Патент USA US2411599код для вставки
v Patented Nov. 26, 1946 I ., 2,411,599 ' UNITED STATES J‘PATENT- OFFICE _ t I \’\2Au’5:91~z rnocass ‘ I. I 7 William J. Sparks, ‘Elizabeth, and Anthony H. . to Standard Gleason, West?eld, N.~J., assignors Oil Development Company, a corporation of Delaware No Drawing. Application November 9, 1940, Seriai No. 365,014 '5 Claims. (01.- 204-162) 2 _ and relates particularly to heteropolymers or in- > terpolymers of an unsaturated ester of the type ~ of methyl acrylate with an iso-ole?n of the type . ~ . ment (under pressure it necessary) at the reaction temperature by exposure of the mixture to ultra violet light, or by treatment with peroxides, par ticularly organic peroxides such as benzoyl per oxide, or by the use of both ultraviolet light and This invention'relates to polymeric materials‘ of isobutylene. Among the'more easily ‘produced synthetic poly peroxide catalysts. , ' ‘ Thus an. object of the invention is to hetero-1 mers are the polymers of methyl acrylate. These polymerize together an' unsaturated ester such polymers are readily produced by heating the as methyl acrylate with an iso-ole?n such as iso-_ butyiene in the presence of a catalyst such as‘ 10 . catalyst, or by exposure of the monomer to ultra ultraviolet light or a peroxide, to produce a tough, violet light. By these means it is possible to pro duce poly-methyl-acrylates which are hard, clear, " ?exible, strong, transparent, white resin. Other objects and details of the‘invention will be ap transparent, thermoplastic resins. Also, iso- > parent from the following description. , butylene can be readily polymerized by a low > In'practicing the invention the ester and the temperature ,. technique into poly-isobutylenes methyl acrylate monomer with a peroxide as a iso-ole?n are mixed in a container under such which range in character from a heavy oil to a pressure as is required to keep the iso-ole?n liquid rubber-like substance, according to the molecu at room temperature. A small quantity of an lar weight.’ These polymers are produced by organic peroxide such as benzoyl peroxide may cooling theisobutylene to low temperatures, usu be also incorporated into the mixture, and the ally below --10° C. and preferably below -40° C., 20 whole is allowed to stand in the presence of ultra and thereafter treating them with a catalyst such violet light for a substantial period of time to as boron tri?uoride. These two polymers are produce the desired lnterpolymer. widely di?erent in their physical characteristics, and it is very desirable to obtain materials hav Example ‘I I ing characteristics intermediate between those of the respective polymers. To the present, how- ' ' A mixture 01' 25 parts of monomeric methyl ever, it had not been found possible to combine. acrylate, having the formula , , these two substances. The respective polymers are mutually incompatible to mixing at ordinary temperatures, since neither one dissolves in nor 30 combines with the other. Also at the low tem peratures required for thepolymerization of iso butylene, the methyl acrylate is non-reactive, and at the normal room temperatures, the iso butylene is substantially nonreactive with boron tri?uoride and like catalysts to produce a high molecular weight polymer. with 25‘ parts 0! liquid isobutylene,_ having the formula ' r /’ ~ Hz . The present‘ invention provides a simple meth od for producing a heteropolymer of the iso and 1 part of benzoyl peroxide was prepared in ole?n with the ester by which a new and im 40 a glass container, under suil‘icient pressure .to proved polymer is ,obtained. This new polymer keep the isobutylene in the liquid state, and the . is an lnterpolymer or heteropolymer of the ester container was sealed to maintain the pressure. ‘ and iso-ol'e?n, characterized by greater toughness and strength than the poly-ole?n, and much less brittleness than the poly-ester. Furthermore, _ The container with the included mixture was then exposed to light rays from a mercury vapor lamp for a period‘of approximately 50 hours.‘ At the close of this period, a substantial strati? cation had occurred in the container, a portion being a solid polymer, the remainder being liquid cording to'the constituent substances. The proc isobutylene. The container was then opened, the ' ess'of-the invention heteropolymerizes the un saturated ester withpthe iso-ole?n by av treat-l v50 excess isobutylene removed, and the solid poly ' the product is a clear, transparent, ?exible, water 'white resin, having- more or less elasticity ac 2,411,599 ' . 3 mer separated; The solid polymer wasdissolved In this instance also a tough, ?exible, strong, in benzol and reprecipitated from the benzol ‘clear, white resin was obtained. A proximate solution by the addition thereto or. a substantial analysis of this resin indicated that the methyl quantity of methyl alcohol. The precipitate was ‘ acrylate had interpolymerized' with the tryptene then dried for a substantial number of hours at’ 5 , in the proportion of approximately 7.3 parts of temperatures between 90 and ‘100° C. under a - methyl acrylate to 1 part oi’ tryptene (mole ra vacuum or 2'! inches. A proximate analysis of a tio 8.5;1). - . sample or the polymer showed the following com _ Example IV position: i , ‘ ' Per cent ' Carbon' lHydrogen 62.43 ‘ > .10 ‘.A similar reaction occurs with 2 methyl bu _ tene-l, having the formula‘ _ 8.70 ' >Oxygen (by di?erence) ___________ __,.-- 28.87 carom-(hon, Ha I For isobutylene the corresponding values are: ' ' .15 A mixture of approximately equal parts of methyl acrylate and the 2 methyl butene-l was .pre pared as in Example I and treated over a similar 85.7 ' Per cent Carbon Hydrogen 14.3 prolonged period with ultraviolet light. In this also atough, ?exible, strong, clear resin For this particular“ sample or methyl acrylate the 20.' instance was obtained on whichv ' approximate analysis corresponding values are: . Carbon . showed the methyl acrylate to be present with the 2 methyl butene-l in the proportion of 3parts methyl acrylate to 1 part of the 2 methyl butene-i Per cent 54.4 ' Hydrogen ' 8.98 (or a mole ratio of 5:2). . Oxygen (by diil'erence) ________________ __ 38.62 25 ' " ' Example‘! Based upon the relative hydrogen values, the co polymer contains approximately 23.5% of iso butylene, and based upon the relative carbon between methyl acrylate and dimeth'allyl, having values, the copolymer contains-25.5% isobutylene, the formula A similar heteropolymerization reaction occurs the respective polymerizates then being present 80 in the heteropolymer in the ratio of approximately. 3 parts of methyl acrylate to 1 part of isobutylene. The interpolymer as thus produced by the A mixture of approximately equal parts. of methyl 'above polymerization procedure is a clear. ‘35 acrylate and dimethallyl were prepared'as in Ex tough, strong resin, completely insoluble in ample I and treatedunder ultraviolet light for ‘a water or aqueous liquids, and strongly resist . ant to acids and alkalies. It is soluble in benzcl ' similar time interval. A similar tough, ?exible,. strong, clear, white resin was obtained which was and aromatic hydrocarbon liquids generally but found to be insoluble in any available solvent in insoluble in oxygenated organic solvents such as - eluding alcohols, ethers, esters and hydrocarbons the alcohols, ethers, aldehydes, and organic acids. 40 as well as chlorinated hydrocarbons. ‘ ' ' The invention is not limited to the heteropoly Example VI merization of methyl acrylate with isobutylene', but may be applied to a considerable number 01' ' other acrylate type esters and iso-ole?ns. Example [I A similar mixture 01' methyl acrylate was pre pared with chloro formula ‘ ethyl vinyl ether‘, having the‘ Methyl acrylate and- dimethallyl I ether react 45 similarly to the reaction‘ in Example I and Exams ple V. A mixture or approximately equal parts _‘ or methyl acrylate with dimethallyl ether, hav ing the formula cHl==o—cH,-o-—clrr-c=cm ' I i I I 60 i ‘HI ‘ Hr . . was prepared as in Example I and treated for a‘ . similar length of time with ultraviolet light. In this instance also a tough, elastic, strong, clear in approximately equal parts and treated ‘with 55 ‘resin was obtainedv which also was found to be insoluble in any of the ordinary solvents. ultra-violet light for a similar period or time. This mixture likewise was found to interpolymer Example VII v ize to yield a clear resin, and a similar‘ proximate analysis showed that-the methyl acrylate and the A similar reaction occurs-between methyl acry ether interpolymerized in the ratio of approxi 60 late and methallyl alcohol, having the formula mately 3 ‘molecules or methyl acrylate to 1 or the CHFC-CHJOH chloro ethyl vinyl ether. This product likewise is a tough, strong, ?exible, clear, white resin. . at A mixture of methyl acrylate and methallyl al Example III ‘35 cohol ‘in approximately equal proportions was The reaction similarly proceeds with methyl prepared as in Example I and subiectedto ultra acrylate and tryptene, having the formula 6H; /CH! CHr-é-—C=CH, . H; A similar mixture of methyl acrylate and tryp violet light for a prolonged time interval as in Example I to produce a similar tough, elastic, strong, clear, white resin in which a similar prox 70 imate analysis showed that the methyl acrylate was present in the proportion of 2 parts to 1 part of the methallyl alcohol (or mole ratio of about‘ 3:2). This copolymer is readily soluble in the tene was prepared as in Example I and treated alcohols thus distinguishing it"from the m a similar time interval with ultraviolet light. 75 lower pure polyester of methyl acrylate. w 0 2,411,599 the 3 to 2 ratio for methyl acrylate and methallyl Example VIII , alcohol under ultraviolet light. A similar reaction occurs between methyl acry ~ Example X late and methallyl acetal, having the formula Similarly methyl methacrylate and chloro ethyl vinyl ether react under ultraviolet light to form C a CH: _ a copolymer similar to that obtained in Example OCHr-C=GHI II containing approximately 3 percent of chlo rine, in which there, appear to be approximately H1 As in previous examples, a mixture of approxi l0 11 molecular parts of the ester with 1 molecular part of the ether. Other tests show. that the mately equal parts of methyl acrylate and the sec methyl methacrylate reacts in generally the same ond constituent, in this instance methallyl acetal, manner to produce similar heteropolymers as in, ' was prepared in approximately equal parts and the case of the simple methyl acrylate. However, treated with ultra-violet light as before. The the reaction under the in?uence of ultraviolet reaction yielded a similar strong, ?exible, clear, ‘ light is noticeably slower, but it is generally more white resin which, however, was found to be in satisfactory, in the presence of peroxide cata soluble in any of the usual solvents. lysts, at elevated temperatures. A similar experiment utilizing a mixture of These resins, being thermo-plastic, are par ocH,-c=cm ' ' methyl acrylate in approximately equal parts with ticularly well adapted for the preparation of 3 methyl butene-l, having the formula molding compositions by themselves or in com CHr-CH-CH=CH1 ' bination with a wide range of fillers, such as the ' inert pigments including ferric oxide, carbon H8 black, chrome green. zinc oxide, lithopone, did not yield a polymerizate, indicating that the absence of the iso-oleiinic structure prevented the ‘barytes and the like, as well as the various or-. occurrence of this reaction. Similarly as the size of the molecule ‘increases, the ratio of interpoly merization decreases. This is well shown in the cellulose ?bers generally and the like, either’v ganic ?llers including paper, cloth, wood ?our, with or without the various dyes which may be applied to the various pigments. vor with the var ious oil soluble dyes which are soluble in the case of tryptene as above indicated, in which the high molecular weight of the tryptene resulted in ‘a much lower proportion of hydrocarbon to 30 present resins. Similarly, being clear, white resins, these materials are useful for transparent molding compositions including lenses, various Similar experiments were conducted with di items of tableware and decorative articles either“: pentene and producedonlynegligible quantities of polymers, possibly because of the high molecu 35 in the clear, white of the pure resin or the clear 1 colors. produced'by dyes or the opaque colors lar weight of the dipen'tene. Similar experiments produced by ?llers with or without pigments, were conducted with safrole, having the formula methyl acrylate in the heteropolymer. The_ resins are good bases for '7 paints, enamelsyvarnishes, _etc.; are good elec trical insulators and are useful for molded in lakes or dyes. 40 sulators either with or without insulating ma Q11. terial fillers. and are particularly useful as re _ placement material for uses where physical properties of the type processed by-leather are desired, since they are sumciently ?exible and 45 'elastic'to serve as leather substitutes, and in and with citronellal, having the formula some instances as replacement for rubber where less elasticity‘ than is characteristic of rubber, even when rubber is heavily loaded with pigment but in these instances also little or no‘interpoly fillers, is desirable. mer was obtained, apparently because of the high 50 By the process of the invention there are thus molecular‘ weight of the substances or possibhr obtained a series of new and useful hetero because they do not contain the polymers in the form of resins of high strength, high toughness, ?exibility, low brittleness, low .solubility in solvents generally and a clear, trans parent character which are particularly useful for lacquers, adhesives, molded articles and the like. grouping. ‘ When dimethallyl is one of the. reacting com ponents, both of the double bonds therein appear to react giving cross-linkages between chains and While there are above disclosed but a limited resulting. in insolubility of the heteropolymer. number of'embodiments of the invention, it is Similar copolymerizations may be effected with methyl methacrylate but‘ the reaction is gener 60 possible to produce still other embodiments ally slower than that with the methyl acrylate, ' without departing from the inventive concept herein disclosed, and it is therefore desired that in spite of the supposed greater activity of the only such limitations be embodied upon the ap methacrylate. However, in this instance the polymerization by 'the ‘use of a peroxide‘ catalyst 1 isgenerally satisfactory. ’ ' ‘ pended claims as are stated therein or required ‘I 05 by the prior: art. 7 Example IX A ‘mixture of approximately equal parts of methyl methacrylate andmethallyl alcohol was 4 prepared with‘ a‘ small quantity of benzoyl per oxide and heatedlto a temperature of 85° C. for This reaction was found to yield ‘ several hours. aheteropolymer in which the methallyl alcohol 1 and methyl methacrylate were present in an ap The invention claimed is: - 1. The polymerization process comprising the steps in combination of mixing a methylacrylate and an alpha ole?n in liquid form at room tem- - perature and interpolymerizing the mixture by the application thereto of ultra violet light to yield a high molecular weight, solid interpolymer of a methyl acrylate and an alpha ole?n. 2. The polymerization process comprising the proximately 1 to 1 'mole ratio as compared with 76 steps in combination of mixing a methylacrylate, ' 9,411,599 an alpha.- ole?n, and an organic peroxide in liquid . iorm'at room temperature and interpolymerizing the mixture by the application thereto of ultra violet light to- yield ahigh molecular weight. solid irlig?nerpolymer of a. methyl acrylate and an alpha. "3. The polymerization process comprising the -steps of mixing methylacrylate and isobutylene 0 . . 8 phenyl ether in liquid i'orm under pressure at’ Y room temperature and polymerizing the mixture by the application thereto of ultra violet'light to yield a high molecular weight, solid inter polymer of a methacrylate and a chlor ethyl phenyi ether. 5. The polymerization process comprising the steps of mixing methylacrylate and dimethallyl in liquid form under pressure at room tempera ‘ in liquid form under pressure at room tempera ture and polymerizing the mixture by the ap-‘ m ture and polymerizing the mixture by the appli plication thereto 0! ultra violet ‘light to yield a cation thereto of ultra‘ violet light to yield a high molecular weight, solid interpolymer 01' a high molecular weight, solid oopolymer 01' a methacrylate and isobutylene. ' 4. The polymerization process comprising the steps of mixing methylacrylate and chlorethyl 1'5 methaorylate and 'dimethallyl. WILLIAM J. SPARKS. - ANTHONY H. GLEASON.