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Patented July 16, 1946 2,404.20‘ UNITED STATES“ PATEN T . OFFICE 18.104.22.168 coronmas or mm nsnzmm Ann vnwr. scam-am ' Gaetano r. D’Alelio, manna, mm'm a» General Electric Company, a corporation of New York No Drawing. Application June 243, 1942, ‘ 1 N0. 448,158 ' ‘30mins. (Cl- 280-86) 2 This invention relates to the preparation of Extensive experiments carried out on the poly merization of divinyl benzene in a dialkyl ben zene indicate that an insoluble, infusible resin is synthetic resin compositions and more particu- ' larly to the preparation of heat-convertible, solu ble,‘ fusible copolymers of divinyl benzene. obtainedv as a gel when ordinary polymerization‘ methods are employed. This gel formation or precipitation takes place in a very short time, e. g., 15-20 minutes. The extreme sensitivity of It is known that polymerization of compounds possessing more than one terminal CH2=C< grouping; providing the system is not conjugated, results in the formation of a cross-linked, insol this resin precludes its use in industrial applica uble, infusible polymer. Examples of such com pounds are glycol dimethacrylate, diallyl suc 10 cinate, diallyl phthalate, diallyl maleate, allyl acrylate, diallyl oxalate, dimethallyl'ether,.etc. Likewise, such polymers as a rule are rather brit tions. By means of this invention I may cause the copolymers to be formed at a much slower rate. thus providing a greater permissible devia tion from any calculated time required to give a maximum yield of partial polymer. The time tle and low in ?exural and impact strength. Also, copolymers made with such compounds contain 15 required depends upon the type as well as the amount of vinyl compound and catalyst present ing more than one CH2=C< group are infusible in the solution. I have found that, by varying and insoluble to a degree proportional to the my conditions. a partially polymerized product amount of compound containing a multiplicity may be obtained in whatever time is desired. of CH:‘=C< groups. Such copolymers ~cannot be molded once formed or cast. Divinyl benzene 20 This behavior is entirely unexpected and unpre polymerized in the usual manner acts in the same _ fashion. When this compound is polymerized an dictable as can be seen from the following ex amples. _ In particular in Example 1 the divinyl benzene solution containing 50 parts divinyl ben insoluble, very hard, infusible, nonworkable mass is obtained. copolymers of divinyl benzene’ which - zene and 0.5 part benzoyl peroxide gelled in 17 nutes and, whereas the vinyl acetate‘ contain are known are insolubleand infusible. Although 25 ing the varied quantities of benzoyl peroxide the copolymeric products of this invention are given in that example polymerizes with almost ' fusibleand soluble, it is a unique property of these copolymers that they possess heat-convertibility , and may, therefore, be converted to an infusible, insoluble material. I have now discovered that divinyl benzene may be partially copolymerized to a soluble and fusi ble heat-convertible copolymer mass, thus mak ing available for commercial use a product here tofore inapplicable. The process by which a sol uble, fusible partial polymer of divinyl benzene may be isolated from a dialkyl benzene having at least two carbon atoms in each alkyl grouping comprises polymerizing the solution of divinyl explosive violence at re?ux temperatures, the mixture of the two had an increase in gelation time from 17 minutes, through 30 and 60 min-‘ 80 utes all the way to 240 minutes. The actual polymerization of the divinyl ben zene in its solution in a dialkyl benzene is car ried out as previously indicated in the presence of both a catalyst and an inhibitor of polymeriza 85 tion. Any suitable method may be employed. However, I prefer to cause polymerization under the influence of external heat in the presence of a catalyst for a period substantially less than benzene in a dialkyl benzene in the presence of 40 that required to cause gelation of ‘the solution. For purposes of economy and convenience I pre both a vinyl-type compound, which acts as an fer to use re?ux temperature and atmospheric inhibitor, and a catalyst of polymerization, for pressure although other elevated temperatures a time less than that required to cause separation of the polymer. The dissolved partial polymer is and pressures ranging from subatmospheric to then precipitated by the addition of a non-sol- 45 superatmospheric pressure may be used. The partial copolymer of divinyl benzene may be pre vent or by evaporation of the volatile constit cipitated from the dialkyl benzene by the addi uents. tion of some non-solvent, e. g., methyl alcohol, Present production of divinyl benzene (mono ethyl alcohol, glycol, etc, mer) is carried out in such a manner that the resulting product is an inseparable mixture of 60 For polymerization catalysts in the polymer ization of divinyl benzene I may use ozone, ozon ides, inorganic super oxides such as barium per ' oxide, sodium peroxide, etc., aliphatic acyl per oxides, e. g., acetyl peroxide, lauryl peroxide, - which there has been no use up until the present stearyl peroxide, etc., peroxides of the aromatic about 20—30% divinyl benzene in diethyl benzene. The present invention isv of special interest be cause it utilizes this inseparable mixture for ‘me. acid series, e. g.. benzoyl peroxide, etc.,‘, ketone ' ' 9,404,990 ' . v " ' 4 methylene malonic acid. malonic acids, e. g., monoethyi ester, monopropyl e. g., acetone peroxide, triacetone peare. ‘peroxides. joxide, alkyl derivatives or hydrogen e, diethyl peroxi peroxide. monomethyl ester, ester, dimethylester. diethyl ester,. monobutyl > ester,vdipropyl ester, monophenyl ester, dipheny'l ester, etc., and homologues oi! the above radicals e. g., ethyl hydrogen peroxid ; etc., mixed organic peroxides, e. g., acetyl benzoyl ‘ peroxide, etc., various per compounds such as and their related compounds. 1 perborates, persulfatcs, perchlorates, etc., alumi In order that those skilled in the art may better as the .halides, e. g., aluminum understand the teachings of the invention the ' chloride, organic and inorganic acids such as following examples are given. metal compounds ‘ methacrylic, hydro?uoric, etc., 10 Example 1 , num salts such of the unsaturated acids as, for instance, cobalt and manganese resinates, linoleates, maleates, benzoyl ‘ Gelation times were determined for a solution ; etc., hydrogen peroxide, etc. However, of divinyl benzene in diethyl benzene for increas Any suitable ‘ peroxide is a preferred catalyst. general, ing concentrations of vinyl acetate. j amount of catalyst may be used but, in 16 1 the catalyst concentration will be within the Parts or Divinyl Vinyl Benso l Gelation 1 range of 0.1-2.0% by weight of divinyl benzene._ 23% sol'n benzene acetate peroxi 0 time I of the partial As inhibitors in the preparation may use with polymerizates or this invention 1 divinyl aryl derivatives compounds of the type Pam Part: 211 so ...... .. 211 so 5 0. so 10s 25 25 0. 2a 10s 7 25 V15 0.50 ‘ Pam Minutes 0.50 11 so - so 240 OHFC . \x' The inhibiting e?ect of vinyl acetate is readily . a member of the class consisting of where X is hydrogen and ‘halogen and alkyl, aryl,‘ carbo alkoxy, carboaroxy. radicals, including those seen from the foregoing chart. Inporder to isolate the soluble, fusible partial _ polymer from any of the above compositions the re?ux times in each case are reduced sufficiently radicals in which one or more hydrogen atoms to‘ prevent gelation. The viscous solution of the partial polymer is poured into methanol and the have been replaced by some substituent grouping, e. g., a halogen and x' is a member of the class ‘ consisting of .halogen and aryl, carboalkoxy, 80 precipitate removed, dried and ground. The nitrile, and acyloxy radicals includ product so obtained is soluble in the usual hydro ing substituted aryl, carboalkoxy, carboaroxy and carbon solvents and completely fusible. The polymerizate contains some vinyl acetate inter acyloxy, e. g., halogen-substituted. Illustrative examples of the radicals represented polymerized with divinyl benzene partial polymer. ‘ carboaroxy, by X and X’ in the above formula are alkyl, e. g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, benzyl, phenethyl, etc., aryl, e. g., phenyl, tolyl, xylyl, xenyl, naphthyl, ethylphenyl, methylnaphthyl, Example 2 I may also make a partial copolymer using a composition of the type: - 40 Styrene ___________ -1 __________________ __ 50 etc., carboalkoxy, e. g., carbomethoxy, carbo Divinyl benzene (217 parts of ‘23% solution ethoxy, carbopropoxy, carbobutoxy, carboiso in diethyl benzene)‘ __________________ -_ 50 carbocyclohexoxy, ' butoxy, carbocyclopentoxy, carbochloroethoxy, carbobromocyclopentoxy, etc., carboaroxy, e. g., carbophenoxy, carbotoloxy, carboxyloxy, carbonaphthoxy, Benzoyl peroxide _____________________ ___ ‘ 0.5 45 carboxenoxy, carbo?uorophenoxy, etc., acyloxy, e. g., acetoxy, ' , propionoxy. " ' Parts by weight butyroxy, isobutyroxy, cyclopentan whichingredients are re?uxed short oi’ gelation, the polymer precipitated and isolated as in-Ex ample 1. ' In preparing the heat-convertible, soluble, ins-1, oxy, cyclohexanoxy, benzo-oxy, toluoxy, naphtho 60 ible copolymers of divinyl benzene, I'may like wise use auxiliary inhibiting materials such as oxy, phenacetoxy, phenpropionoxy, chloropro carbon tetrachloride, copper, sulfur, hydroxyl pionoxy. bromocyclopentanoxy, ?uor'obenzo-oxy, compounds, amines, as disclosed in my copend iodotoluoxy, etc., and homologues of the forego ing application Serial No. 448,158, ?led concur», ' ing radicals. Illustrative examples oi! the compounds which 55 rently herewith, now U. 8. Patent 2,363,836, is sued Nov. 28, 1944, or- certain allyl derivatives, I may use to prepare the soluble, fusible copoiy for example, their alcohols, aldehydes, ketones, mers of divinyl benzene are: vinyl halides,'e. g., esters, etc., many examples oi! which are given vinyl chloride, vinylidene chloride, vinyl bromide, in my copending application Serial No. 448,155, vinyl iodide, vinylidene bromide, etc., acrylic ‘acids, e.,g., acrylic acid, methacrylic acid, chloro 60 now U. 8. Patent 2,378,195, issued June 12, 1945, both applications being assigned to the same as signee as the present invention.v Typical exam ples are given below. acrylate, ethyl acrylate, methyl chloroacrylate, pmpyl acrylate, isopropyl Example 3 acrylate, butyl acrylate; isobutyl acrylate, iso 65 butyl methacrylate, bromoisobutyl acrylate, phenyl acrylate, ?uorophe'nyl acrylate, benzyl acrylate, benzyl methacrylate, ethyl chloroacry late, etc., aryl ethylenes, e. g., styrene, methyl _ Parts by weight Divinyl benzene (196 parts or 23% solu tion in diethyl benzene) ....... -.-..--.‘..- 45 Styrene _ -styrene, tolyl ethylene, bromotolyl ethylene, etc., 70 Allyl chloride Benzoyl peroxide vinyl esters, e. g., vinyl acetate, vinyl propionate, - 5 *; 4'5 0.26 vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl cyclopentanoate, vinyl cyclohexanoate, vinyl The above ingredients were heated at the boil ing point of‘the reacting mixture for 55 minutes. benzoate. vinyl methylbenzoate, etc., nitrile‘ de The solution containing the partial polymer was rivatives of acrylic acid, e. g., acrylonitrile, meth 75 poured into methanol. The product was tritu ' acrylonitrile, etc., malonic acids and esters, of . aeoqaao 5_ rated, dried and ground. when submitted to a hot plate test at 140° C., the partial polymer was Example 7 v easily fusible. , > Parts by weight Styrene ____ Example 4 ‘ 90 Divinyl benzene (43.5 parts or 23% solu Parts by weight Styrene ______________________ ___ ______ __ 2.5 tion in diethyl benzene) ______________ __ 10 - Divinyl benzene (206 parts 01' 23% solu Benzoyl peroxide ___..______-_________-___ tion in diethyl benzene) _______________ __ 47.5 0.50 The above ingredients were heated atthe re ?ux temperature of the reacting'mix'ture for a period of 15 minutes. The partial polymer was Allyl acetate _________________________ __ 47.5 I Benzoyl peroxide __________________ __’___ Methallyl alcohol ___.-. _________________ __ 10 0.25 The above ingredients were re?uxed for 35 separatedirorn the solvent by pouring the viscous. minutes. The product was precipitated by pour-' solutioninto methanol. The precipitated prod ing the viscous solution into methanol, thorough uct was triturated, dried and ground. The usual ly triturated, and ground. The partial polymer fusibility was displayed on the hot plate at. ?owed readily when placed on a hot plate at 15 140° C. 140° C. What I claim as new and desire to secure by ' Example 5 . . Letters Patent of the United States is: 20 polymerized product produced in accordance Styrene ; _____________________________ -1 12.5 Divinyl benzene (163 parts of 23% solu with claim 2. v ‘ ‘ 2. The process which comprises polymerizing tion in diethyl benzene). ____________ __ 37.5 a composition comprising a solution of divinyl ' benzene in a dialkyl benzene having at least two ‘ Allyl alcohol ____' ________ __~ ___________ __ 37.5 Benzoyl peroxide _____________________ __ . l. The heat-convertible, fusible, partially co-. Parts by weight 0.25 25 carbon atoms in each alkyl grouping, in the pres The above ingredients were heated/at the re ?ux temperature for 40 minutes. The partial ' polymer was precipitated by pouring the viscous solution into methanol. The product was trit urated, dried and ground. At the temperature. ence of both vinyl acetate and a catalyst for the polymerizationbfor a periodless than required to cause gelation of the solution, and isolating ‘ .‘ the heat-convertible, fusible, partially polymer-vv ized product, the vinyl acetate and divinyl ben of the hot plate, e. g;, 140° C., the resin was 30 zene being present in the said solution in an easily fusible. » amount, by weight, corresponding to from 5 to 75 parts of the former to‘ from 50 to 25 parts 01' ~ Example 6 the latter. Parts by weight Styrene _______________________________ __ 75 Divinyl benzene (109 parts of 23% solution ' in diethyl benzene) __________________ _- 25 Methallyl alcohol ____1 _________________ __ 25 85 . 3. The process‘ which comprises polymerizing, under heat, divinyl benzene in a. diethyl benzene solution in the presence of benzoyl peroxide and vinyl acetate for a period of time less than re quired to cause gel'ation of the solution, the vinyl The above ingredients were heated at the boil 40 acetate and divinyl benzene being present in the said solution in an amount, by weight, corre ing temperature of the reacting mixture for 20 Benzoyl peroxide ______________________ __ 0.5 sponding to from. 5 to 75 parts of the former to The partial polymer was precipitated ' from 50 to 25 parts of the latter, and thereafter by pouring the viscous solution into methanol. the heat-convertible, fusible, partial It was then triturated, dried and ground. The 45 isolating polymer of divinyl benzene so produced. polymer was fusible at‘ 140° C. 0n the hot plate. GAETANO F. D’ALE'LIO. minutes.