxysilane, 4-aminobutylethyldiethoxysilane, 4-aminobutyldimethylmethoxysilane, 4-aminobutylphenyldimethoxysilane, 4-amino-butylphenyldiethoxysilane, 4-amino(3-methylbutyl)methyldimethoxysilane, 4-amino(3-methylbutyl)methyldiethoxysilane, 4-amino(3-methylbutyl)trimethoxysilane, 3-aminopropylphenylmethyl-n-propoxysilane, 3-aminopropylmethyldibutoxysilane, 3-aminopropyldiethylmethylsilane, 3-aminopropylmethylbis(trimethylsiloxy)silane, 11-aminoundecyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltris(2-ethylhexoxy)silane, N-(6-aminohexyl)-3-aminopropyltrimethoxysilane, N-benzyl-N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-vinylbenzyl-N-(2-aminoethyl)-3-aminopropylpolysiloxane, N-vinylbenzyl-N-(2-aminoethyl)-3-aminopropylpolysiloxane, 3-ureidopropyltriethoxysilane, 3-(m-amino-phenoxy)propyltrimethoxysilane, m- and/or p-aminophenyltrimethoxysilane, 3-(3-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropylmethylbis(trimethylsiloxy)silane, 3-aminopropyltris(trimethylsiloxy)silane, 3-aminopropylpentamethyldisiloxane, N,N-bis-(3-trialkoxysilylpropyl)-amine or any desired mixture of such aminosilanes.
Preferred aminosilanes are 3-aminopropyl silanes, like 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and/or 3-aminopropylmethyldiethoxysilane.
If the process of the present invention comprises a silylation reaction the itaconate functional polymer may comprises reactive groups that are reactive with silyl groups, preferred silyl-reactive groups may also be selected from one or more groups containing active hydrogen such as hydroxyl or primary or secondary amine and/or a diester of a carbonic acid (carbonate group).
Such silyl-reactive groups may conveniently be introduced into the itaconate functional polymer by use of one or more of the following monomers during polymerisation: monomers comprising an activated unsaturated moiety and also a plurality of hydroxyl and/or imino (primary or secondary) groups
A further aspect of the invention provides a modified itaconate functional polymer obtained and/or obtainable by a process of the invention.
Acid Monomers
Copolymers of the invention may optionally comprise acid functional monomer(s) (also denoted acid monomers) as described herein which may be either part of the itaconate functional monomers or the non itcaonate functional monomers.
Suitable acid monomers can be monofunctional or difunctional in acid functionality. Preferred monomers are acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, maleic acid, and maleic anhydride. More preferred monomers are acrylic acid, methacrylic acid, and itaconic anhydride. The most preferred acid functional monomer is itaconic anhydride.
It will be understood that when referring to acid functional and/or acidic components herein this may relate to acidic moieties and/or potential acidic moieties which under the conditions of use may form acidic groups (e.g. anhydrides). An acid bearing monomer could be polymerised as the free acid or as a salt, e.g. the ammonium and/or alkali metal salt thereof. References herein to acids should therefore also be understood to include suitable salts and/or derivates thereof (such as anhydrides and/or acid chlorides thereof).
Preferred hydrophilic monomers comprise, advantageously consist essentially of, at least one ethylenically unsaturated carboxylic acid although other acid groups such as optionally substituted organo phosphoric and/or sulphonic acids may also be used.
Examples include phosphated alkyl(meth)acrylates, sulphonic acids (and derivatives thereof) of arylalkylenes, sulphonic acids (and derivatives thereof) of alkyl(meth)acrylates and/or other organo substituted sulphonic acids (such as acrylamidoalkyl sulfonic acids).
Preferred arylalkylene sulphonic acids are those where the arylalkylene moiety comprises optionally hydrocarbo substituted styrene, conveniently optionally C 1-10 hydrocarbyl substituted styrene more conveniently optionally C 1-4 alkyl substituted styrene. Useful acids are sulphonic acid substituted derivatives of stryenic compounds selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, di-methyl styrene and/or mixtures thereof. Especially preferred is styrene p-sulphonic acid and its corresponding acid chloride styrene p-sulphonyl chloride.
Preferred phosphated organo acids comprise phosphated (meth)acrylates optionally substituted for example with one or more hydroxyl groups, for example phosphated hydroxy(meth)acrylates and C 1-4 alkyl esters thereof.
Other preferred acid monomers comprises partial acids of multivalent esters, more preferably. half esters of diesters, most preferably mono acid half itaconate esters (i.e. those esters of Formula 1 where either Ra or Rb is H). Itaconic acid is also another example of a suitable (di)acid functional monomer.
More preferred acids have one ethylenic group and one or two carboxy groups. Most preferably the acid(s) (and/or suitable acid derivative(s) thereof) are selected from the group consisting of: acrylic acid (and copolymerisable oligomers thereof), beta carboxy ethyl acrylate, citraconic acid, mesaconic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, methacrylic acid, methylene malonic acid, anhydrides thereof, salts thereof, acid chlorides thereof, combinations thereof in the same species and/or mixtures thereof.
Especially preferred acidic monomers are selected from: acrylic acid, methacrylic acid, beta carboxy ethyl acrylate, methylene malonic acid, maleic anhydride, itaconic acid, itaconic anhydride, phosphated hydroxyl ethyl methacrylate (phosphated HEMA), phosphated hydroxyl ethyl acrylate (phosphated HEA), phosphated hydroxyl propyl methacrylate (phosphated HPMA), phosphated hydroxyl propyl acrylate (phosphated HPA), sulphonated styrene (and its chloride), 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and ethylmethacrylate-2-sulphonic acid.
Particularly preferred acid monomers are acrylic acid, methacrylic acid, beta carboxy ethyl acrylate, itaconic acid, and/or itaconic anhydride.
For emulsion polymerization acrylic acid, methacrylic acid, beta carboxy ethyl acrylate, and/or itaconic acid may be convenient. For SAD copolymerization, acrylic acid, methacrylic acid, and/or itaconic anhydride are preferred.
Preferably the acid monomer may be used in a total amount of up to 10%, preferably from 0 to 10%, more preferably from about 0.1% to about 5%, even more preferably from about 0.1% to about 3%, most preferably from about 0.5% to about 2.5% by weight of the relevant monomer composition.
Conveniently the acid monomer may be used in a total amount sufficient that the resultant polymer has an acid value (AV) of between 3 and 100 mg KOH per g of solid polymer, preferably from 8 to 80 mg KOH per g, more preferably from 15 to 65 mg KOH per g, and most preferably from 15 to 45 mg KOH per g.
Usefully the amount of acid monomer used satisfies both the acid value (AV) and weight limits herein, but it will be appreciated that depending on the monomer used the AV specified herein may be achieved using weight percentages outside those preferred wt-% values given herein. Where there is an apparent inconsistency herein between any weight % of monomer or other component and the acid values specified it will be appreciated that satisfying the AV is generally the more desirable objective. If necessary the values for weight % of the relevant ingredients can be modified appropriately in a manner well known to a skilled person.
Other Non Itaconate Functional Monomers
Block [B] comprises moieties other than itaconate functional moieties. Such moieties may comprise monomers that can undergo crosslinking, that can improve adhesion of the coating to various substrates, that can enhance the colloidal stability of the polymer emulsion, or that can be used to affect Tg, or polymer polarity.
Conveniently block [B] may comprise (meth)acrylate monomers having alkyl moieties comprising between 1 and 20 carbon atoms, styrene, alpha-methyl styrene, (meth)acrylonitrile, (meth)acryl amide or alkylated(meth)acryl amides, diacetone acryl amide, acetoacetoxyethyl methacrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, silane functional monomers, such as 3-methacryloxypropyl trimethoxysilane (Geniosil GF31, ex Wacker), ureido functional monomers, such as Plex 6852-O (ex. Evonik), i-bornyl(meth)acrylate, polyethylene(meth)acrylate, polypropylene(meth)acrylate.
Block [B] may also comprise crosslinking monomers that can induce crosslinking of the copolymer composition. Crosslinking can occur at ambient temperatures (using for instance diacetone acryl amide combined with adipic dihydrazide), at elevated temperatures (stoving conditions in which for instance copolymerized hydroxyethyl(meth)acrylate reacts with hexamethoxy methyl melamines), as 2C composition (copolymerized hydroxyethyl(meth)acrylate reacting with polyisocyanates, such as Bayhydur 3100), or as UV coating (when polymers or oligomers having multiple unsaturated groups are admixed. Typical examples include di- or tri-functional multifunctional acrylates such as trimethylol propane triacrylate or ethoxylated or propoxylated versions thereof).
Optionally block [B] may also comprise least one polymer precursor(s) of Formula 5









where Y denotes an electronegative group,

R 6 is H, OH or an optionally hydroxy substituted C 1-10 hydrocarbo

R 7 is H or a C 1-10 hydrocarbo;

R 8 is a C 1-10 hydrocarbo group substituted by at least one activated unsaturated moiety; and; either:

A represents a divalent organo moiety attached to both the —HN— and —Y— moieties so the -A-, —NH—, —C(═O)— and —Y— moieties together represent a ring of 4 to 8 ring atoms, and R 7 and R 8 are attached to any suitable point on the ring; or

A is not present (and Formula 5 represents a linear and/or branched moiety that does not comprise a heterocyclic ring) in which case R 7 and R 8 are attached to R 6 ; and m is an integer from 1 to 4.

The ring moiet(ies) of Formula 5 are each attached to R 8 and in Formula 3 when m is 2, 3 or 4 then R 8 is multi-valent (depending on the value of m). If m is not 1 R 7 and —Y— may respectively denote the same or different moieties in each ring, preferably the same respective moieties in each ring. R 7 and R 8 may be attached at any suitable position on the ring.
Preferred monomers of Formula 5 comprise, conveniently consist essentially of, those where: A represents an optional substituted divalent C 1-5 hydrocarbylene; and
—Y— is divalent —NR 9 — (where R 9 is H, OH, optionally hydroxy substituted C 1-10 hydrocarbo or R 8 ) or divalent O,
More preferred monomers of Formula 5 comprise those where: m is 1 or 2
—Y— is —NR 8 — (i.e. where Formula 5 is attached to R 8 via a ring nitrogen), A represents a divalent C 1-3 hydrocarbylene; R 6 is H, R 7 is a C 1-10 hydrocarbo; and

R 8 comprises a (meth)acryloxyhydrocarbo group or derivative thereof (e.g. maleic anhydride).

Monomers represented by Formula 5 include some monomers informally referred to as ureido monomers. Further suitable ureido monomers of Formula 3 are described in “Novel wet adhesion monomers for use in latex paints” Singh et al, Progress in Organic Coatings, 34 (1998), 214-219, (see especially sections 2.2 & 2.3) and EP 0629672 (National Starch) both of which are hereby incorporated by reference. Conveniently the monomers of Formula 3 may be used as a substantially pure compound (or mixture of compounds) or may be dissolved in a suitable solvent such as a suitable (meth)acrylate or acrylic derivative for example methyl methacrylate.
Other and/or additional components may be used in those cases where higher molecular weights are desired, such as suitable multi functional (meth)acrylates or divinyl aromatics. Typical examples include di-, tri-, or tetra-functional (meth)acrylates, especially difunctional (meth)acrylates and divinyl benzene. Typical concentrations are less than 10%, more preferred less than 5%, even more preferred between 0.05 and 4%, most preferred between 0.1 and 2.5%, and even most preferred between 0.15 and 1.5% by weight based on total monomers.
A further aspect of the invention provides for a coating composition comprising a polymer as described herein. The polymer can be introduced to the coating composition in different ways, non limiting examples of which are described below:
By Blending or Admixing.
The polymer can be mixed with a preformed latex. This can be done by dissolving emulsifying, or dispersing the polymer first and next admixing it with a second emulsion(s). The second emulsion(s) can be any type of polymer emulsion, including polyvinyl compositions, comprising sequential, oligomer supported, gradient morphology emulsions, polyurethane emulsions, urethane-acrylate emulsions, alkyd emulsions, and/or polyester emulsions.
Using Surfactant
The low molecular weight polymer, which is dissolved emulsified, or dispersed in water, is used as stabilizer for the emulsion polymerization step. An example of such a process can be found in Comparative example 1 in WO2005/097854.
Use in a Pigment Dispersant
The polymer can also be added to a coating composition by first mixing it in a pigment dispersion. In this case the polymer is added to a pigment dispersion comprising inorganic pigment particles and the mixture grinded until a stable pigment dispersion is obtained. Next, the pigment dispersion is added to a polymer emulsion(s) to form a pigmented coating.
Preferred application areas for compositions and/or coatings or the invention include wood coatings, such as joinery, industrial wood, parquet, and decorative applications, adhesive and graphic arts applications, such as inks, adhesives, overprint varnishes, film coatings, coatings for application on various plastics, such as polystyrene, polyester, PVC, polypropylene, polyethylene, or application to glass or metal.
Other aspects and embodiments of the invention are given below.
One aspect of the invention relates to an aqueous sequential vinyl polymer emulsion comprising 30% by weight (preferably at least 40%) of polymer obtained or obtainable from one or more higher itaconate diester(s).
The term “activated unsaturated moiety”, is used herein to denote a species comprising at least one unsaturated carbon to carbon double bond in chemical proximity to at least one activating moiety. Preferably the activating moiety comprises any group which activates an ethylenically unsaturated double bond for addition thereon by a suitable electrophilic group. Conveniently the activating moiety comprises oxy, thio, (optionally organo substituted)amino, thiocarbonyl and/or carbonyl groups (the latter two groups optionally substituted by thio, oxy or (optionally organo substituted) amino). More convenient activating moieties are (thio)ether, (thio)ester and/or (thio)amide moiet(ies). Most convenient “activated unsaturated moieties” comprise an “unsaturated ester moiety” which denotes an organo species comprising one or more “hydrocarbylidenyl(thio)carbonyl(thio)oxy” and/or one or more “hydrocarbylidenyl(thio)-carbonyl(organo)amino” groups and/or analogous and/or derived moieties for example moieties comprising (meth)acrylate functionalities and/or derivatives thereof. “Unsaturated ester moieties” may optionally comprise optionally substituted generic α,β-unsaturated acids, esters and/or other derivatives thereof including thio derivatives and analogues thereof.
Preferred activated unsaturated moieties are those represented by a radical of Formula 6.









where n′ is 0 or 1, X 6 is oxy or, thio; X 7 is oxy, thio or NR 17 (where R 17 represents H or optionally substituted organo), R 13 , R 14 , R 15 and R 16 each independently represent a bond to another moiety in Formula 6, H, optional substituent and/or optionally substituted organo groups, where optionally any of R 13 , R 14 , R 15 and R 16 may be linked to form a ring; where at least one of R 13 , R 14 , R 15 and R 16 is a bond; and all suitable isomers thereof, combinations thereof on the same species and/or mixtures thereof.
The terms “activated unsaturated moiety”; “unsaturated ester moiety” and/or Formula 6 herein represents part of a formula herein and as used herein these terms denote a radical moiety which depending where the moiety is located in the formula may be monovalent or multivalent (e.g. divalent).
More preferred moieties of Formula 6 (including isomers and mixtures thereof) are those where n′ is 1; X 6 is O; X 7 is O, S or NR 7 .
R 13 , R 14 , R 15 and R 16 are independently selected from: a bond, H, optional substituents and optionally substituted C 1-10 hydrocarbo, optionally R 15 and R 16 may be linked to form (together with the moieties to which they are attached) a ring; and where present R 17 is selected from H and optionally substituted C 1-10 hydrocarbo.
Most preferably n′ is 1, X 6 is O; X 7 is O or S and R 13 , R 14 , R 15 and R 16 are independently a bond, H, hydroxy and/or optionally substituted C 1-6 hydrocarbyl.
For example n′ is 1, X 6 and X 7 are both O; and R 3 , R 4 , R 5 and R 6 are independently a bond, H, OH, and/or C 1-4 alkyl; or optionally R 5 and R 6 may together form a divalent C 0-4 alkylenecarbonylC 0-4 alkylene moiety so Formula 6 represents a cyclic anhydride (e.g. when R 15 and R 16 together are carbonyl then Formula 6 represents a maleic anhydride or derivative thereof).
For moieties of Formula 6 where n′ is 1 and X 6 and X 7 are both O then when one of (R 13 and R 14 ) is H and also R 13 is H, Formula 6 represents an acrylate moiety, which includes acrylates (when both R 13 and R 14 are H) and derivatives thereof (when either R 13 and R 14 is not H). Similarly when one of (R 13 and R 14 ) is H and also R 15 is CH 3 , Formula 6 represents an methacrylate moiety, which includes methacrylates (when both R 13 and R 14 are H) and derivatives thereof (when either R 13 and R 14 is not H). Acrylate and/or methacrylate moieties of Formula 5 are particularly preferred.
Conveniently moieties of Formula 6 are those where n′ is 1; X 6 and X 7 are both O; R 13 and R 14 are independently a bond, H, CH 3 or OH, and R 15 is H or CH 3 ; R 16 is H or R 15 and R 16 together are a divalent C═O group.
More conveniently moieties of Formula 6 are those where n′ is 1; X 6 and X 7 are both O; R 13 is OH, R 4 is CH 3 , and R 15 is H and R 6 is a bond and/or tautomer(s) thereof (for example of an acetoacetoxy functional species).
Most convenient unsaturated ester moieties are selected from: —OCO—CH═CH 2 ; —OCO—C(CH 3 )═CH 2 ; acetoacetoxy, —OCOCH═C(CH 3 )(OH) and all suitable tautomer(s) thereof.
It will be appreciated that any suitable moieties represented by Formula 6 could be used in the context of this invention such as other reactive moieties.
Vinyl Polymer
Whilst the term vinyl polymer is commonly used to refer to thermoplastic polymers derived by polymerization from compounds containing the vinyl group (CH 2 ═CH—), the term “vinyl polymer” is used herein more broadly to denote any polymer (whether thermoplastic or not) that comprises (e.g. as repeat units therein) and/or is derived from monomers and/or polymer precursors comprising one or more of the following moieties: activated unsaturated moieties (such as acrylates and/or methacrylates); any olefinically unsaturated moieties (such as vinyl moieties); mixtures thereof; and/or combinations thereof within the same moiety.
There is an increasing demand to use bio-renewable monomers in order to improve the sustainability of the polymers used in for example coating applications. In view of concerns about depletion of fossil fuel resources or an increase in carbon dioxide in the air that poses a global-scale environmental problem in recent years, methods for producing raw materials of these polymers from biomass resources have attracted a lot of attention. Since these resources are renewable and therefore have a carbon-neutral biomass, such methods are expected to gain in particular importance in future. It is therefore a preferred feature of the present invention and the aspects described herein that where possible the monomers (especially the higher itaconate diesters such as DBI) as far as possible are biorenewable.
Preferably at least 30 wt-%, more preferably at least 50 wt-%, and especially 70 wt-% of the olefinically unsaturated monomers used to form the polymers of the invention are derived from at least one bio-renewable olefinically unsaturated monomer. Bio-renewable monomers may be obtained fully or in part from bio-renewable sources. Thus it is preferred to also measure the carbon-14 content to determine the biorenewability.
The content of carbon-14 (C-14) is indicative of the age of a bio-based material. It is known in the art that C-14, which has a half life of about 5,700 years, is found in bio-renewable materials but not in fossil fuels. Thus, “bio-renewable materials” refer to organic materials in which the carbon comes from non-fossil biological sources. Examples of bio-renewable materials include, but are not limited to, sugars, starches, corns, natural fibres, sugarcanes, beets, citrus fruits, woody plants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, and pullulan, and a combination thereof.
C-14 levels can be determined by measuring its decay process (disintegrations per minute per gram carbon or dpm/gC) through liquid scintillation counting. In one embodiment of the present invention, polymer A and or polymer B comprise at least about 1.5 dpm/gC (disintegrations per minute per gram carbon) of carbon-14, more preferably at least 2 dpm/gC, most preferably at least 2.5 dpm/gC, and especially at least 4 dpm/gC.
It is preferred that the higher itaconate diesters such as DBI are biorenewable, however other monomers used in the present invention may also be biorenewable. Examples of bio-renewable monomers include but are not limited to bio-based acrylics obtained by for example using bio-derived alcohols such as bio-butanol and include (meth)acrylic acid and alkyl(meth)acrylate, where alkyl is preferably selected from methyl, ethyl, butyl or 2-ethylhexyl.
Acrylic acid can be made from glycerol, as is disclosed by Arkema, or from lactic acid as described by U.S. Pat. No. 7,687,661. Methacrylic acid can be prepared from ethene, methanol and carbon monoxide (all bio-renewable), as disclosed by Lucite International Ltd.
Olefinically unsaturated bio-renewable monomers which may additionally provide a contribution to improved coating properties include α-methylene butyrolactone, α-methylene valerolactone, α-methylene γ-R 3 butyrolactone (R 3 can be an optionally substituted alkyl or optionally substituted aryl); itaconates such as dialkyl itaconates (including DBI) and monoalkyl itaconates, itaconic acid, itaconic anhydride, crotonic acid and alkyl esters thereof, citraconic acid and alkyl esters thereof, methylene malonic acid and its mono and dialkyl esters, citraconic anhydride, mesaconic acid and alkyl esters thereof.
Other non-acid functional, non-crosslinking monomers include diesters of itaconic acid. Preferred examples of such monomers include dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-i-propyl itaconate, di-n-butyl itaconate, di-i-butyl itaconate, and di-2-ethyl hexyl itaconate.
Another useful set of useful bio-renewable monomers include N—R 2 , α-methylene butyrolactam (R 2 can be an optionally substituted alkyl or optionally substituted aryl); N—R 2 , α-methylene γ-R 1 butyrolactam; N-alkyl itaconimids; itaconmonoamids; itacondiamids; ialkyl itaconamides, mono alkyl itaconamides; furfuryl(meth)acrylate; fatty acid functional (meth)acrylates such as DAPRO FX-522 from Elementis and Visiomer® MUMA from Evonik.
It is appreciated that certain features of the invention, which are for clarity described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely various features of the invention, which are for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
The object of the present invention is to solve some or all of the problems or disadvantages (such as identified throughout the application herein) with the prior art.
Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.
The term “comprising” as used herein will be understood to mean that the list following is non exhaustive and may or may not include any other additional suitable items, for example one or more further feature(s), component(s), ingredient(s) and/or substituent(s) as appropriate.
The terms ‘effective’, ‘acceptable’ ‘active’ and/or ‘suitable’ (for example with reference to any process, use, method, application, preparation, product, material, formulation, compound, monomer, oligomer, polymer precursor, and/or polymers described herein as appropriate) will be understood to refer to those features of the invention which if used in the correct manner provide the required properties to that which they are added and/or incorporated to be of utility as described herein. Such utility may be direct for example where a material has the required properties for the aforementioned uses and/or indirect for example where a material has use as a synthetic intermediate and/or diagnostic tool in preparing other materials of direct utility. As used herein these terms also denote that a functional group is compatible with producing effective, acceptable, active and/or suitable end products.
Preferred utility of the present invention comprises as a coating composition.
In the discussion of the invention herein, unless stated to the contrary, the disclosure of alternative values for the upper and lower limit of the permitted range of a parameter coupled with an indicated that one of said values is more preferred than the other, is to be construed as an implied statement that each intermediate value of said parameter, lying between the more preferred and less preferred of said alternatives is itself preferred to said less preferred value and also to each less preferred value and said intermediate value.
For all upper and/or lower boundaries of any parameters given herein, the boundary value is included in the value for each parameter. It will also be understood that all combinations of preferred and/or intermediate minimum and maximum boundary values of the parameters described herein in various embodiments of the invention may also be used to define alternative ranges for each parameter for various other embodiments and/or preferences of the invention whether or not the combination of such values has been specifically disclosed herein.
Thus for example a substance stated as present herein in an amount from 0 to “x” (e.g. in units of mass and/or weight %) is meant (unless the context clearly indicates otherwise) to encompass both of two alternatives, firstly a broader alternative that the substance may optionally not be present (when the amount is zero) or present only in an de-minimus amount below that can be detected. A second preferred alternative (denoted by a lower amount of zero in a range for amount of substance) indicates that the substance is present, and zero indicates that the lower amount is a very small trace amount for example any amount sufficient to be detected by suitable conventional analytical techniques and more preferably zero denotes that the lower limit of amount of substance is greater than or equal to 0.001 by weight % (calculated as described herein).
It will be understood that the total sum of any quantities expressed herein as percentages cannot (allowing for rounding errors) exceed 100%. For example the sum of all components of which the composition of the invention (or part(s) thereof) comprises may, when expressed as a weight (or other) percentage of the composition (or the same part(s) thereof), total 100% allowing for rounding errors. However where a list of components is non exhaustive the sum of the percentage for each of such components may be less than 100% to allow a certain percentage for additional amount(s) of any additional component(s) that may not be explicitly described herein.
In the present invention, unless the context clearly indicates otherwise, an amount of an ingredient stated to be present in the composition of the invention when expressed as a weight percentage, is calculated based on the total amount of monomers in the composition being equivalent to 100% (thus for example components (a)+(b)+(c)+(d) total 100%). For convenience certain non monomer ingredients (such as for example chain transfer agents (CTA)) which fall outside the definitions of any of components (a) to (d) may also be calculated as weight percentages based on total monomer (i.e. where the weight of total monomers alone is set at 100%). As the weight % of monomers (for example for components (a) to (d)) by definition total 100% it will be seen that using monomer based weight % values for the non-monomer ingredients (i.e. those components outside (a) to (d)) will mean the total percentages will exceed 100%. Thus amounts of non-monomer ingredients expressed as monomer based weight percentages can be considered as providing a ratio for the weight amounts for these ingredients with respect to the total weight of monomers which is used only as a reference for calculation rather than as a strict percentage. Further ingredients are not excluded from the composition when (a)+(b)+(c)+(d) total 100% and weight percentages based on total monomers should not be confused with weight percentages of the total composition.
The term “substantially” as used herein may refer to a quantity or entity to imply a large amount or proportion thereof. Where it is relevant in the context in which it is used “substantially” can be understood to mean quantitatively (in relation to whatever quantity or entity to which it refers in the context of the description) there comprises an proportion of at least 80%, preferably at least 85%, more preferably at least 90%, most preferably at least 95%, especially at least 98%, for example about 100% of the relevant whole. By analogy the term “substantially-free” may similarly denote that quantity or entity to which it refers comprises no more than 20%, preferably no more than 15%, more preferably no more than 10%, most preferably no more than 5%, especially no more than 2%, for example about 0% of the relevant whole.
The terms ‘optional substituent’ and/or ‘optionally substituted’ as used herein (unless followed by a list of other substituents) signifies the one or more of following groups (or substitution by these groups): carboxy, sulpho, formyl, hydroxy, amino, imino, nitrilo, mercapto, cyano, nitro, methyl, methoxy and/or combinations thereof. These optional groups include all chemically possible combinations in the same moiety of a plurality (preferably two) of the aforementioned groups (e.g. amino and sulphonyl if directly attached to each other represent a sulphamoyl group). Preferred optional substituents comprise: carboxy, sulpho, hydroxy, amino, mercapto, cyano, methyl, halo, trihalomethyl and/or methoxy.
The synonymous terms ‘organic substituent’ and “organic group” as used herein (also abbreviated herein to “organo”) denote any univalent or multivalent moiety (optionally attached to one or more other moieties) which comprises one or more carbon atoms and optionally one or more other heteroatoms. Organic groups may comprise organoheteryl groups (also known as organoelement groups) which comprise univalent groups containing carbon, which are thus organic, but which have their free valence at an atom other than carbon (for example organothio groups). Organic groups may alternatively or additionally comprise organyl groups which comprise any organic substituent group, regardless of functional type, having one free valence at a carbon atom. Organic groups may also comprise heterocyclyl groups which comprise univalent groups formed by removing a hydrogen atom from any ring atom of a heterocyclic compound: (a cyclic compound having as ring members atoms of at least two different elements, in this case one being carbon). Preferably the non carbon atoms in an organic group may be selected from: hydrogen, halo, phosphorus, nitrogen, oxygen, silicon and/or sulphur, more preferably from hydrogen, nitrogen, oxygen, phosphorus and/or sulphur.
Most preferred organic groups comprise one or more of the following carbon containing moieties: alkyl, alkoxy, alkanoyl, carboxy, carbonyl, formyl and/or combinations thereof; optionally in combination with one or more of the following heteroatom containing moieties: oxy, thio, sulphinyl, sulphonyl, amino, imino, nitrilo and/or combinations thereof. Organic groups include all chemically possible combinations in the same moiety of a plurality (preferably two) of the aforementioned carbon containing and/or heteroatom moieties (e.g. alkoxy and carbonyl if directly attached to each other represent an alkoxycarbonyl group).
The term ‘hydrocarbo group’ as used herein is a sub-set of a organic group and denotes any univalent or multivalent moiety (optionally attached to one or more other moieties) which consists of one or more hydrogen atoms and one or more carbon atoms and may comprise one or more saturated, unsaturated and/or aromatic moieties. Hydrocarbo groups may comprise one or more of the following groups. Hydrocarbyl groups comprise univalent groups formed by removing a hydrogen atom from a hydrocarbon (for example alkyl). Hydrocarbylene groups comprise divalent groups formed by removing two hydrogen atoms from a hydrocarbon, the free valences of which are not engaged in a double bond (for example alkylene). Hydrocarbylidene groups comprise divalent groups (which may be represented by “R 2 C═”) formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon, the free valences of which are engaged in a double bond (for example alkylidene). Hydrocarbylidyne groups comprise trivalent groups (which may be represented by “RC≡”), formed by removing three hydrogen atoms from the same carbon atom of a hydrocarbon the free valences of which are engaged in a triple bond (for example alkylidyne). Hydrocarbo groups may also comprise saturated carbon to carbon single bonds (e.g. in alkyl groups); unsaturated double and/or triple carbon to carbon bonds (e.g. in respectively alkenyl and alkynyl groups); aromatic groups (e.g. in aryl groups) and/or combinations thereof within the same moiety and where indicated may be substituted with other functional groups
The term ‘alkyl’ or its equivalent (e.g. ‘alk’) as used herein may be readily replaced, where appropriate and unless the context clearly indicates otherwise, by terms encompassing any other hydrocarbo group such as those described herein (e.g. comprising double bonds, triple bonds, aromatic moieties (such as respectively alkenyl, alkynyl and/or aryl) and/or combinations thereof (e.g. aralkyl) as well as any multivalent hydrocarbo species linking two or more moieties (such as bivalent hydrocarbylene radicals e.g. alkylene).
Any radical group or moiety mentioned herein (e.g. as a substituent) may be a multivalent or a monovalent radical unless otherwise stated or the context clearly indicates otherwise (e.g. a bivalent hydrocarbylene moiety linking two other moieties). However where indicated herein such monovalent or multivalent groups may still also comprise optional substituents. A group which comprises a chain of three or more atoms signifies a group in which the chain wholly or in part may be linear, branched and/or form a ring (including spiro and/or fused rings). The total number of certain atoms is specified for certain substituents for example C 1-N organo, signifies a organo moiety comprising from 1 to N carbon atoms. In any of the formulae herein if one or more substituents are not indicated as attached to any particular atom in a moiety (e.g. on a particular position along a chain and/or ring) the substituent may replace any H and/or may be located at any available position on the moiety which is chemically suitable and/or effective.
Preferably any of the organo groups listed herein comprise from 1 to 36 carbon atoms, more preferably from 1 to 18. It is particularly preferred that the number of carbon atoms in an organo group is from 1 to 12, especially from 1 to 10 inclusive, for example from 1 to 4 carbon atoms.
As used herein chemical terms (other than IUPAC names for specifically identified compounds) which comprise features which are given in parentheses—such as (alkyl)acrylate, (meth)acrylate and/or (co)polymer—denote that that part in parentheses is optional as the context dictates, so for example the term (meth)acrylate denotes both methacrylate and acrylate.
Certain moieties, species, groups, repeat units, compounds, oligomers, polymers, materials, mixtures, compositions and/or formulations which comprise and/or are used in some or all of the invention as described herein may exist as one or more different forms such as any of those in the following non exhaustive list: stereoisomers (such as enantiomers (e.g. E and/or Z forms), diastereoisomers and/or geometric isomers); tautomers (e.g. keto and/or enol forms), conformers, salts, zwitterions, complexes (such as chelates, clathrates, crown compounds, cyptands/cryptades, inclusion compounds, intercalation compounds, interstitial compounds, ligand complexes, organometallic complexes, non-stoichiometric complexes, π-adducts, solvates and/or hydrates); isotopically substituted forms, polymeric configurations [such as homo or copolymers, random, graft and/or block polymers, linear and/or branched polymers (e.g. star and/or side branched), cross-linked and/or networked polymers, polymers obtainable from di and/or tri-valent repeat units, dendrimers, polymers of different tacticity (e.g. isotactic, syndiotactic or atactic polymers)]; polymorphs (such as interstitial forms, crystalline forms and/or amorphous forms), different phases, solid solutions; and/or combinations thereof and/or mixtures thereof where possible. The present invention comprises and/or uses all such forms which are effective as defined herein.
Polymers of the present invention may be prepared by one or more suitable polymer precursor(s) which may be organic and/or inorganic and comprise any suitable (co)monomer(s), (co)polymer(s) [including homopolymer(s)] and mixtures thereof which comprise moieties which are capable of forming a bond with the or each polymer precursor(s) to provide chain extension and/or cross-linking with another of the or each polymer precursor(s) via direct bond(s) as indicated herein.
Polymer precursors of the invention may comprise one or more monomer(s), oligomer(s), polymer(s); mixtures thereof and/or combinations thereof which have suitable polymerisable functionality. It will be understood that unless the context dictates otherwise term monomer as used herein encompasses the term polymer precursor and does not necessarily exclude monomers that may themselves be polymeric and/or oligomeric in character.
A monomer is a substantially monodisperse compound of a low molecular weight (for example less than one thousand daltons) which is capable of being polymerised.
A polymer is a polydisperse mixture of macromolecules of large molecular weight (for example many thousands of daltons) prepared by a polymerisation method, where the macromolecules comprises the multiple repetition of smaller units (which may themselves be monomers, oligomers and/or polymers) and where (unless properties are critically dependent on fine details of the molecular structure) the addition or removal one or a few of the units has a negligible effect on the properties of the macromolecule.
A oligomer is a polydisperse mixture of molecules having an intermediate molecular weight between a monomer and polymer, the molecules comprising a small plurality of monomer units the removal of one or a few of which would significantly vary the properties of the molecule.
Depending on the context the term polymer may or may not encompass oligomer.
The polymer precursor of and/or used in the invention may be prepared by direct synthesis or (if the polymeric precursor is itself polymeric) by polymerisation. If a polymerisable polymer is itself used as a polymer precursor of and/or used in the invention it is preferred that such a polymer precursor has a low polydispersity, more preferably is substantially monodisperse, to minimise the side reactions, number of by-products and/or polydispersity in any polymeric material formed from this polymer precursor. The polymer precursor(s) may be substantially un-reactive at normal temperatures and pressures.
Except where indicated herein polymers and/or polymeric polymer precursors of and/or used in the invention can be (co)polymerised by any suitable means of polymerisation well known to those skilled in the art. Examples of suitable methods comprise: thermal initiation; chemical initiation by adding suitable agents; catalysis; and/or initiation using an optional initiator followed by irradiation, for example with electromagnetic radiation (photo-chemical initiation) at a suitable wavelength such as UV; and/or with other types of radiation such as electron beams, alpha particles, neutrons and/or other particles.
The substituents on the repeating unit of a polymer and/or oligomer may be selected to improve the compatibility of the materials with the polymers and/or resins in which they may be formulated and/or incorporated for the uses described herein. Thus the size and length of the substituents may be selected to optimise the physical entanglement or interlocation with the resin or they may or may not comprise other reactive entities capable of chemically reacting and/or cross linking with such other resins as appropriate.
Another aspect of the invention broadly provides a coating composition comprising the polymers and/or beads of the present invention and/or as described herein.
A further aspect of the invention provides a coating obtained or obtainable from a coating composition of the present invention.
A yet other aspect of the invention broadly provides a substrate and/or article having coated thereon an (optionally cured) coating composition of the present invention.
A yet further aspect of the invention broadly provides a method of using polymers of the present invention and/or as described herein to prepare a coating composition.
A still further aspect of the invention broadly provides a method for preparing a coated substrate and/or article comprising the steps of applying a coating composition of the present invention to the substrate and/or article and optionally curing said composition in situ to form a cured coating thereon. The curing may be by any suitable means, such as thermally, by radiation and/or by use of a cross-linker.
Preferred coating compositions are solvent coating compositions or aqueous coating compositions, more preferably are aqueous coating compositions.
Optionally aqueous coating compositions may also comprise a co-solvent. A co-solvent, as is well known in the coating art, is an organic solvent employed in an aqueous composition to ameliorate the drying characteristics thereof, and in particular to lower its minimum film forming temperature. The co-solvent may be solvent incorporated or used during preparation of polymers of the invention or may have been added during formulation of the aqueous composition.
The compositions of the invention are particularly useful as or for providing the principle component of coating formulations (i.e. composition intended for application to a substrate without further treatment or additions thereto) such as protective or decorative coating compositions (for example paint, lacquer or varnish) wherein an initially prepared composition optionally may be further diluted with water and/or organic solvents, and/or combined with further ingredients or may be in more concentrated form by optional evaporation of water and/or organic components of the liquid medium of an initially prepared composition.
The compositions of the invention may be used in various applications and for such purposes may be optionally further combined or formulated with other additives and/or components, such as defoamers, rheology control agents, thickeners, dispersing and/or stabilizing agents (usually surfactants and/or emulsifiers), wetting agents, fillers, extenders, fungicides, bacteriocides, coalescing and wetting solvents or co-solvents (although solvents are not normally required), plasticisers, anti-freeze agents, waxes, colorants, pigments, dyes, heat stabilisers, levelling agents, anti-cratering agents, fillers, sedimentation inhibitors, UV absorbers, antioxidants, reactive diluents, neutralising agents, adhesion promoters and/or any suitable mixtures thereof.
The aforementioned additives and/or components and the like may be introduced at any stage of the production process or subsequently. It is possible to include fire retardants (such as antimony oxide) to enhance fire retardant properties.
The compositions of the invention may also be blended with other polymers such as vinyl polymers, alkyds (saturated or unsaturated), polyesters and or polyurethanes.
The coating composition of the invention may be applied to a variety of substrates including wood, board, metals, stone, concrete, glass, cloth, leather, paper, plastics, foam and the like, by any conventional method including brushing, dipping, flow coating, spraying, and the like. The coating composition of the invention may also be used to coat the interior and/or exterior surfaces of three-dimensional articles. The coating compositions of the invention may also be used, appropriately formulated if necessary, for the provision of films, polishes, varnishes, lacquers, paints, inks and adhesives. However, they are particularly useful and suitable for providing the basis of protective coatings for substrates that comprise wood (e.g. wooden floors), plastics, polymeric materials, paper and/or metal.
The carrier medium may be removed from the compositions of the invention once they have been applied to a substrate by being allowed to dry naturally at ambient temperature, or the drying process may be accelerated by heat. Crosslinking can be developed by allowing to stand for a prolonged period at ambient temperature (several days) or by heating at an elevated temperature (e.g. 50° C.) for a much shorter period of time.
In addition, the present invention relates to the use of the present organic particles/beads (optionally nano and/or micro sized) in any of the following uses:
As particles for encapsulating particles of a colorant composition, and to colorant compositions comprising the organic nano particles and/or micro particles of the present invention. Colorant denotes any coloured material (including materials which absorb or reflect UV or IR radiation instead of or in addition to visible light) and includes dyes and pigments. Dyes are generally soluble in the medium to which they are added and are typically (but not exclusively) organic liquids. Pigments are generally insoluble in the medium to which they are added and typically (but not exclusively) inorganic solids. Preferably the colorant is a dye. Encapsulating of particles of colorant composition may take place suspending particles of colorant composition in the solution prior to emulsification or during emulsification, so that particles of colorant composition is encapsulated in the nano particles during curing of the solution. Alternatively, the particles of colorant composition may be added after the curing reaction, so that the encapsulation takes place during the optional agglomeration process.
A non limiting list of other end uses for the beads of the invention include:
Use in binders for a toner composition, and toner compositions may comprise the particles of the present invention;
As additives for sheet moulded compounds (also denoted herein as SMC), where the presence of the particles (particularly spray dried particles) leads to lower density products;
As plastic pigment, particularly for coatings, such as paper coatings, where the presence of the particles may provide high gloss or tuneable gloss properties of the product;
As fillers in composite materials and particularly in concrete, where for example the use of the particles as micro fillers may increase strength, lower porosity, reduce density and/or prevent water penetration into the structure;
As filler for coatings, where for example the particles may provide anti blocking properties to the coating, increase scratch resistance, lower abrasion, increase drying speed, reduce the required amount of solvent, and reduce shrink;
As filler for waxes, where for example the particles may provide a lubricating effect, reduce weight, reduce abrasion and/or act as a high temperature filler;
Mono disperse particles of the invention may be used for spacers for example in display applications;
As hybrid colorant, where for example a colorant (preferably pigment) particle may interact with the particles of the invention in several ways. In one option pigment particles may be dispersed in the emulsion prior to curing of the resin and monomer. The pigment particles (which are usually hydrophobic) will tend to migrate inside the hydrophobic droplets of the solution. Curing the solution will form particles in which a pigment core is encapsulated within a shell of cured polymer. In another option the pigment particles may be co agglomerated with the nano particles to form micro particles. Both methods can produce pigments which are dispersible in water and which can be either partially accessible or inaccessible for direct contact with ambient atmosphere or other materials.
In adhesives, where for example the particles may be used as a filler or as a shrink reducing agent, since the particles will be inert during curing of the adhesive. As the particles will be strongly connected to the adhesive they will have no detrimental effect on adhesive strength.
As encapsulating agent for active ingredients that may be added to the emulsion prior to curing and remain in the particle upon curing. The resulting particles, which contain the active ingredient, are more easily dispersible and the active ingredient is protected. Examples of active ingredients are dyes and UV blockers.
As an ingredient in compositions suitable for use in personal care and/or as topical medicaments.
It will be appreciated that some of the above uses may overlap.
Depending on the desired properties of the topical medicament and/or personal care composition, particles of the invention (organic nano particles and/or micro particles) may be present in an amount from 0.001 to 99%, preferably 0.1 to 80%, more preferably 0.5 to 50%, most preferably 1 to 20% by weight of the total composition. Any suitable, conventional ingredients suitable for such applications may be used, such as those well known to a skilled formulator of such compositions.
Topical medicament indicates a composition which is formulated for the delivery of a therapeutically active agent to, or via, the skin. A wide variety of active agents may be delivered using such formulations, including agents that are intended for treatment of the skin, such as anti acne agents, and systemically active agents for which the skin is merely the route of administration, rather than the site of action.
Non limiting examples of personal care compositions (which may or may not be applied topically) include: cosmetic compositions, hair care products, insect repellents, oral hygiene compositions, self tanning products, sunscreens, toiletry compositions, mixtures thereof, and/or combinations in the same composition.
Cosmetic composition indicates a composition that may be used on the body to modify its appearance. Non limiting examples of such compositions may include: after sun compositions, blushers, colour cosmetics, eye shadows, face creams, face masks, foundations, lip balms, lipsticks, moisturisers, powder formulations, temporary tattoos and other forms of body art; and toner cleansers. Cosmetic compositions may be applied as any suitable formulation type, non limiting examples of which include: creams, dispersions, emulsions (such as water in oil (w/o), oil in water (o/w), water in oil in water (w/o/w) and oil in water in oil (o/w/o), although emulsions where the continuous phase is aqueous such as o/w and w/o/w are preferred), gels, lotions, milks, ointments, pastes, powders, roll on, salves, serums, solutions, spray, sticks and suspensions.
Hair care composition indicates a composition that may be used on animal hair, preferably on human hair, most preferably on the human head. Non limiting examples of such a composition may include suitable: conditioners, creams, foams, gels, hair dyes, hair colorants, hair styling products, hot oil treatments, lotions, mascaras, masks, mousses, muds, rinses, shampoos, styling sprays and/or waxes.
Oral hygiene composition indicates a composition that may be suitable for use in oral hygiene, dental treatment and/or be otherwise applied to the buccal and/or oral cavity. Non limiting examples of such a composition may include suitable: chewing gums, dentifrices, denture cleansing formulations, flosses, glass ionomer cements, lozenges, mouth sprays, mouthwashes, tooth paints, tooth pastes and/or tooth powders.
Sunscreen indicates a composition that may be used on the body to provide protection against the sun's rays or other UV sources. Non limiting examples of such compositions may also include: sun blockers and/or tanning lotions.
Toiletry composition indicates a composition that may be used on the body to clean, scour, wash, perfume and/or reduce odour. Non limiting examples of such a composition may include suitable: anti microbial compositions, bath products (e.g. bath foams and bath salts), deodorants, detergents, perfumes, soaps and/or shower gels
Many other variations embodiments of the invention will be apparent to those skilled in the art and such variations are contemplated within the broad scope of the present invention.
Further aspects of the invention and preferred features thereof are given in the claims herein.
Tests
Minimum Film Forming Temperature
The minimum film forming temperature (MFFT) of a dispersion as used herein is the temperature where the dispersion forms a smooth and crack free coating or film using DIN 53787 and when applied using a Sheen MFFT bar SS3000.
Koenig Hardness
Koenig hardness as used herein is a standard measure of hardness, being a determination of how the viscoelastic properties of a film formed from the dispersion slows down a swinging motion deforming the surface of the film, and is measured according to DIN 53157 NEN5319.
Glass Transition Temperature (Tg)
As is well known, the glass transition temperature of a polymer is the temperature at which it changes from a glassy, brittle state to a plastic, rubbery state. The glass transition temperatures may be determined experimentally using Differential Scanning calorimetry (DSC), taking the peak of the derivative curve as Tg, or calculated from the Fox equation. Thus the Tg, in Kelvin, of a copolymer having “n” copolymerised comonomers is given by the weight fractions W of each comonomer type and the Tgs of the homopolymers (in Kelvin) derived from each comonomer according to the equation:





1
Tg

=



W
1


Tg
1


+


W
2


Tg
2


+

…







W
n


Tg
n








The calculated Tg in Kelvin may be readily converted to ° C.
Solids Content
The solids content of an aqueous dispersion of the invention is usually within the range of from about 20 to 65 wt-% on a total weight basis, more usually 30 to 55 wt-%. Solids content can, if desired, be adjusted by adding water or removing water (e.g. by distillation or ultrafiltration).
pH Value
The pH value of the dispersion of the invention can be from 2 to 10 and mostly is from 6 to 9.5.
Blocking
Block Resistance Measurement [Includes Blocking and Early Blocking]:
Step 1: Blocking:
A 100 micron wet film of the aqueous emulsion of the invention to which 10% butyldiglycol is added is cast on to a paper substrate and dried for 16 hours at 52° C.
Step 1: Early Blocking:
A 250 micron wet film of the aqueous emulsion of the invention to which 10% butyldiglycol was added, is cast on to a paper substrate and dried for 24 hours at room temperature.
Step 2: Blocking and Early Blocking:
After cooling down to room temperature two pieces of coated film are placed with the coated side against each other under a load of 1 Kg/cm.sup.2 for 4 hours at 52° C. After this time interval the load on the samples is removed and the samples are left to cool down to room temperature (22+−2° C.). When the two coatings can be removed from each other without any damage to the film (do not stick) the block resistance is very good and assessed as a 5. When they however completely stick together, block resistance is very bad and assessed as a 0.
Gas Chromatography Mass Spectrometry (GCMS)
to confirm polymerisation is substantially complete the content of free itaconate ester monomers content can be determined by GCMS. The GCMS analyses were performed on a Trace GC-DSQ MS (Interscience, Breda, the Netherlands) equipped with a CTC combi Pal robotic autosampler for head space has been used. The carrier gas was Helium and a CP Sil 5 low bleed/MS, 25 m×0.25 mm i.d., 1.0 μm (CP nr. 7862) column has been used.
The GC-oven was programmed from 50° C. (5 min) followed by different sequential temperature ramps of 5° C./min to 70° C. (0 min), 15° C./min to 220° C. (0 min), and ending with 25° C./min to 280° C. (10 min). A continuous Helium flow of 1.2 ml/min was used. A hot split injection at 300° C. was performed on a programmed temperature vaporizer (PTV). The injection volume was 1 μl. The MS transfer line and ion source were both kept at 250° C. The samples were measured with single ion monitoring (SIM). For the specific case of dibutyl itaconate (DBI) the masses 127.0 and 59.0 Da were used, for the internal standard (iso butyl acrylate) the masses 55.0 and 73.0 were applied. The sample solutions were approximately 500 mg in 3 ml of internal standard solution (iso butyl acrylate in acetone). The calibration was performed with 5 different concentration levels from 0 to 500 ppm. The calculation was performed using Microsoft Excel with a linear calibration curve.
Molecular Weight
Unless the context clearly dictates otherwise the term molecular weight of a polymer or oligomer as used herein denotes weight average molecular weight (also denoted as M w ). M w may be measured by any suitable conventional method for example by Gas Phase Chromatography (GPC—performed similarly to the GCMS method described above) and/or by the SEC method described below. GPC method is preferred
Determination of Molecular Weight of a Polymer Using SEC
The molecular weight of a polymer may also be determined using Size Exclusion Chromatography (SEC) with tetrahydrofuran as the eluent or with 1,1,1,3,3,3 hexafluoro isopropanol as the eluent.
1) Tetrahydrofuran
The SEC analyses were performed on an Alliance Separation Module (Waters 2690), including a pump, auto injector, degasser, and column oven. The eluent was tetrahydrofuran (THF) with the addition of 1.0 vol % acetic acid. The injection volume was 150 μl. The flow was established at 1.0 ml/min. Three PL MixedB (Polymer Laboratories) with a guard column (3 μm PL) were applied at a temperature of 40° C. The detection was performed with a differential refractive index detector (Waters 410). The sample solutions were prepared with a concentration of 20 mg solids in 8 ml THF (+1 vol % acetic acid), and the samples were dissolved for a period of 24 hours. Calibration is performed with eight polystyrene standards (polymer standard services), ranging from 500 to 4,000,000 g/mol. The calculation was performed with Millennium 32 software (Waters) with a third order calibration curve. The obtained molar masses are polystyrene equivalent molar masses (g/mol).
2) 1,1,1,3,3,3 Hexafluoro Isopropanol
The SEC analyses were performed on a Waters Alliance 2695 (pump, degasser and autosampler) with a Shodex RI-101 differential refractive index detector and Shimadzu CTO-20AC column oven. The eluent was 1,1,1,3,3,3 hexafluoro isopropanol (HFIP) with the addition of 0.2M potassium trifluoro acetate (KTFA). The injection volume was 50 μl. The flow was established at 0.8 ml/min. Two PSS PFG Linear XL columns (Polymer Standards Service) with a guard column (PFG PSS) were applied at a temperature of 40° C. The detection was performed with a differential refractive index detector. The sample solutions were prepared with a concentration of 5 mg solids in 2 ml HFIP (+0.2M KTFA), and the samples were dissolved for a period of 24 hours. Calibration is performed with eleven polymethyl methacrylate standards (polymer standard services), ranging from 500 to 2,000,000 g/mol. The calculation was performed with Empower Pro software (Waters) with a third order calibration curve. The molar mass distribution is obtained via conventional calibration and the molar masses are polymethyl methacrylate equivalent molar masses (g/mol).
Standard Conditions
As used herein, unless the context indicates otherwise, standard conditions (e.g. for drying a film) means a relative humidity of 50%±5%, ambient temperature (which denotes herein a temperature of 23° C.±2°) and an air flow of (less than or equal to) 0.1 m/s.
The following examples are provided to further illustrate the processes and compositions of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way. Unless otherwise specified all parts, percentages, and ratios are on a weight basis. The prefix C before an example indicates that it is comparative.
Various registered trademarks, other designations and/or abbreviations are used herein to denote some of ingredients used to prepare polymers and compositions of the invention. These are identified below by chemical name and/or trade-name and optionally their manufacturer or supplier from whom they are available commercially. However where a chemical name and/or supplier of a material described herein is not given it may easily be found for example in reference literature well known to those skilled in the art: such as: ‘McCutcheon's Emulsifiers and Detergents’, Rock Road, Glen Rock, N.J. 07452-1700, USA, 1997 and/or Hawley's Condensed Chemical Dictionary (14th Edition) by Lewis, Richard J., Sr.; John Wiley & Sons.
In the examples the following abbreviations/monomers may be used:
AMBN is 2,2′-Azodi(2-methylbutyronitrile).

AMPS denotes 2-acrylamido-2-methylpropane sulfonic acid

BA=n-butyl acrylate (may be bioenewable)

BMA=n-butyl methacrylate (may be prepared using bio-renewable alkanols)

CEA denotes beta carboxy ethyl acrylate

DBI denotes di(n-butyl) itaconate (also known as dibutyl 2-methylidenebutanedioate)

(may be bio-renewable)

DMI=dimethyl itaconate (may be bio-renewable)

HFIP denotes hexafluoro isopropanol

KTFA denotes potassium trifluoro actetate

MAA=methacrylic acid (may be biorenewable)

MMA=methyl methacrylate (may be prepared using bio-renewable alkanols)

STY denotes styrene;



EXAMPLES
Example 1
poly(IAn-co-BMA)-block-polyBA—RITP
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 50 parts of acetonitrile, 20.56 parts of itaconic anhydride, 26.17 parts of butyl methacrylate, 0.94 parts of iodium, and 2.34 parts of AMBN. A mild nitrogen flow was started and the reactor contents are heated to 80° C. After stirring for 4 hours at 80° C., a second shot of 46.73 parts of butyl acrylate in 41.44 parts of acetonitrile is added and the mixture is allowed to stir for another 3 hours after which the reactor contents are cooled back to room temperature.
The solids content of the polymer solution is 51%.
Example 2
poly(IAn-co-BMA)/polyBA—CCTP
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 50 parts of acetonitrile, 21.56 parts of it aconic anhydride, 27.45 parts of butyl methacrylate, 0.0098 parts of cobalt catalyst according to EP788518, and 0.98 parts of AMBN. A mild nitrogen flow was started and the reactor contents are heated to 80° C. After stirring for 4 hours at 80° C., a solution of 49.01 parts of butyl acrylate, and 0.98 parts of butyl acrylate in 41.44 parts of acetonitrile is added over a period of 2 hours after which the mixture is allowed to stir for another 2 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution is 52.5%.
Example 3
poly(IAn-co-MMA)/polyBA—CCTP
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 50 parts of acetonitrile, 26 parts of itaconic anhydride, 23 parts of butyl methacrylate, 0.0098 parts of cobalt catalyst according to EP788518, and 0.98 parts of AMBN. A mild nitrogen flow was started and the reactor contents are heated to 80° C. After stirring for 4 hours at 80° C., a solution of 49.01 parts of butyl acrylate, and 0.98 parts of butyl acrylate in 41.44 parts of acetonitrile is added over a period of 2 hours after which the mixture is allowed to stir for another 2 hours. Next, the reactor contents are cooled back to room temperature.
The solids content of the polymer solution is 52.5%.
Example 4
poly(IAn-co-EA-co-DAAM)-block-polyBA—RAFT
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 33.05 parts of methyl ethyl ketone, and 2.56 parts of Rhodixan A1. This mixture was stirred at room temperature while leading through nitrogen gas. Next the mixture was heated to 75° C. At reaction temperature, 10% of a first monomer feed, consisting of 8.93 parts of methyl ethyl ketone, 14.61 parts of itaconic anhydride, 9.84 parts of ethyl acrylate and 5.36 parts of diacetone acrylamide, was added, followed by a mixture of 0.30 parts of AMBN and 5.06 parts of methyl ethyl ketone. The reaction mixture was stirred at 75° C. for 15 minutes. The remainder of the first monomer feed was added over a period of 1 hour at 75° C. After a waiting period of 4 hours, a second monomer feed consisting of 8.93 parts of methyl ethyl ketone and 29.82 parts of butyl acrylate was added over a period of 1 hour at 75° C. Next, the reaction mixture was stirred at 75° C. for another 6 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution was adjusted to 50.0% using methyl ethyl ketone. The number average molecular weight of the block copolymer was 3.3 kg/mole, while the weight average molecular weight was 4.3 kg/mole.
Example 5
poly(IAn-co-DAAM)-block-polyBA—RAFT
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 33.05 parts of methyl ethyl ketone, and 2.56 parts of Rhodixan A1. This mixture was stirred at room temperature while leading through nitrogen gas. Next the mixture was heated to 75° C. At reaction temperature, 10% of a first monomer feed, consisting of 8.93 parts of methyl ethyl ketone, 24.45 parts of itaconic anhydride, and 5.37 parts of diacetone acrylamide, was added, followed by a mixture of 0.30 parts of AMBN and 5.06 parts of methyl ethyl ketone. The reaction mixture was stirred at 75° C. for 15 minutes. The remainder of the first monomer feed was added over a period of 1 hour at 75° C. After a waiting period of 4 hours, a second monomer feed consisting of 8.93 parts of methyl ethyl ketone and 29.82 parts of butyl acrylate was added over a period of 1 hour at 75° C. Next, the reaction mixture was stirred at 75° C. for another 6 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution was adjusted to 50.0% using methyl ethyl ketone. The number average molecular weight of the block copolymer was 3.4 kg/mole, while the weight average molecular weight was 4.5 kg/mole.
Example 6
poly(EA-co-DBI-co-AA)-block-BA—RAFT
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 33.05 parts of methyl ethyl ketone, and 2.56 parts of Rhodixan A1. This mixture was stirred at room temperature while leading through nitrogen gas. Next the mixture was heated to 75° C. At reaction temperature, 10% of a first monomer feed, consisting of 8.93 parts of methyl ethyl ketone, 7.89 parts of ethyl acrylate, 19.09 parts of dibutyl itaconate, and 2.84 parts of acrylic acid was added, followed by a mixture of 0.30 parts of AMBN and 5.06 parts of methyl ethyl ketone. The reaction mixture was stirred at 75° C. for 15 minutes. The remainder of the first monomer feed was added over a period of 1 hour at 75° C. After a waiting period of 4 hours, a second monomer feed consisting of 8.93 parts of methyl ethyl ketone and 29.82 parts of butyl acrylate was added over a period of 1 hour at 75° C. Next, the reaction mixture was stirred at 75° C. for another 6 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution was adjusted to 50.0% using methyl ethyl ketone. The number average molecular weight of the block copolymer was 3.2 kg/mole, while the weight average molecular weight was 4.3 kg/mole.
Example 7
poly(DMI-co-MAA-co-MA)-block-polyBA—RAFT
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 33.05 parts of methyl ethyl ketone, and 2.56 parts of Rhodixan A1. This mixture was stirred at room temperature while leading through nitrogen gas. Next the mixture was heated to 75° C. At reaction temperature, 10% of a first monomer feed, consisting of 8.93 parts of methyl ethyl ketone, 20.54 parts of dimethyl itaconate, 4.65 parts of methacrylic acid, and 4.62 parts of butyl acrylate was added, followed by a mixture of 0.30 parts of AMBN and 5.06 parts of methyl ethyl ketone. The reaction mixture was stirred at 75° C. for 15 minutes. The remainder of the first monomer feed was added over a period of 1 hour at 75° C. After a waiting period of 4 hours, a second monomer feed consisting of 8.93 parts of methyl ethyl ketone and 29.82 parts of butyl acrylate was added over a period of 1 hour at 75° C. Next, the reaction mixture was stirred at 75° C. for another 6 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution was adjusted to 50.0% using methyl ethyl ketone. The number average molecular weight of the block copolymer was 3.2 kg/mole, while the weight average molecular weight was 4.3 kg/mole.
Example 8
poly(AA-co-DBI-co-EA-co-DAAM)-block-polyBA—RAFT
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 33.05 parts of methyl ethyl ketone, and 2.56 parts of Rhodixan A1. This mixture was stirred at room temperature while leading through nitrogen gas. Next the mixture was heated to 75° C. At reaction temperature, 10% of a first monomer feed, consisting of 8.93 parts of methyl ethyl ketone, 3.16 parts of acrylic acid, 17.68 parts of dibutyl itaconate, 4.95 parts of ethyl acrylate, and 4.03 parts of diacetone acrylamide was added, followed by a mixture of 0.30 parts of AMBN and 5.06 parts of methyl ethyl ketone. The reaction mixture was stirred at 75° C. for 15 minutes. The remainder of the first monomer feed was added over a period of 1 hour at 75° C. After a waiting period of 4 hours, a second monomer feed consisting of 8.93 parts of methyl ethyl ketone and 29.82 parts of butyl acrylate was added over a period of 1 hour at 75° C. Next, the reaction mixture was stirred at 75° C. for another 6 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution was adjusted to 50.0% using methyl ethyl ketone. The number average molecular weight of the block copolymer was 3.1 kg/mole, while the weight average molecular weight was 4.4 kg/mole.
Example 9
poly(AA-co-DBI-co-EA)-block-poly(BA-co-BMA)—RAFT
To a round-bottomed flask equipped with a condenser, thermometer and mechanical stirrer, were added 33.05 parts of methyl ethyl ketone, and 2.56 parts of Rhodixan A1. This mixture was stirred at room temperature while leading through nitrogen gas. Next the mixture was heated to 75° C. At reaction temperature, 10% of a first monomer feed, consisting of 8.93 parts of methyl ethyl ketone, 3.66 parts of acrylic acid, 15.47 parts of dibutyl itaconate, and 10.68 parts of ethyl acrylate was added, followed by a mixture of 0.30 parts of AMBN and 5.06 parts of methyl ethyl ketone. The reaction mixture was stirred at 75° C. for 15 minutes. The remainder of the first monomer feed was added over a period of 1 hour at 75° C. After a waiting period of 4 hours, a second monomer feed consisting of 8.93 parts of methyl ethyl ketone and 23.86 parts of butyl acrylate and 5.96 parts of butyl methacrylate was added over a period of 1 hour at 75° C. Next, the reaction mixture was stirred at 75° C. for another 6 hours. Next, the reactor contents are cooled back to room temperature. The solids content of the polymer solution was adjusted to 50.0% using methyl ethyl ketone. The number average molecular weight of the block copolymer was 3.3 kg/mole, while the weight average molecular weight was 4.3 kg/mole.