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VVVVYVVVVA. 90 8O 7O 6O Ao 4O 3O 2O ?O Oozayyzerolyzed APOLYWAA OA Coaoa Yayaar Adol

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VVVVYVVVVA. 90 8O 7O 6O Ao 4O 3O 2O ?O Oozayyzerolyzed APOLYWAA OA Coaoa Yayaar Adol Oct. 26, 1943. G. F. D'AELO 2,332,900 SYNTHETIC COMPOSITIONS COMPRISING HYDROLYZED, ACETALIZED, AND/OR KETALIZED FOLYMERS OF ALLYL ESTERS Filed July 23, 1940 F--foo% wow-A/Yoarolyzeo Awo wow-ace.774L/Zala aolym1aar Of COAOLYMAAR OA a AOLYMEAIZABLE suasamyCae CoA1aa/s/wg any 8O A. to aSTEAR AAA. A/YYA -AZ VVVVVVV /VVMVVVN AYYYY/MA. A/VVVVVVVN foo;6 Aderalized/VVVVYVVVVA. 90 8o 7O 6o ao 4o 3o 2o ?o oozayyzerolyzed APOLYWAA OA Coaoa YaYaar Adol. Ywata oar Coao Yafear inventor : Gaetano F. O'Alelio. 9 (AEO. Patented Oct. 26, 1943 - 2,332,900 UNITED STATES PATENT OFFICE 2,332,900 SYNTHETIC COMPOSITION COMPRISING HYDROLYZED, ACETALIZED, AND/OR KE. TALZED POLYMERS OF ALLY ESTERS Gaetano F. D'Alelio, Pittsfield, Mass, assignor to General Electric Company, a corporation of ew York application July 23, 1940, Serial No. 346,981 4 Claims. (C. 260-66) This invention relates to the production of new compositions may be prepared by partially hy materials having valuable and characteristic drolyzing (saponifying) a mixed polymerization properties that make them especially suitable for product of two different vinyl esters (or a vinyl use in industry, for example in molding, laminat ester and an ester of acrylic acid, each of said ing, coating and adhesive applications, and for 5 esters having a single other purposes. The invention is concerned more particularly with the production of composi CBecC tions of matter comprising an acetalized, a ketal N ized or an acetalized and ketalized product of grouping and no other polymerizable grouping, polymerization of a polymerizable mass compris 0 and reacting the partially hydrolyzed product ing at least One ester selected from the class con with an aldehyde or a ketone to introduce acetal sisting of allyl esters and their homologues. or ketal groups into the product. In such Such esters may be described more specifically acetalized or ketalized products the reaction as esters containing the grouping takes place between the aldehyde or ketone and the vinyl alcohol part of the copolymer, which R. R. alcohol results from hydrolysis of the vinyl ester ch-t-t- portion of the copolymer reactant. k Taking vinyl chloride and vinyl acetate as ill where R is a member of the class consisting of lustrative of the compounds previously suggested hydrogen and hydrocarbon radicals (e. g., alkyl, as suitable for forming a copolymer that sub aryl, aralkyl, alkaryl, hydrocarbocyclic, etc.) and sequently might be acetalized or ketalized, the R’ is a member of the class which is the same following structural formulas illustrate the steps as R and in addition a halogen atom. For pur in the production of the acetal derivative: pose of brevity in describing the invention the Copolymer reactant before hydrolysis term “allyl ester' is used generally hereafter 25 -CH-C-C-C-CH-CH-CH-CH to designate both the parent allyl ester and the homologues thereof. bi (bcoch, (bcoch, & The scope of the present invention also in vinyl vinyl vinyl vinyl cludes compositions comprising the product of chloride acetate acetate chloride reaction of a substance comprising a 30 After hydrolysis N / C=O-containontaining bi bH &H by organic compound selected from the class con -- it still sisting of aldehydes, ketones and mixtures of al 35 After formalization dehydes and ketones with a substance compris-, ing a hydrolyzed copolymer of a plurality of co stretty-eirbi 8-CH-) bi polymerizable materials, at least one of which is an allyl ester. In the production of the latter It will be noted that in this acetalization reaction compositions the other organic compound (or 40. a six-membered ring is formed. Such a ring is compounds) that is copolymerized with the allyl produced regardless of the acetalizing or ketaliz ester prior to hydrolysis and acetalization, ketal ing agent employed. ization or acetalization and ketalization prefer I have discovered that synthetic compositions ably is a compound selected from the class Con which are different form, and in many respects 45 Superior to, Organic artificial masses heretofore sisting of ketones, ethers and nitriles each hav known can be prepared by acetalizing, ketalizing ing at least one or acetalizing and ketalizing a partially or com / pletely hydrolyzed product of partial or complete CH-scC polymerization of a polymerizable mass compris grouping and unsaturated alkyl resins obtained 50 ing an allyl ester (e. g., diallyl oxalate, allyl by esterifying a polyhydric alcohol with an alpha, acrylate, diallyl maleate, etc.); or by acetalyzing, beta polycarboxylic acid containing aliphatic un ketalizing or acetalizing and ketalizing a par saturation between the alpha and beta carbon tially or completely hydrolyzed product of partial atoms. or complete copolymerization of a plurality of co It has been suggested heretofore that synthetic polymerizable materials including at least one 2 2,882,900 allyl ester. The following structural formulas compounds copolymerizable therewith, for ex illustrate the formation of these new synthetic ample Organic compounds containing a single compositions, more particularly the production / of an acetalized, specifically formalized, deriva CarC tive of a polymer of allyl oxalate as I postulate 5 the reactions involved: grouping or containing at least one / Polumeric body before hydrolysis CHC N O grouping and one or more other polymerizable groups, e. g., one or more additional CH=C groupings. I then cause the hydrolyzed poly 5 meric body to react with a N C=O-containing / -ch-bH-CH-bti-CH-CH-CH-bt Organic compound selected from the class con After hydrolysis sisting of aldehydes, ketones and mixtures of aldehydes and ketones until at least some of the -CH-CH-CH-CH-CH-CH-CH-CH hydroxyl groups of the hydrolyzed polymer have (HOH &H.OH bitoh &H,0H been replaced by the corresponding acetal, ketal Allyl allyl allyl allyl or acetal and ketal groups. For example, I may alcohol alcohol alcohol alcohol lx 25 hydrolyze the polymeric substance to at least 10 per cent, more particularly from 25 to 100 After formalization per cent, of that theoretically possible and then -CH-CH-CH-CH-CH-CH-CH-CH acetalize, ketalize or acetalize and ketalize the bH, &H, 3B &B, hydrolyzed polymer until at least 10 per cent of 30 the hydroxyl groups of the hydrolyzed polymer (-CH-) (-CH-) have been replaced by acetal, ketal or acetal and It will be noted that the above formalized hy- . ketal groups. In some cases, for instance where drolysis product of polymeric allyl oxalate con the resistance of the product to water is of sec tains an eight-membered ring. The differences Ondary consideration, the hydrolyzed polymer between an acetalized, ketalized or acetalized and may have Only a minor proportion (that is, less ketalized product of hydrolysis of a polymeric than 50 per cent) of its hydroxyl groups replaced vinyl ester (or a copolymer of a vinyl ester and by acetal, ketal or acetal and ketal groups. For another polymerizable organic compound) and most applications, however, it is usually desirable an acetalized, ketalized or acetalized and ketal that at least 50 per cent, say 60 to 100 per cent, ized product of hydrolysis of a polymericallyl 4. of the hydroxyl groups of the hydrolyzed polymer ester (or a copolymer of an allyl ester and an be replaced by acetal, ketal or aceta and ketal other compound copolymerizable therewith) at groups. Particularly valuable products are ob once are apparent from a comparison of the tained when the polymeric body is hydrolyzed above formula for the formalized product of to from 60 to 100 per cent of that theoretically hydrolysis of polymerized allyl oxalate with the possible and the hydrolyzed polymer is acetalized, formula for the formalized hydrolysis product ketalized or acetalized and ketalized until from of copolymerized vinyl chloride and vinyl acetate, 75 to 100 per cent of the hydroxyl groups of the which latter contains a six-membered ring. hydrolyzed polymer have been replaced by the When an ally ester having one 50 corresponding acetal, ketal or acetal and ketal / groups. CH=C In order that those skilled in the art better grouping and at least one other polymerizable may understand how to practice this invention, grouping is polymerized, cross-linkage occurs. the following more detailed description is given: It was quite surprising and unexpected to find 55 Preparation of polymeric body that such cross-linked polymers could be acet In effecting polymerization of a polymerizable alized, ketalized or acetalized and ketalized par mass comprising as an essential component an ticularly in view of the fact that these materials allyl ester or an allyl ester and at least one other are infusible and substantially insoluble in all organic compound copolymerizable therewith, the the ordinary solvents. I have also found that mass is polymerized in the presence or absence such reaction products of a hydrolyzed, poly of a polymerization catalyst, e. g., benzoyl per merized allyl ester with an aldehyde, a ketone Oxide in a concentration within the range of 0.1 or a mixture of an aldehyde and a ketone, as to 2.0 per cent by weight of the whole, and at well as acetalized, ketalized or acetalized and normal or at elevated temperatures, e.g., at from ketalized cross-linked copolymers produced from room temperature (20 to 30' C.) to 130° C. a polymerizable mass comprising an allyl ester Ordinarily I use temperatures within the range and another organic compound (or compounds) of 60 to 120° C. in causing the mass to polymer copolymerizable with the allyl ester, are suff ize. Additional examples of polymerization cata ciently thermoplastic that, unlike the starting lysts that may be used are given in various co polymeric body, they can be molded under heat pending applications of mine, for instance in and pressure to a desired shape.
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