Патент USA US2396261код для вставки
2,396,261 Patented Mar. 12, 1946 UNITED STATES PATEN' OFFICE 2,396,261 PRODUCTS Jesse Harmon, Wilmington, Del, assignor to E. 1. (iii ll’ont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 22, 19%, Serial No. 523,466 5 Claims. (Cl. 260—488) merization.” The designation “telomer" is de This invention relates to new halogen-contain rived from the Greek “te1os" meaning “end” and ing organic chemical products and to a process the Greek "mer” meaning “part.” “Telomers” for their preparation. More paticularly, this in differ from simple compounds or polymers in that vention relates to the reaction of vinyl acetate the end groups vof the chain formed from the with carbon tetrachloride and to the products vinyl compound are characteristic. They di?er obtained therefrom. from polymers or interpolymers in that they have It ‘is known that when an unsaturated com a lower molecular weight and in chemical and pound such as vinyl acetate is treated with‘a physical properties. They are usually liquids or peroxygen catalyst, polymers are obtained. Fur thermore, when a mixture of two or more un 10 semi-liquids. The broader aspect of telomeriza— tion is more completely described in pending ap saturated compounds, such as vinyl acetate and plication Serial No. 438,466 ?led April 10, 19%2. vinyl chloride is subjected to polymerizing con The reaction between carbon tetrachloride and ditions in the presence of a peroxygen catalyst, vinyl acetate can be carried out at any tempera interpolymers are formed. The macromolecules thus produced have physical properties which are of greater interest than their chemical prop erties. For example,‘such solid polymers or in terpolymers can be formed into ?bres and ?lms while the chemical properties are characteristic ture between room temperature (25° C.) and ap proximately 150° C. to produce the 1:1 addition product and liquid products having a plurality of vinyl acetate units and ends from one mole cule of carbon tetrachloride. A ratio of vinyl of the multiplicity of repeating groups present 20 acetate to carbon tetrachloride of between 10 to 3 and 1 to 10 parts by weight is employed in rather than reactivity of the molecule as a unit. this reaction. The reaction is preferably carried However, it has not previously been discovered out in the presence of from 0.01 to 5% (based that vinyl acetate can‘ be converted into liquid on the weight of vinyl acetate) of a polymeriza products of relatively low molecular weight by treatment under suitable conditions with carbon 25 tion catalyst, such as benzoyl peroxide, which is e?ective for the polymerization of vinyl acetate tetrachloride. and ineffective as a Friedel-Crafts catalyst. By An object of this invention is the production Friedel-Crafts catalysts are meant such com of compounds which are represented by the gen pounds as aluminum chloride or boron tri?uoride eral formula 30 as used in alkylation or acetylation reactions as 0 ClzF-CHzCH-J-Cl described in Chemical Reviews 17, 327-392 (1935) . 00011; The catalysts operable in the present invention have been designated “telomerization catalysts” in which n is an‘ integer. Further objects will in Hanford and Joyce copending application, appear from the description given hereinafter. These objects are accomplished by the follow 35 Serial No. 438,466, ?led April 10, 1942. The time for the reaction of carbon tetrachloride with ing invention which‘ comprises reacting vinyl vinyl acetate is not critical, being dependent acetate with carbon tetrachloride preferably in upon temperature, catalyst and the presence of the presence of a compound which is a cata an inert diluent such as benzene or isooctane. lyst for the polymerization of vinyl acetate and a non-catalyst for the 'Friedel-Crafts reaction. 40 When temperatures of approximately ‘70° to 80° , C. are employed, the reaction readily takes place The novel reaction products obtained by this at atmospheric pressure. When higher tempera invention can be represented by the general for tures are employed, the reactants are placed in mula a sealed container capable of withstanding the 45 autogenous pressure developed, or even higher pressures that may be employed. where n is an integer and in general has a value In the preferred procedure, the reaction is of from 1 to approximately 8. When n in the stopped when the major part of the low boiling above formula is unity, the compound is a simple ‘ vinyl acetate and carbon tetrachloride reactants addition product of carbon tetrachloride to vinyl 50 have been used and the products are concentrated acetate. However, where the value of n is greater by vaporization of the volatile unreadted carbon than unity, the compounds are not simple ad dition products. For simplicity, these latter com pounds have been called "telomers" and the proc ess for their production has been termed “telo tetrachloride and vinyl acetate. The reaction , ‘ product is not a single molecular species but is a mixture of structurallyhomologous compounds differing from one another by the number of vinyl 2 2,896,261 acetate units which comprise the chain between the chlorine and CCl: groups. For many appli cations, the mixture can be employed per se in corrected) when heated at a rate of 10° C. per minute. The analysis for this hydrazone was: I\_l:l6.4% (Dumas); calculated for asmuch as it is a mixture of functionally similar compounds of varying chain length. Further The reaction products obtained from carbon more, where the average number of vinyl acetate tetrachloride and vinyl acetate have chlorine which is capable of replacement or further reac tion by chemical ragents, for example, halogen can be removed by treatment with a methanolic solution'of hydrogen chloride followed by treat ever, the addition product of carbon tetrachlo ment withconcentrated aqueous alkali. ride to vinyl acetate and the lower molecular As catalysts which are useful in the promotion weight products, such as those having two or of this reaction, there can be used any catalyst three vinyl acetate units can be distilled at, re duced pressure.‘ Products having more than 15 effective for the polymerization of vinyl acetate eight vinyl acetate units tend to be solid. ‘ and ineffective in the Friedel-Crafts reaction. Useful catalysts include compounds having di This invention is further illustrated but not units present is large, for example, three to eight, the compounds are subject to decomposition when heated and it is, therefore, undesirable to subject such a mixture to distillation. How 10 limited by the following example in which the parts given are by weight. Example pounds such as diacyl peroxides such as benzoyl 20 Into a reaction vessel equipped with a re?ux condenser were placed 172 parts of vinyl acetate ~ and -769 parts of carbon tetrachloride. rectly linked oxygen atoms, e. g., peroxygen com After re peroxide, propionyl peroxide, lauroyl peroxide; dialkyl peroxides such as diethyl peroxide; other peroxides such as ascaridol, cyclohexanone per oxide, diethyl perdicarbonate hydrogen peroxide. tertiary butyl hydroperoxide, ozone, ozonides, ?uxing for a few minutes, 0.3 part of benzoyl per 25 etc. Other catalysts include amine oxides such , oxide was added, after which the temperature of as trimethylamine oxide; ultra-violet light in the the boiling mixture gradually rose from 73° to 84° presence of photo sensitizers such as diacetyl. C. over a period of ten hours. No additional rise mercury, alkyl iodides and acetone; and metal in temperature 'was noted when a similar addi alkyls. Especially useful when the reaction is tional amount of catalyst was added. After dis 30 carried out in an aqueous emulsion are water sol‘ tillation of unreactedvinyl acetate and carbon uble persulfates, perborates, and percarbonates, tetrachloride by heating on a water bath at a for example, sodium, potassium, or ammonium pressure of 20 centimeters of mercury (absolute), persulfate, perborate, or percarbonate. Emulsi a total ‘of 336 parts of a colorless, oily liquid refying agents and/or a buffer may be employed mained; When this liquid was subjected to vac .85 with a persulfate or a similar catalyst when an uum distillation, two principal fractions 'were aqueous system is used. Furthermore, oxidizable obtained. The ?rst fraction boiled at 62.5° C. at sulfoxy compounds such as bisul?te may be ad 0.9 millimeter and underwent no decomposition vantageously employed in conjunction with a upon standingfor several weeks. This material persulfate or similar catalyst in aqueous systems. was found to contain 59.3% chlorine. The cal 40 It is to be understood that carbon tetrachloride culated value for the chlorine content of the 1 and vinyl acetate can react to form the addition to 1 addition product of vinyl acetate to car product and products of low molecular weight bon tetrachloride, (CC13(CH2CHOCOCH3)CD is when no catalyst is present, however, the reac 59.1%. tion requires a longer period of time. For this The higher boiling product, which had a boil 45 reason, the addition of small amounts of a cat ing point of 107°. C. at 1.5 mm. pressure, had a alyst of the type hereinbefore mentioned is ad vantageous. " chlorine content of 43.0%. The calculated chlo rine content of a compound having two vinyl ace- ' The compounds obtained by the process of this tate units combined with one carbon tetrachlo invention are useful as plasticizers, solvents, and 50 in other applications. Forv many such uses, sep ride unit aration of the individual compounds is unneces ~ (CC1sCH'2CI-I(OCOCH3)CH2CH(OCOCH3)C1) sary in view. of the fact that the compounds all is 42.2%. Attempted distillation of higher boil have the same functional groups and differ only ing products present in the reaction product, even in the number of'vinyl acetate units present. By under diminished pressure, is accompanied by 55 virtue of the presence of active halogen in the 1:1 some decomposition. ' , addition product and products having a plurality The 1:1 addition compounds and the products of vinyl acetate units and ends from one molecule having a plurality of vinyl acetate units and ends of carbon tetrachloride produced in this reaction, from one molecule of carbon tetrachloride which hydrolysis or other chemical reactions convert are obtained from vinyl acetate and carbon tetra 60 these compounds to other materials having fur chloride by therpresent novel reaction react with ther utility for special applications. Thus, hy aldehyde reagents such as phenylhydrazine and drolysis gives rise to polyhydroxy compounds use semicarbazide hydrochloride, indicating that ful in resin or coating compositions. the products formed are alpha-chloroesters of The above description and examples are in 65 acetic acid. For example, the semibarbazone of tended to be illustrative only. Any modi?cation the 1 to 1 addition product of vinyl acetate and of, or variation therefrom, which conforms to carbon tetrachloride was found to darken at 160° the spirit of the invention, is intended to be in C. and melt with decomposition at 192° C. (un cluded within the scope of the claims. corrected); it contained 19.3% nitrogen as de What is claimed is: ‘ termined by the Dumas method. The calculated 70 1. A liquid mixture of compounds of the for nitrogen content of the compound mula is 19.3%. , A 2,4-dinitrophenylhydrazone i was readily prepared and found to melt at 173° C. (un 75 wherein n is an integer from one to eight. momma 2. A liquid having the general formula - ' chchcmca?nm ChC—CHxCHC1—O-COCH5 3 of obtaining Ipolychlorinated compounds which comprises reacting at 25450” ' C. vinyl acetate with from 0.3 to 10 parts, per part of vinyl acetate, of carbon tetrachloride. _ cmco" wherein n is an integer from one to eight. 3. A liquid of the formula. 4. A process 5 . I 5. Process of claim 4 wherein a. peroxy poly merlzatlon catalyst is employed. ‘ JESSE HARMONY.