Патент USA US2407480код для вставки
Patented Sept. 1-0, 1946 2,407,479 ‘UNITED STATES PATENT, OFFICE 2,407,479 INTERPOLYMERIZATION PRODUCTS Gaetano F. D’Alelio, Pitts?eld, Mass., assignor to General Electric Company, a corporation 01' New York No Drawing. Application October 31, 1939, Serial No. 302,167 1; Claims. (01. use-42) 1 . This invention relates to the production of new materials having valuable and characteristic properties that make them especially suitable for use in industry, for example in molding, laminat 2 to proceed to a. limited degree. One reason for this is because the unreacted alcohol and acid groups then unreasonably limit the solubility of the partial ester in polymerizable monomers. An ing, casting, coating and adhesive applications, other reason is that the presence of such unre and for other purposes. The invention is con cerned more particularly with compositions of matter comprising an interpolymer (copolymer) or interpolymers of at least one polymerizable esteri?cation product of at least one polyhydric alcohol, at least one alpha unsaturated alpha beta polycarboxylic acid and at least one esteri?able monohydroxy organic compound with at least one acted groups makes the ?nal copolymerization product of such low resistance to the action of water, weak alkalies, etc., that it is unsuited for the usual commercial applications. I have discovered that these di?iculties can be obviated by producing the copolymer from an un saturated alkyd resin which has been internally F modi?ed by an esteri?able monohydroxy organic other polymerizable compound containing the grouping -—CH=C<, e. g., ethylene compounds such as vinyl esters, acrylic esters, alkacrylic esters, itaconic esters, allyl esters. etc. For pur monobasic acid. pose of brevity, the above-described esteri?ca tion product is hereafter designated generally as terrupt and shorten the chain of the ultimate esteri?cation product. These modi?ed unsatu a “modi?ed unsaturated alkyd resin.” rated alkyd resins are more fluid and more solu Speci? cally the invention relates to the production of synthetic, polymerized materials consisting of the compound, speci?cally a monohydric alcohol or a These mono-esteri?able com pounds interesterify with the polyhydric alco hol and the polycarboxylic acid, serving to in ble in, and compatible with, polymerizable monomers than the unmodi?ed unsaturated alkyd resins.- It was surprisingly found that product of polymerization of a mixture of co polymerizable materials consisting of (1) a poly despite the shortening of the ester chain by merizable monohydric alcohol polyester of an 25 modifying the unsaturated alkyd resin with a alpha unsaturated alpha beta polycarboxylic acid mono-esteri?able compound, the thus modi?ed and (2) a polymerizable esteri?cation product se unsaturated alkyd resin had substantially, the lected from the class consisting of polymerizable same copolymerizing capacity with polymerizable esteri?cation products of a polyhydric alcohol, an compounds containing a -—CH=C< grouping as alpha unsaturated alpha beta polycarboxylic acid 30 the unmodi?ed unsaturated alkyd resins. This anda monocarboxylic acid, polymerizable esteri was quite unexpected and could not have been ?cation products of a monohydric alcohol, a poly predicted from the known properties of unsatu hydric alcohol and an alpha unsaturated alpha rated alkyd resins. beta polycarboxylic acid, and polymerizable ester i?cation products of a monohydric alcohol, a poly In carrying the present invention into e?'ect a polymerizable esteri?cation product of a poly hydric alcohol, an alpha unsaturated alpha beta hydric alcohol, an alpha unsaturated alpha beta polycarboxylic acid and a monocarboxylic acid. polycarboxylic acid and a mono-esteri?able or The unmodi?ed unsaturated alkyd resins, that ganic compound is prepared in accordance with is, unmodi?ed esteri?cation products of a poly technique now well known to those skilled in hydric alcohol with an alpha unsaturated alpha ~10 the alkyd resin art. Any polyhydric alcohol beta polycarboxylic acid, do not lend themselves containing at least two esteri?able aliphatic hy»v readily to the production of copolymers with other droxyl groups, or mixtures of such alcohols, may polymerizable materials. Because of their ex be used in preparing the modi?edunsaturated tended linear structure and advanced resinous alkyd resin. Examples of such polyhydric alco nature, it is quite difficult to obtain homogeneous hols are ethylene glycol, di-, tri- and tetra-eth mixtures or solutions of such alkyd resins with many polymerizable monomeric materials. It is especially dif?cult and costly to obtain copoly mers of uniform characteristics when the ratio of unsaturated alkyd resin to the polymerizable acid, or mixtures of such acids, may be reacted with the polyhydric alcohol or alcohols to form monomer is high, say 90 or 95 parts of unsat urated alkyd resin to 5 or 10 parts of the poly merizable monomer. Also, it is not feasible to prepare an unsaturated alkyd resin of low molec the polymerizable resin. Examples of such poly carboxylic acids are maleic, monohalomaleic,' fumaric, monohalofumaric, citraconic, mesa conic, acetylene dicarboxylic, itaconic acid and ylene glycols, propylene glycol, trimethylene gly col, thiodiglycol, glycerine, pentaerythritol, etc. Any alpha unsaturated alpha beta polycarboxylic ular weight merely by allowing the esteri?cation 65 its homologues as, for instance, alpha methyl ita 2,407,470 3 conic acid. alpha ethyl itaconic acid, alpha alpha dimethyl itaconic acid, etc. Part of these un saturated polycarboxylic acids, that is. up to ' about 75 mol per cent, may be replaced by non carboxylic acids, unsaturated alcohol esters of saturated monocarboxylic acids, etc. More specific examples of compounds contain ing a —CH=C< grouping are the unsaturated alcohol esters, e. g., the allyl, methallyi, crotyl, ethylenic polycarboxylic acids, e. g., the satu rated aliphatic polycarboxylic acids such as suc propargyl, l-chloraliyl, 2-chlorallyl, cinnamyi, cinic, adipic, glutaric, pimelic, sebacic, azelaic, suberic, tricarballylic, tartaric, citric, etc., cyclic polycarboxylic acids, more specifically the satu 1-phenyl-2-propyn-1-yl, 3-methyl-4-nonyn-3-yl, 4-methyl-5-decyn-4-yl, 4-methyl-5-undecyn-4 3-methyl allyl, vinyl, methvinyl, Z-phenyl allyl, etc, esters of saturated and unsaturated, ali rated cycloaliphatic polycarboxylic acids such as 10 yl, phatic and aromatic, monobasic and polybasic the cyclopropane dicarboxylic acids, the cyclo acids such, for instance, as acetic, propionic, hexane dicarboxylic acids, the alkyl cycloalkane butyric, valerlc, caproic, acrylic, alkacrylic (e. g., polycarboxyllc acids, etc., and the aromatic poly methacrylic, ethacrylic, etc.), crotonic, oxalic, carboxylic acids, e. g., phthalic, benzoyl phthalic, terephthalic, benzophenone - 2,4’ dicarboxylic 15 malonic, succinic, glutaric, adipic, pimelic, su beric, azelaic, sebacic, maleic, fumaric, citraconic, acids, etc. Anhydrides of the polycarboxylic mesaconic, itaconic and its homologues (e. g., acids, if available, also may be used. The term alpha methyl itaconic, alpha ethyl itaconic, al “polycarboxylic acid” as used generally herein pha alpha dimethyl itaconic, etc.), acetylene and in the appended claims therefore is intended dicarboxylic, benzoic, toluic, phenyl acetic, 20 to include within its meaning the anhydrldes of phthalic, terephthalic, benzoyl phthalic, benzo the acids. phenone-2,4' dicarboxylic, cinnamic, etc.; the Various mono-esteri?able compounds may be saturated alcohol esters, e. g., the methyl, ethyl, incorporated into the unsaturated alkyd resin in propyl, butyl, isobutyl, ethylene glycol, glycerol, order to modify the same. Thus, in producing etc., esters of the unsaturated aliphatic the copolymers of this invention I may use an 25 monobasic and polybasic acids, illustrative ex unsaturated alkyd resin which has been modi?ed by incorporating therein a saturated or unsatu- _ amples of which appear above; vinyl cyclic com pounds, e. g.- styrene, vinyl naphthalene, vinyl rated, normal or isomeric monohydric alcohol, or cyclohexane, methylene-tetrahydronaphthalene, mixtures thereof, a saturated or unsaturated vinyl furane, divinyl benzene, etc.; unsaturated monocarboxylic acid, or mixtures thereof, or both 30 ethers, e. g., ethyl vinyl ether, diallyl ether, allyl such esterifiable monohydroxy organic com pounds. Examples of monohydric alcohols ethyl ether, divinyl ether, vinyl allyl ether, meth which may be used as modi?ers of the alkyd resin methyl vinyl ketone, methyl methvinyl ketone, ethyl methvinyl ketone, divinyl ketone, methyl allyl ketone, etc.; methylene malonic esters; are propyl, isopropyl, butyl, isobutyl, amyl, iso~ amyl, hexyl, octyl, decyl, dodecyl to octadecyl, inclusive, allyl, methallyi, 1-chlorallyl, 2-chlor allyl, crotyl, cinnamyl alcohols, S-hydroxy bu allyl propyl~ ether, etc.; unsaturatedketones, e. g., ' 2-chlorobutadiene; etc. Preferred organic com pounds which are used in carrying the present tene-l, etc. The use of methyl and ethyl alco invention into e?ect are compounds having at hols is not precluded, but in general these alco least one CH2=C< grouping, e. g., acrylic esters hols are less suitable because of their lower boil 40 such as ethyl acrylate, alkacrylic esters such as ing points. As monobasic acids may be used, for ethyl methacrylate, etc. For certain applica example, the unsubstituted saturated or unsatu tions, as for instance in the production of so rated, normal or isomeric acids containing only called “solventless varnishes," I prefer to co one esteri?able group such as acetic, propionic, polymerize the modi?ed unsaturated alkyd resin butyric to stearic, inclusive, benzoic, acrylic, 45 with a monohydric alcohol ester of an alpha methacrylic, cinnamic, etc., acids of drying, unsaturated alpha beta polycarboxylic acid, e. g., semi-drying and non-drying oils, e. g., the acids diethyl itaconalte, diallyl maleate, diallyl ita of tung oil, linseed oil, rape seed oil, soya bean conate, etc. oil, castor oil, etc. The mono-esteri?able com To achieve copolymerization of,the modified pound may be introduced into the esteri?cation 50 product before, during or after the esteri?cation of the polyhydric alcohol with the polycarboxylic acid under conditions that interesteri?cation of the mono-esteri?able compound with the incom pletely esteri?ed polyhydric unsaturated alkyd resin with the monomeric or partially polymerized organic compound contain ing a -CH=C< grouping, a solution of the said resin in the said organic compound first prefer ably is effected, The organic compound employed alcohol-polycar 55 advantageously may act as a carrier for a small boxylic acid reaction product is obtained. That is, the mono-esteri?able compound must be in troduced into the reaction mass before all of the acid groups of the polybasic acid or all of the amount of a polymerization. catalyst. Examples of polymerization catalysts which may be used are ozone, ozonides, inorganic super-oxides such as barium peroxide, sodium peroxide, etc., all alcohol groups of the polyhydric alcohol have 60 phatic acyl peroxides, e. g., acetyl peroxide, lauryl been esteri?ed. peroxide, stearyl peroxide, etc., peroxides of the In carrying the present invention into effect aromatic acid series, ‘e. g., ‘benzoyl peroxide, organic compounds containing the polymerizable various per-compounds such as perborates, per grouping -CH=C<, or mixtures thereof, are in 65 sulfates, perchlorates, etc., aluminum salts such terpolymerized with one or more modified un saturated alkyd resins, such as above described, to produce new and valuable compositions. Il lustrative examples of compounds containing as the halides, e. g., aluminum chloride, organic and inorganic acids such as methacrylic, hydro ?uoric, etc., metal compounds of the unsaturated acids as, for instance, cobalt and manganese such a grouping are esters containing ethylenic or acetylenic unsaturation in either the alcohol 70 resinates, linoleates, maleates, etc. \Benzoyl per oxide is the preferred catalyst. Any suitable radical or the acid radical, or in both, e. g., satu amount of catalyst may be used, but in general rated and unsaturated alcohol esters of unsatu the catalyst concentration will be within the rated monocarboxylic and polycarboxylic acids, range of 0.1 to 2.0 per cent by weight of the unsaturated alcohol esters of non-ethylenic (e. g., aromatic and saturated aliphatic) poly 75 whole. 2,407,479 5 . When rapidity of interpolymerization between . 6 copolymer: of modi?ed unsaturated alkyd resins the components is of secondary importance, co with -CH=C< compounds-Continued polymerization may be e?ected merely under the in?uence of heat, light, or heat and light and in > ‘ cnmmua of the absence of an accelerator of polymerization. 5 Resin Parts —CH=C<eompound Parts copolymer after 24 hours at 70° 0. The rate of copolymerizationand the properties of the ?nal product vary with the time, temper D._._. 90 Diallyl itaoonate._... 10 Very viscous. ature and, if a catalyst is used, also with the B___-. 90 Diallyl itaconate..-.. 10 Staff; clear, elastic, gel catalyst concentration. Copolymerization may e. 1r_____ 9o \ Dlaliyl itaoonate.-... 10 Hard, clear. be eifected at .from room temperature (20° to 90 Diallyl ltaconate...__ 10 Hard, clear. 30° C.) to temperatures above 100° C., for ex ample about 130° C., but ordinarily I use temper 90 Diallyl itaeouate._-.. o0 Diallyl itaeonate atures within the range of 60° to 120° C. in cans ing the mixed components to interpolymerize. In order that those skilled in the art better 15 B.____ may understand how the present invention may be carried into effect, the following examples are given by way of illustration. All parts are by D____. weight. Reference is ?rst made to the com ponents, and proportions thereof, used in the 20 B___.. preparation of the modi?ed unsaturated alkyd I~‘_____ resins. These resins (identified by letter desig F..__. nations) were copolymerized with —CH=C< 10 Soft, clear, gel-like. 5 Firm, clear, gel-like. vinyacetate. 90 Mietthallyl methacrya e. 90 Glyteol dimethacrye. 90 Glygil dimethacry- 10 Hard, clear. 10 Hard, clear. 10 Hard, clear. 00 0:31:01 dimethacrye. 10 Hard, translucent. 90 90 9o 90 90 Glytcol dimethacrye. Glygol dimethacrya e. Glycol dimethacrye. M‘eihallyl methacry-. .a e. Glygol dimethacry- 10 10 10 10 10 Flrm,translucent gel. Hard, clear. Hard, clear. Hard, clear. Very ?rm,gel-like. compounds in varying amounts, using 1% by H___._ weight of the mixed components of benzoyl per~ 25 oxide as an accelerator oi‘ polymerization. A brief description of the properties of the copolymer after 24 hours’ interpolymerization at 70° C. is _A_____ 10 Diallyl oxalate ..... __ B_____ 90 Diallyl oxalate _____ __ 10 Hard, C_____ 90 Diallyl oxalate ..... -. 10 Fill?lti, translucent gel a e. D 90 E 90 Modified unsaturated alkyd resins Composition rts) parts) and soya bean acids (15.2 parts) . maleic . Very ?rm, gel-like. Diallyl oxalate . _ . 10 _ . 10 10 Gel-like. ?rm, clear. Firm, clear. rubbery. Dlally maleate_ _ . 10 Hard, clear. Diallyl maieate.- . 90 Hard, clear. Diethyl itaconate..._ 90 Diallyl itaconate.__.. l0 Veil-g soft, clear, gel e. l0 Vulairky soft, clear, gel 90 10 Diallyl itaconate___-. Diethyl itaconate__._ 10 10 Soft. clear, gel-like. e. Hard, clear. Hard, clear. l0 Elli-£1, translucent gel 1 e. l0 Self?é translucent gel 1 e. 80 Diallyl itaconate_._._ 20 Hard, clear, resilient. M ..__ 80 Diethyl itaconate__._ 20 Soft, clear, resilient. N __.__ 90 Diailyl itaconate__-.. 10 Hard, clear. N_____ 0_____ 90 90 Diethyl itacoi'late_.-_ Diallyl itaccnate_.___ 10 10 Slightly soft. clear. Hard, translucent. 10 10 10 10 Soft, clear, gel-like. Soft, clear, gel-like. Very ?rm, slightly translucent. Soft, clear, gel-like. O__... 90 Diethyl itaconate_... Diethyl itaconate._.. Diallyl itaconate___-. Diallyl itaconate_._._ Diethyl itaconate. anhydride (21.93 pa rts) _ ery. Diethyl itaconate. 10 Diallyl itaconate. 10 Veil; ?rm, clear, gel Clear, viscous. Diallyl maleate- _ Diallyl maleate. _ l0 10 Firm, clear. gel-like. Clear, gel-like, soft. K Diethylene. glycol (35.4 parts), maleic anhydride (27.95 65 L_____ parts) and linseed oil acids (7.7 parts) Ethylene glycol (18 parts), maleic anhydride (27.93 parts) . M____ 90 Diallyl maleate. . _ 10 Firm, clear. 90 Diallylmaleate ____ .. 10 Fllrréi, translucent gel 80 Diallyl maleate .... -. 20 vFirm, clear. resilient. N___.. 90 Diallyl maleate- __ l0 and octyl alcohol (3 .9 parts) _ Ethylene glycol (35.4 parts), maleic anhydride (29.4 parts; , 1 e. 0___._ octyl alcohol (13 parts) and acetic anhydride (11.8 parts 90 Diallyl maleate.-. _ 10 Soft, clear, gel-like. 90 Diallyl maleate ____ _- 10 VerLy firm, clear, gel 10 10 10 10 Firm, clear, gel-like. Firm, clear. gel-like. Firm, clear, gel-like. Firm, clear, gel-like. 1’9. 90 90 Ethyl aervlate 90 Vinyl acetate. 90 Methyl methacr Characteristics of copolymer after 24 hours at 70° C. 10 Clear, tough. insoluble and infusable. B..-__ 90 Diethyl itaconate_... 10 Hard, clear, gel-like. C_..__ 90 10 D..." H.._-. A...“ B___.. B..." 90 Diethyl itaconate.._. 90 Diethyl itaconate____ 10 Diallyl itaeonate...__ 90 Diallyl itaconate_.___ 90 Diallyl itaeonate 10 Clear, very viscous. 10 Very firm, gel-like. 90 Hard, ear. 10 Hard, clear. gel-like. 5 Hard, clear. O..--- 90 Diallyl itaeonate .... .. 10 Diethyl itaoonate. . .. - methyl methacrylate. Very firm, gel-like, translucent. 90 Styrene _______ ._ 90 Ethyl acrylate ..... ._ 0. 10 Firm, clear, gel-lkie. l0 Firm, clear. gel-like. 10 Firm, clear, gel-like. 90 90 Vinyl acetate ...... .. Styrene ............ .. l0 10 Firm, clear, gel-like. Firm, clear. gel-like. 90 Ethyl acryiate _____ .. 10 Hard, clear. K..." 90 Methylmethacrylate. 10 Hard, clear. K.____ K_____ 90 Vinyl acetate ...... _. Styrene ............ __ 10 10 Hard, clear. Hard, clear. L_____ Ethyl acrylate ..... .. 10 70 L_____ 90 Methylmethacrylate. 10 Filrgl, translucent gel L_____ 90 Vinyl acetate ...... _. 10 L_____ 90 Styrene..- .......... _. 10 80 Vinyl acetate ...... .. J translucent gel 1 e. 1 e. translucent gel e. ‘ Filri'krn, translucent. gel .. 90 Methylmethacrylate. ' Diallyl oxalate ..... .. Hard, translucent. 90 Q with -CH=C'< compounds 90 10 Slightly soft, clear. P_____ C'opolymers of modi?ed unsaturated alkyd resins Resin Parts ~CH=C<eompound Parts Diallyl maleate-.. M____ 75 M‘_.._ . 80 Methyl methacrylate > 10 Solft, translucent rub e. 90 90 Ethylene glycol (17.7 parts) , maleic anhydnde (26.46 parts) A...“ Very viscous, clear. M__.. Ethylene glycol (18 parts), muleic anhydride (29.4 parts‘, octyl alcohol (2.6 partsl and stearic acid (5.16 parts). and acetic anhydride (7.08 parts). Very viscous, clear. Very viscous, clear. Diallyl oxalate. _ Dgallyl oxalate. . 90 Diallyl itaconate__.-. 90 Diethyl itaconate_..- L_____ 10 10 10 l0 Soliitk. clear, elastic, gel e. 10 Hard, clear. 10 rm, ear. 10 Firm, clear, gel-like. 90 s . Diethyleno glycol (30.6 plat?) , parts) and decyl alcohol Diallyl oxalate _____ __ Diallyl phahalate. . . . Diallyl succinate. - _.. Diethyl itaconate._ ._ phthalic anhydride (8.9 parts) and‘liusced oil acids (10.1 parts . Ethylene glycol (17.4 parts). maleic anhydride (28.8 parts) and stearic acid (3.4 parts) ‘ Diethylene glycol (20.4 parts), maleic anhydride (16.6 ear. Diallyl maleate._ __ Diallyl maleate.. Diallyl maleate__ Diallyl itaconate. Ethylene glycol (66 parts), itaconic acid (130 parts) and acetic anhydride ( 12 parts). Diethylenc glycol (19.6 parts), ltaconic acid (26 parts) and stearic acid (2.25 parts) . Glycerine (12.2 parts), itaconic acid (19.5 parts) and linseed oil acids (14.2 parts) Glycerine (65 parts ), itaconic acid (16.5 parts) and linseed oil fatty acids (140 Soft, translucent. e. given. Glycerine (12.2 partsgaitaconic acid (11.2 parts), phthalio ' anhydride (5.4 parts) and soya bean acids (13.9 parts). Ethylene glycol (6 parts), itaconic acid (14.3 parts) and octadecyl alcohol (5.4 parts). Ethylene glycol (10.6 parts), itaconic acid (14.4 parts) and I decyl alcohol (3.7 part E thylene glycol (15 parts), itaconic acid (31 parts) and tung oil acids (65 parts . Diethylene glycol (31.8 parts), maleic anhydride (27.9 parts) and tung oil acids (7.6 parts). Ethylene glycol (12 parts), maleic anhydride (11.76 parts), 90 translucent gel e. 20 Hard, clear. 20 Hard, clear. 2,407,479 7 as herelnbefore mentioned. Incertain cases, instead 01 copolymerizing a single -CH=C< compound with a single modi with - H=C< compounds-Continued ‘ Characteristics oi Resin Parts -—CH=C<compound Parts fied unsaturated alkyd resin, I may copolymerize copolymer after24 > 8 for instance accelerators of polymerizationesuch Cop‘olu'mers of modi?ed unsaturated alkyd resins hours at 70° G. a plurality of the said compounds with a single modified unsaturated alkyd resin or with a. plu Bib lacrylate _____ .. Hard, quite resilient. y Hard, uite resilient. Hard, c ear. St Soit,clear. . Soft, clear. ene .... .. Et lacryl Met yl methacrylate. Hard, translucent. Hard, clear. ' St Translucent, rubbery. ne ............ ._ mil”: acrylate ..... .. Firm, clear, gel~like. Methyl methacrylate. Firm, clear, gel-like. Vinyl acetate ...... _. Styrene ...... .. Firm, clear, gel-like. Firm, clear, gel-like. Ethyl acrylate. Vinyl acetate ______ -_ C .'._.. Methyl methacrylate. Hard. r ._--. St Hard. Et ii acrylate _____ ._ Vinyl acetate ....... ._ Styrene ____________ __ 1--.... 10 per cent of a -CH=C< compound. it will be understood, of course, that the invention is not limited to these particular proportions of com ponents. The incorporation of a small amount, ' Firm, clear, gel-like. Firm, clear, gel-like. 20 e. g., 3 or 4 per cent, of certain —CI-I=C< com pounds, for example diallyl itaconate and other unsaturated monohydric alcohol esters of alpha Soit, clear, gel-like. Boi't, clear, gel-like. Methallyl methacry, late. Glycol dimethacry Firm, clear, gel-like. Firm, translucent gel like. Firm, clear, gel-like. Firm, clear, gel-like. H Mb->Ar1~HIa late. Mei'ihailyl methacry a e. Glycol dimethacry late. Methallyl methacry Glycol dimethacry late. Methallyl methacry late. Glycol dimothacry unsaturated alpha beta polycarboxylic acids, into a modi?ed unsaturated alkyd resin has a bene ?cial effect upon such alkyd resins, yielding prod ucts of improved properties as compared with a modi?ed unsaturated alkyd resin which has been Hard, clear. polymerized in the absence of such a —CH=C< Hard, clear. compound. However, somewhat better results Fill-m,e. translucent gel 30 usually are obtained when the —CH=C< com pound constitutes, say, 6 or 8 per cent by weight of the mixed starting components. In most cases the mixed components are so proportioned that the —~CH=C< compound constitutes from 10 to Hard, slightly trans 35 90 per cent by weight of the whole, but the use of higher amounts is not precluded. Thus, in the lucent. Firm, translucent gel like. ‘ Somewhat turbid, slightly resilient. Somewhat turbid, slightly resilient. late. 88‘8888888 8 8 8 merizing from, by weight, 10 to 90 per cent of 15 modified unsaturated alkyd resin with from 90 to Firm, clear, gel-like. ene ............ ._ Met yl methacrylate. Although in the foregoing examples I have shown the production of interpolymers by copoly Firm, clear, gel-like. q ____, 2 R.____ service application. Soft, cloudy. Hard, translucent. Ethyl acrylate. - Vinyl acetate. _ ?._____ rality of such resins. In this way it is possible to obtain a composition comprising a mixture of 10 interpolymers best adapted to meet a. particular Methallyl methacry late. Glycol. dimethacry late. Glycol dimethacry late.‘ Slightly soft, clear. Slightly soft translu Metthallyl methacry e. production of organic plastic vmasses or coating compositions for certain particular applications, the --CH=C< compound may constitute, say, 96 Hard, translucent. 40 or 97%, or more, by weight of the whole, depend Firm, gel-like translu ing, for example, upon the particular starting cent. components employed and the particular prop Firm‘; gel-like translu Methallyl mcthacry late. Glycol dimethacry late. Glycol dimethacry . late. Methallyl methacry cen . cen . Mletthallyl methacrya e. 10 Gllycol dimethacryate. Methallyl methacryGllycol dimethacry- Diallyl succin e. 90 The interpolymerization products 01' this in 10 Very ?rm, translucent. 10 ltrlibber‘y, gel-like trans 10 Bolt, opaque, gel-like. . ate. erties desired in the copolymer. Very ?rm, translucent. ucen vention have a wide rangeof properties. _ 10 Very soft, clear gel-like. _ 10 Very soit, clear gel-like. l0 Firm, clear, gel-like. 50 tion (temperature, time, pressure, presence or 10 Soft, clear, gel-like. Diallyl oxalate _____ __ l0 Firm, clear. Diallyl succinate- . _ __ 10 Firm, clear. Diallyl oxalate ...... ._ l0 Firm, translucent gel absence of catalyst, kind of catalyst used, if any, as well as the catalyst concentration, etc.) and the extent of the interpolymerization, they vary from soft, ?exible, soluble bodies to hard, rigid 0. 90 Diallyl succinate___-_ 10 80 Diallyl oxalate ..... _- 20 Firm, resilient, clear. 80 Diallyl succinate-.__- 20 Hard, clear. Firm, translucent gel 90 Diallyl oxalate. __ __ l0 Slightly so! t, clear. 90 90 Diallyl succinate_--._ Diallyl oxalate _____ .- 10 l0 Slightly soit, clear. _ 'l‘rganséucent, fairly e. ar 90 Diallyl succinate._.-. 10 90 Diallyl oxalate _____ -. 10 90 90 Diallyl oxalate._ Diallylsuccinate. Diallyl succina 10 90 90 90 Diallyl succinate. Diallyl oxalate. De pending, for example, upon the particular modi ?ed unsaturated alkyd resin and the particular --CH=C< compound employed, the particular proportions thereof, the conditions of polymerize . 10 10 . Translucent, hard. Soft, clear, gel-like. Bolt, clear, gel-like. Hard, clear. Hard, clear. l0 Firm, clear, gel-like. 10 Firm, clear, gel-like. It will be understood, of course, that my inven tion is not limited to the production of copolymers of the particular modi?ed unsaturated alkyd resins with the particular -CH=C< organic 55 masses of varying resistance to solvents. In in termediate stages of copolymerization some form fluid compositions of varying intrinsic viscosities and may be so used. For coating or impregnating applications where the presence of a small 60 amount of solvent in the cured composition is not objectionable, the mixed polymerizable ma terials may be diluted with volatile or non-vola tile solvents to viscosities best adapted to meet the particular service application, and then may 65 be copolymerized after application of the solu compounds set forth in the above examples and ' ' tion to the particular article to be coated or im pregnated. By suitable selection of the start ing materials and the conditions of interpoly merization, interpolymcrs can be obtained in an that modi?ed unsaturated alkyd resins and 70. insoluble, infusible state practically resistant to the destructive e?ect of other chemical bodies -CH=C< compounds other than those above such as acids, bases, solvents and the like. given by way of illustration may be employed in These new compositions may be used alone producing the new interpolymerization products or with ?llers, dyes, pigments, opaci?ers, lubri of this invention. Also, polymerization catalysts other than benzoyl peroxide may be employed, 75 cants, plasticizers, or other modifying agents in, 9 2,407,479 for example, casting, molding and laminating 90 per cent of a polymerizable esteri?cation prod uct of a monohydric alcohol, a polyhydric alcohol and an alpha unsaturated alpha beta polycar boxylic acid. 6. As a new product, a synthetic resin consist ing of an interpolymer of diallyl maleate and a applications, as adhesives, impregnants and sur face coating materials. In coating, impregnat ing and similar applications the mixed compo nents, without added solvent, may be applied to the object to be treated and polymerized as here; inbe'iore described, with or without the appli polymerizable esteri?cation product of a mono cation of pressure, to form the copolymer in situ. hydric alcohol, a polyhydric alcohol and an al They may be used as impregnants for many por pha unsaturated alpha beta polycarboxylic acid. ous bodies, such as cork, pottery, felts, or fabri 10 7. A hard, clear synthetic resin obtained by cated bodies with interstices, such as the wind polymerization of a mixture composed of, by ings of electrical coils, netted ?bers, interwoven weight,labout 10 per cent of diallyl maleate and ?brous materials, etc. They also may be used about 90 per cent of a polymerizable esteri?ca for protectively coating impervious articles such as metals, e. g., iron or copper wire, or for coat tion product of ethylene glycol, itaconic acid and 15 acetic anhydride. ing or coating and impregnating articles such ‘ 8. A hard, clear synthetic resin obtained by as paper, wood, cloth, glass ?bers in felted, woven polymerization of a mixture composed of, by or other form, concrete, linoleum, synthetic weight, about 10 per cent of diallyl maleate and boards, etc. They also may be employed in the about 90 per cent of a polymerizable esteri?ca production of wire enamels and winding tapes. 20 tion product ofv ethylene glycol, itaconic acid and The mixed components or partial interpolymers octadecyl alcohol. thereof, with or without modifying agents, may 9. A composition comprising the product of be cast and molded under heat or under heat polymerization of a polymerizable mixture in and pressure. They also may be molded by in cluding (1) a polymerizable unsaturated alkyd jection, extrusion or compression molding tech 25 resin obtained by reaction of ingredients com nique whereby they are heat- and pressure-hard prising a polyhydric alcohol, a monocarboxylic ened to yield numerous molded articles of manu acid and itaconic acid and (2) a polyallyl ester facture for industrial, household and novelty of an alpha unsaturated alpha beta polycarbox , uses. ylic acid, said ester being compatible with the ‘What I claim as new and desire to secure by 80 resin of (1). Letters Patent of the United is: 10. A composition comprising the product of l. A synthetic, polymerized material consist polymerization of a polymerizable mixture in ing of the product of polymerization of a mixture cluding (1) a polymerizable unsaturated alkyd of copolymerizable materials consisting of a poly resin obtained by reaction of ingredients com: merizable monohydric alcohol polyester of an 35 prising a monohydric alcohol, a polyhydric alcm alpha unsaturated alpha beta polycarboxylic acid hol and an alpha unsaturated alpha beta poly and a polymerizable esteri?cation product of a carboxylic acid and (2) a polyallyl ester of an al monohydric alcohol, a polyhydric alcohol and a pha unsaturated alpha beta polycarboxylic acid, plurality of polycarboxylic acids at least one of said ester being compatible with the resin of (1). which is an alpha unsaturated alpha beta poly 40 11. A composition comprising the product of carboxylic acid. polymerization of a polymerizable mixture in 2. A synthetic, polymerized material consisting cluding (l) a polymerizable unsaturated alkyd of the product of polymerization of a mixture resin obtained by reaction of ingredients com of copolymerizable materials consisting of a poly prising a monohydric alcohol, a‘ polyhydric al merizable monohydric alcohol polyester of an 45 cohol and itaconic acid and (2) a polyallyl ester alpha unsaturated alpha beta polycarboxylic acid of an alpha unsaturated alpha beta polycarbox and a polymerizable esteri?cation product of a ylic acid, said ester being compatible with the monohydric alcohol, a polyhydric alcohol and resin of (1). an alpha unsaturated alpha beta polycarboxylic 12. A composition comprising the product of acid. 50 polymerization of a‘ polymerizable mixture in 3. A synthetic, polymerized composition con cluding (1) diallyl itaconate and (2) a polymer sisting of an interpolymer obtained by polymeri izable unsaturated alkyd resin obtained by reac zation of a mixture of copolymerizable materials tion of ingredients comprising a monohydric al consisting of a polymerizable monohydric alcohol cohol, a polyhydric alcohol and an alpha unsat polyester of an alpha unsaturated alpha beta 55 urated alpha beta polycarboxylic acid, said resin polycarboxylic acid and a polymerizable esteri? being compatible with the diallyl itaconate of cation product of a monohydric alcohol, a polyhy ( l. dric alcohol, a monocarboxylic acid and an alpha ' 13. A composition comprising the product of unsaturated alpha beta polycarboxylic acid. polymerization of a polymerizable mixture in 4. A synthetic, resinous composition consisting cluding (1) a polymerizable unsaturated alkyd of the product of polymerization of a mixture 60 resin obtained by reaction of ingredients com of copolymerizable materials consisting of, by prising a monohydric alcohol, a polyhydric alco weight, from 10 to 90 per cent of a polyallyl ester hol and a plurality of polycarboxylic acids at of an alpha unsaturated alpha beta polycarbox least one of which is an alpha unsaturated alpha ylic acid and from 90 to 10 per cent of a poly beta polycarboxylic acid and (2) a polymerizable 65 merizable esteri?cation product of a polyhydric monohydric alcohol polyester of an alpha un alcohol, a monohydric alcohol and an alpha un saturated alpha beta polycarboxylic acid, said saturated alpha beta polycarboxylic acid. ester being compatible with the resin of (1) . 5. A synthetic, resinous composition obtained 14. A composition as in claim 13 wherein the by polymerization of a mixture of copolymeri polyester of (2) is a polyallyl ester of an alpha 70 zable materials consisting of, by weight, about 10 unsaturated alpha beta polycarboxylic acid. per cent of a polyallyl ester of an alpha unsatu rated alpha beta polycarboxylic acid and about GAETANO F. D'ALEIJO. 11 l 112 Certi?cate of Correction Patent No. 2,407,479. ‘ September 10, 1946. GAETANO F. D’ALELIO It is hereby certi?ed that errorsv appear in the printed speci?cation of the above numbered patent requiring correction as follows: Column 5, line 73, in the table, fourth column thereof, following “methyl methacrylate” insert 5; column 6, line 13, same table, third column thereof, for “viny acetate” read vinyl acetate; same line, fourth column, under “Parts” insert 5; line 32, same table, third column thereof, for “Dially” read D'i'allyl; same'table, line 63, ?fth column thereof, for “gel-lkie” read gel-like; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent O?ice. Signed and sealed this 13th day of May, A. D. 1947. [m] LESLIE FRAZER, First Assistant Oommissz'oner of Patents.