1.ApplicationNumber: US-47400454-A
1.PublishNumber: US-2920063-A
2.Date Publish: 19600105
3.Inventor: MELAMED SIDNEY

4.Inventor Harmonized: SIDNEY MELAMED()

5.Country: US
6.Claims:

7.Description:
(en)AROMATIC ACID AMIDES F AMINOALKYL VINYL ETHERS AND THEIR-POLYMERS Sidney Melamed, Philadelphia, Pa., assignor to Rohm & Haas Company, Philadelphia, Pa a corporation of I Delaware I v I No Drawing. Application December 8, 1954 Serial No. 474,004 I a 16 Claims. c1.'z6,0-ss.5
I t I CH2=ICHOANRCOR where A is a'straight-ch'ain or branched-chain alkylene group having 2 to -18 carbon atoms of which at leasttwo in a chain separate the adjoining nitrogen and ether oxygen atoms;
R is H, phenyl, tolyl benzyl, cyclohexyl, or an .alkyl group having 1 to 18 carbon atoms;
R is phenyl, tolyhxylyl or these groups in which the benzene ring is substituted with halogen (especially chlorine), nitro groups, or hydroxyl groups. I
In general, the new compounds of the present invention may be prepared by reacting an amine of Formula II:
II 'CH ='CHOANHR I in which the symbols Aand .R have the same meaning as given above with'an ester or chloride of such aromatic acids as: benzoic, p-bromobenzoic, o-chlorobenzoic, pchlorobenzoic, 2,4-dichlorobenzoic, p-nitrobenzoic, o-ni- :trobenzoic, salicylic: (o-hydroxybenzoic) Zm-hydroxyben- :zoic, p-hydroxybenzoic, protocatechuic 3,4-dihydroxybenzoic, pyrocatechuic (-2,3-,dihydroxybenzoic), vanillic =(Z-hydroxy-3-rnethoxy-benzoic),, ,B-resorcylic (2,4-dihy- -droxybenzoic), a-resorcylio(3,5-dihydroxybenzoic), 'y-
resorcylic- (2,6-dihydroxybenzoic), gallic (3,4,5 -trihy-..
droxybenzoic), m-toluic, o-toluic, p-toluic, 2,3-xylic, 3,4-
xylic, 2,6-xylic, 2,4-xylic,tand-v2,5-xylic. 1
Representative amines of Formula II include the following: a
'CH CHOCH(Ci5H33)CH NHg I I The vinyl aminoalkyl ether may have anN substituent tmh rithanzhrd os aand;thepreferredmethyl .gioup,
cyclohexyl.
'dioxane.
such as ethyl, butyl, phenyl, r'nethylphenyl, benzyl, cyclohexyl, and so on, typical compounds then being C./9 mm.), 'CHZ=CHOCH2CHZNHC4HQ, (distilling at (distilling at 72-73 C./ 120 mm.) I
CH =CHOCH CH NHCH C H and CH =CHOCH CH NHC H in which C H is When the production of the new monomeric amides is accomplished by reaction of an ester with a vinyl ether of Formula II, the reaction may be effected in the presence of an alkali metal alkoxide such as sodium methoxide in an amount of 1 to 10%, preferably about 5%, on
the weight of the reactants. However, the presence of this alkoxide is not essential. The reaction may be'effected in the presence of a solvent, preferably in an alcohol corresponding to'the alkyl group'of the ester that is reacted. Thus when a methyl ester is used, reaction in methanol is preferred. While the reaction may be effected at room temperature, shorter times are involved-if higher temperatures are employed. 'For example, the reaction mixture maybe refluxed at to 80C. -or higher for 4 to 8 hours. The product may be obtained-by stripping off solvent or-by adding a nonsolvent to efiect precipitation of the product. It may be purified-by recrystallization from suitable solvents, if desired. a
When the chloride of the aromatic acid is reacted with the vinyl ether of Formula II, the reaction may be carried out in the presence of excess amine, such as two or more moles of amine to one mole of the acid chloride, or in the presence 'of an inorganic alkaline material such as sodium or potassium hydroxide or carbonate as an acceptor for the hydrogen chloride liberated by the reactions The reaction is preferably carried out in a'solvent, such as benzene, ether, acetonitrile, chloroform or When inorganic bases are employed as acid acceptors, mixtures, such as benzene or chloroform and water, may be preferably employed. The temperatures of reaction may vary widely but are preferably kept low, such asfrom 'l0 to 25 C., for a period of 1 to 4 hours. When the substituent R on the'nitrogen atom is other than hydrogen, the use. ofthe acidchloride as a reactant is preferred.
v The monomeric compounds of-the present invention, other than those derived from aromatic acids containing hydroxyl or nitro groups in. the benzene nucleus, are readily polymerized and producehomopolymers as well as copolymers having a wide range of molecular weights x including average molecular weights of 5000 to 50,000 or lysts or initiators of the acyclic azo type. In such commore. Theyvmay be polymerized in the presence of catapound the N=N group is attached to aliphatic carbon atoms,'at least one of which is tertiary. Typical azo carbons bonded. to the tertiary carbon atoms has its re- .maining valences satisfied by at least one element from the class consisting of oxygen and nitrogen; Polymerization may be effected in bulk, in'solution, or in emulsion systems. To effect polymerization the amidoalkyl vinyl ether and the acyclic azo catalyst are mixed directly or in the presence of an inert solvent and the mixture is maintained between 60 and C. until the desired extent 'of polymerizationis attained; Solvents that may asaopea be used in polymerization include methanol, ethanol, iso propanol, butanol, dimethylformamide, dimethylacetamide, toluene, benzene, xylene, and so on. The amount of catalyst may be varied from about 0.1 toabout 5% of the 'weightof the monomers. The polymerization is best carried outin an inert atmosphere, such as nitrogen gas.
For polymerization in solution, concentrations of monomer from about 50 to 90% are suitable. The course of polymerization/maybe readily followed from the increase in viscosity of the solution. The catalyst may be added in increments if desiredwith or'without additional solvent.
For bulkyp olymerization, the preferred temperatures are from about 70 to 80 C. and the optimum proportion of catalyst is from 0.3% to 3%: of. the monomer weight.
The oopolymerization may also berefiected by an .aqueous emulsion system using suitable emulsifyingor dispersing-agents such asthehigher, alkylaryl. polyethoxyethanols, such as the. ethylene oxide modified alkyl phenols in which the alkyl group or groups has or have from 8 to 18 or more carbon atomssuch as octyl, dodecyl,
- and octadecyl and which contain from'6 .to 20' or more ethylene oxide units per molecule.
Examples of comonomers of monoethylenically unsaturated type which can thus ;be copolymerizedwith the monomers of the invention include vinylidene'halides drophilic, in character. Their water-solubility may be increased by reaction with an alkylene oxide, especially such 'as vinyl fluoride, vinyl chloride, vinyl bromide,
vinyl iodide, 1,1-difluoroethylene, 1,1-dichloroethylene;
'vinylidene hydrocarbons such as isobutylene, 1,3.-buta diene, styrene; halovinylidene hydrocarbons -such,.'as12- fiuOrO-LB-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro- -1,3-'butadiene;. 1 acrylic, haloacrylic and alkacrylic :esters,
nitriles and amides such as ethyl acrylate, methyl metha'crylate,--v butyl-: methacrylate, methoxymethyl methf acrylate; chloroethyl- .methacrylate, 'beta-diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile; acrylamidegmethacrylamide; vinyl carboxylates such as vinyl formate; -vinyl acetate, vinyl chloroacetate, vinyl ibutyrate, vinyl laurate;-unsaturated aldehydes andketones such as acrolein,. methacrolein, methyl vinyl ketone; N-vinyl imides-such asN-vinylphthalimide, N-vinyl-succinimidepunsaturated..ethercsuch; as, .vinyl ethyl .ether,
Vinyloxyethylurea, aminoethyl vinyl ether, formamidoethyl .vinyl ether; other .vinyl monomers such as vinylpyridine, N-vinyl caprolactam;- and other polymerizable or copolymerizable .unsaturate's such as tetrafluoroethylmonomers may be modified by reaction withnumerous materials. One important; class of such materials includezthe alkylene oxides such as ethylene oxide, propylene oxide, or. trimethylene oxide. Anywhere from ,1 mole to. 100 moles of alkylene oxide may be reactedper hydroxyl .group in the monomeric or polymeric. compounds. Preferably. one to 10 moles of ethylene .oxide are "employed. 'The reaction with the .alkylene-coxi'de mayzbe carried out in an alkaline aqueous solution' of 1%- to 5% of sodium or potassium hydroxideor-carstituents' in the amine I as well as the molecular size of theiamine and the-acid whose derivative isreacted with theamine. Where A- is short, as in the case of ethylene or propylene, and R is small, as inthe case of hydrogen or methyl, and the acid from which the amide is 013-? tained contains aplu'ra'lityof hydroxyl groups, themonomeric amide ofz-thepresent invention is ..essentially hybonate'at awtemperature of 50-'l001C. for a period of 11-- ethylene oxide, and this expedient may even be employed to impart water-solubility to the monomeric amides or polymeric amides of the present invention derived from amines in which A and R are somewhat larger -than=propylene or methylrespectively, and; ,even from those monomers derived from aromaticacids which contain a single hydroxyl group in the aromatic nucleus. When the-hydrophobic component or componentsof the monomeric compounds are 'large'and adequate hydroxyl or hydroxyl-terminated-oxyethylene units are present to impart. strong shydrophilic ,character ,to the acid A residue in the compounds, the productshave surface-activity and their polymers also possess this v characteristic. Such compounds areuseful as wetting agents, dispersing agents and emulsifying agents in the textile, leather, and paper industries, Thesehydrophiliccompounds are also usetul as humectants ,orsoftenersas in cosmetics, suchas hand or facial-lotions, and may be used forthes of tening of cellophane, rayon, ,wrapping papers, tobacco and the like. For thispurposethey may becombinedwith; conyentionalsoftening agents such-as glycerine, the lower \glycols, 1 such. as; ethylene glycol, diethylene glycol, and
urea.
- Those-monomeric compounds ;.which;'containa ,large y p obi o p: nd. a-r ative s a l-0 nodm content, insuflicient to; offset 1; the hydrophobic. character of the main part of the molecule, are valuable,,as; -wax substitutes and ascornponentspf compositions intended to coat or impregnate leather, paper, cellophane, or 1 textiles with; a-:water,-repell ent- ,or-;-waterrproofing.finish.
. 'lzhe lmonomeric,amidesof"thmpresent inventiontwhqsc amido::nitrogen:carry a;hydr,ogen atom and those which carry hydroxyl groups are capable of reacting;with alde- 'hydesp: such. as;.1-fo1:maldehyde: or; acetaldehyde, or acids such as acetic, lauricgphthaiic; :andzmalei'c acidsi Hence theyzmay betem'ployed ras modifying; components in, con- ;junction withvrother reactiveresin-forming materials, such as the aminoplasts@ofizzwhichwurea-formaldehyde, melamine-formaldehyde, and .mixed melaminenureaaformaldehyde condensatesare representative; in alkyd;types of condensation products, such as glycerol-phthalates, an d styrene-maleic anhydride copolymers.
Like the monomers, the polymers obtained have a .wide range of properties and mayrange:-'from watersoluble to water-insoluble and highly water-repellent compounds. In allrof such polymers, however, the-presenceof'hydroxyl'groups and H-atoms on the-amide nitrogen provides reaction sites for the cross-linking of th'e'polymers' by condensation with difunctional reacting' --materials such as diacids, aldehydes, and so on. Like the monomers,-. the polymers and copolymers of themonomeric compounds ot. the present invent-ion are useful as :modifying components of reactive thermosetting types 'of'resin-forming compositions including the aminoplasts mentioned above, the alkyds, epoxides,'phenQl-aIdehyde-resins,and so on. a The water-soluble and water-sensitive polymers and copolymers may 'be'used as dressing, finishing, conditioningand coating agents for paper, leather, and textiles of all: sorts. They are especially valuable as warp sizes and ,as th ickeners or protective colloids in conjunction with;other;dispersiblematerials, such as glue, gelatin, .starch dextrin andthe like. Certain of the polymers .as well as-eopolymers which have proper balance-.betweena highly hydrophobic portion in the molecule and a :strongly, hydrophilic portion are useful as wetting, agents, dispersing agents and so on. Others "of' the'polymers which have a highly hydrophobic character may; be .converted to suitable wetting agents by reaction with alkyleneaoxides and especially ethylene oxide to introduce sufficient thereof to impart a strongly hydrophilic portion to the polymer-molecule; 1*. The; polymers 'which are of water-soluble character are useful inwater-based emulsion paints,-such as those based on emulsions of polyvinyl acetate or polyacrylates, when added in amounts of 1% to 3% of the weight of the main resin in the emulsion. Such additions improve the brushing characteristics of the paints and impart better wet-edge characteristics so that application of the paint to an adjoining area may be effected after substantial periods of time with less risk of lifting the previously applied coating or excessive thickness where the edges overlap.
The monomeric compounds of the present invention may be copolymerized in relatively small proportions ranging from 1 to 10 mole percent or more with 99-90 or less mole percent of other non-reactive monomers such as methyl methacrylate to impart to the copolymer obtained the capacity to react with other materials and thereby adapting the polymer of the other type of comonomer to be used as a modifier for aminoplasts, alkyd resins and epoxy resins. Such products are quite useful as pigment-binding compositions in the coating of papers or the pigment-dyeing of textiles. The copolymers may be used in a wide range of proportions from 15% to 25% by weight of the pigment in the case of coating of papers to 200% on the weight of the pigment in the case of pigment-dyeing of certain textiles. In these compositions, such pigments as clay, titanium dioxide, calcium carbonate, zinc'oxide, lithopone and the like may be used.
The monomers themselves are useful as insecticides, bactericides and fungicides, those containing chlorine or nitro groups being especially effective as insecticides, and
.those containing hydroxyl groups being effective as bac tericides. Both thev monomers and polymers which contain chlorine substituents in the aryl nucleus and in which there is no free hydrogen attached to the amido nitrogen are valuable plasticizers for various resinous materials, especially polymers of vinyl chloride, vinylidene chloride, tetrafluoroethylene, chlorotrifluoroethylene, and copolymers containing a predominant proportion of one of the preceding materials with another of such materials or with vinyl acetate, acrylonitrile, or esters of acrylic acid or methacrylic acid, such as the methyl, ethyl, propyl, or butyl esters thereof. Those monomers and polymers of the present invention which contain a high proportion of chlorine relative to hydrocarbon content are useful for reducing flammability of formed gmasses, such as fibers, filaments, films, or sheets of iordinarily flammable materials, and they may be intro- .duced into such former masses by the incorporation of :-15% by weight of the chlorine-containing amides or polyamides of the present invention into the mass of filmforming material, such as a molten mass or solution thereof in an organic solvent,.prior to the formation of the article from such molten mass or solution. Such chlorine-containing amides or polyamides of the present invention may also be applied as coatings to cellulosic articles, such as paper, felts or fabrics made of wood pulp, cotton or rayon fibers for the purpose of reducing the flammability thereof. The following examples are illustrative of the invention:
Example 1 (a) A l-liter 4-necked flask equipped with stirrer, thermometer, condenser and dropping funnel is charged with 152 g. (1.1 mole) of potassium carbonate (anhydrous), 150 g. of water, 250 ml. of toluene and 174 g. (2.0 moles) of Z-aminoethyl vinyl ether. The mixture is cooled to 5 C. and stirred and 281 g. (2.0 moles) of benzoyl chloride is added dropwise with the temperature kept below C. with an ice-acetone bath. The addition is completed in 4 hours; the mixture is stirred at 25 C. for 1 hour and filtered. The layers are separated and the toluene layer is dried with MgSO filtered, and acetone is added to precipitate the product, 2-benzamidoethyl vinyl ether, which is recrystallized from anhydrous ether and isobtained in 64% yield. -It has a MP. of 55.5-56.5 C. Analysis shows a 7.3% nitrogen content as compared to 7.25% N theoretical.
(b) The procedure ofv part (a) hereof is repeated substituting two moles of o-toluic acid chloride for the benzoyl chloride of part (a). A colorless product, 2-(0 toluylamidoethyl) vinyl ether, is obtained.
(c) The procedure of part (a) hereof is repeated except that two moles of the chloride of 2,3-xylic acid is substituted for the benzoyl chloride. A crystalline white solid product is obtained.
(d) The procedure of part (a) hereof is repeated substituting two moles of S-aminopentyl vinyl ether for the vinyl ether of part (a). The product is a white crystalline solid having a waxy feel.
(e) The procedure of part (a) hereof is repeated replacing the vinyl ether thereof with two moles of phenylaminoethyl vinyl ether. I
(f) The procedure of part (a) hereof is repeated replacing the vinyl ether with two moles of benzylaminoethyl vinyl ether.
(g) The procedure of part (a) hereof is repeated substituting two moles of N methyl-2-aminoethyl vinyl ether for the vinyl ether of part (a).
Example 2 (a) The procedure of Example 1(a) is carried out substituting two moles of 2-methylaminoethyl vinyl ether for the vinyl ether of Example 1(a) and substituting two moles of p-nitro benzoyl chloride for the benzoyl chloride of Example 1(a). A 71% yield is obtained of the N- methyl-N-vinyloxyethyl-p-nitro benzamide having a melting point of 51.l-52.5 C. and nitrogen content of 11.0% (as compared to a theoretical nitrogen content of 11.2% The product is a useful insecticide particularly as a stomach poison for the control of armyworms.
(b) The procedure of part (a) hereof is repeated substituting two moles of Z-aminoethyl vinyl ether. for the vinyl ether of part (a). An ofi-white crystalline product is obtained.
(0) The procedure of part (a) hereof is repeated sub: stituting two moles of phenylaminoethyl ether for the vinyl ether of part (a) hereof.
(d) The procedure of part (a) hereof is repeated substituting two moles of cyclohexylaminoethyl vinyl ether for the vinyl ether of part (a) hereof. The white crystalline product obtained has a waxy feel.
Example 3 (a) The procedure of Example 1(a) is repeated substituting two moles of vinyloxyisobutylamine for the vinyl ether of Example 1(a) and substituting two moles of o-chlorobenzoyl chloride for the benzoyl chloride of Example 1(a). A 79% yield of the amide is obtained having a melting point of 6061 C. and having a nitrogen content of 5.4% (theoretical 5.5% N). The polymer when used in 5% concentration in hydrocarbon solvent such as deodorized kerosene or Stoddard solvent'is useful as a fly or moth spray.
(b) The procedure of part (a) hereof is repeated substituting two moles of 2-amino-1-hexadecylethyl vinyl ether for the vinyl ether of part (a) hereof. The product is a white crystalline material of waxy character. A solution of 10% of the waxy amide thus obtained in deodorized kerosene is applied by spraying to a glove leather. There is imparted a highly water-repellent finish on the leather.
Example 4 (a) The procedure of Example 1(a) isrepeated substituting two moles of salicylic acid chloride for the benzoyl chloride. The solid amide thus obtained is dispersed in ethanol and 1% of sodium ethoxide is introduced. Then ethylene oxide is introduced. Then ethylene oxide (10 moles per mole of amide) is introduced Example Ten parts-by weightof benzamidoethyl vinyl-ether obtained by the procedure OilExahtple 1(a) is heated to 75 C. and 0.2 part byweight of dimethylazoisobutyrate is in'tr-oduced withiagitation. The mixture is agitated and heated at 75 C. for 16 hours, after whichthepolymer is precipitated withacetone. A 55% .yield of polymer is obtained;
Example 6 Ten parts by weight of 2-(o-chlorobenzamido)isobutyl vinyl ether obtained by the procedure of Example 3(a) is heated to 75 C. in 0.2 part of' dimethylazoisobutyrate and is introduced as a-catalyst. After agitating at 75 C. for16 hours, .the polymer is precipitated with acetone.
Example 7 ,(a) Five parts by weight of 2-benzamidoethyl vinyl ether and five parts by weight of methyl methacrylate are dissolved in ten parts by weight of dimethylformarnide. Then 0.2 part by weight of dimethylazoisobutyrate is added as a catalyst and the mixture is agitated and heated at 75 C. for 18hours. The copolymer obtained isprecipitated by the addition of methanol. It is readily dyed by means of numerous dyes, including acid .wool dyes.
b) Ten parts by weight of N-methyl-Z-benzamidoethyl vinyl ether and 90 parts by weight of acrylonitrile are dissolved in 120 parts by weight of dimethylformamide.
Two parts by weight of dimethylazoisobutyrate is added as a catalyst, and the mixture is stirred at 70 C. for 20 hours. The resulting dimethylformamide solution of' the copolymer is diluted with an additional 250 parts by weight of dimethylformamide and then spun through a spi-nnerette into a dilute aqueous solution of dimethylformamide containing about 5 to 10% of dimethyl formamide. The resulting fibers after drying and stretching show good tensile strengths and can be readily dyed with acid wool dyes.
(c) Three parts by weight of 2-(o-chlorobenzamido)- isobutyl vinyl ether, parts by weight of vinyl chloride, parts by weight of water, 0.3 part of dimethyl azoisobutyrate, and 2 parts of sodium lauryl sulfate are charged to an autoclave swept free of air and heated at 55 C. for 16 hours with agitation. The polymer isolated by coagulation is washed well with water, dried and dissolved in acetone. Fibers, films or filaments cast or formed from a 20% solution of the copolymer show low f flammability and increased toughness and flexibility over unmodified polyvinyl chloride.
It. is to be'understoodthat changes and variations may bemade .:without, departing from the spirit and scopeof thevinvention as,defined'in the appended claims.
1. Agcompound :having the formula CHFCHOANRCOR where:
A is an alkylene group having 2 to 18 carbon atoms of which at least two in a chain separate the adjoining nitrogen and etherv oxygen atoms,
R is selected from the group consisting of hydrogen, phenyl, tolyl, benzyl, cyclohexyl, and alkyl groups have ing 1 to 18 carbon atoms, and
R is selected from the-group consisting of phenyl, tolyl, and xylyl' groups and said groups substituted by a member, selected fromzthe group consisting of halogen, nitro, and hydroxyl 1 groups.
2. A polymer of a compound defined in claim 1.
3. Z-benZamidoethyl vinyl ether.
4. N-methyl-Z-henzamidoethyl vinyl ether.
5. N-methyl-Z (p-nitrobenzamido) ethyl vinyl ether.
ethyl vinyl 11. A- copolymer of 1 to 10 mole percent of. Z-benzamidoethyl vinyl etherwith 99 to mole percent of at least one other monoethylenically unsaturated copolymerizable compound.
1.2. A copolymer of- 1 to 10 mole percent of N-methyl- Z-benzamidoethyl vinyl ether with 99 to 90 mole percent of at least one other monoethylenically unsaturatedcopolymerizable compound.
13. A copolymer of; 1 to 10 mole percent of 2,2-dimethyl-Z-(o-chlorobenzamido)ethyl vinyl ether with 99 to 90 mole percent of at least one other monoethylenically unsaturated copolymerizable compound.
14. A copolymer of 2-benzamidoethyl vinyl ether with methyl methacrylate.
15. A copolymer of N-rnethyl-Z-benzamidoethyl vinyl ether with acrylonitrile.
16. A copolymer of, 2,2-dimethyl-2-(o-chlorobenzamido),ethyl vinyl etherwith vinyl chloride.
References Cited in the file of this patent UNITED STATES PATENTS 2,449,192 Behrenset a1. Sept. 14, 1948 2,571,325 Zentner et al. Oct. 16, 1951 2,572,560 Ham Oct. 23, 1951 2,601,251 Bruson June 24, 1952 2,686,173 Sauer Aug. 10, 1954