Патент USA US2408610код для вставки
Patented Oct. 1', 1946-’ ' 2,408,609 } UNITED. STATES PATENT ‘orrlca BESINS OF HIGH CHLOBINE CONTENT Oliver w. can, Niagara Falls, N. ‘2., assignor to E. L du Pont de Nemours 8: Company, Wil mington, Del., a corporation of Delaware No Drawing. Application May 24, 1943, ' ' ' ' Serial No. 488,215 2 Claims.‘ . - 1 , ‘ (on. zen-ass) _ This invention relates to the preparation of certain new and useful chlorine-containing res inous materials. More particularly,‘it* relates to - 2 I invention is tosecure these 'improved'properties - with resins of the vinyl chloride-trichlorethylene copolymer type by incorporating additional chlo the preparation of new and valuable, resins by introducing chlorine into resins previously pre pared by copolymerizing vinyl chloride and tri rine in these resinous products. These and still further objects will be apparent from the en suing disclosure of certain preferred embodi chlorethylene. ments of my invention. . In my copending application, sci-19.1 No. 488,213 illed contemporaneously herewith, I have dis - . In incorporating additional chlorine into the copolymeric resins prepared by copolymerizing closed the preparation of new and valuable 10 vinyl chloride prefer to feed resins by copolymerizing vinyl chloride and tri thecopolymer chlorethylene. As disclosed in that application, desired, water ' the amount of trichlorethylene presentv in the and trichlorethylene, ordinarily I chlorine gas into a suspension of in anysuitable organic liquid. If in small amounts may be present - in the slurry or suspension of the copolymer in tion should normally range from 1 to 5% by 1.5 the organic liquid, as I have found that a small . monomeric material subjected to copolymeriza weight. Copolymeric resins of the most satis factory character, as described in said copending application, are ordinarily prepared by copoly merizing a mixture of vinyl chloride and trichlor amount of- water under these circumstances functions as catalyst and renders chlorination more rapid and veillcient. ' ' As an illustration, it is possible to suspend the ethylene wherein the trichlorethylene content» 20 copolymer of trichlorethylene and vinyl chloride in an organic liquid such as carbon tetrachloride ranges from 1.5% to 3%. and supply chlorine gas thereto, actinic radia--' I have now found that resins prepared by the copolymerization of trichlorethylene and vinyl tion being supplied to the reactants by placing‘ chloride as disclosed in said copending applica tion can be much improved in character, espe cially as regards their heat stabilities, by chlori nating the copolymeric resins so that they are of increased chlorine content. For best results a light source in contact with the suspension or slurry. \ From time to time samples of the prod uct may be withdrawn and tested to ‘determine? chlorine content. At the beginning it is desir able to heat the suspension or slurryin order to initiate the reaction, but as the reaction.pro-‘ ' I have found that the resins prepared by copoly merizing vinyl chloride and trichlorethylene 80 ceeds exothermically during the latter stages should be chlorinated to a‘ chlorine content fall cooling is usually essential in order to maintain a temperature low enough to prevent excessive ing within the range 64% to 66% by weight. In losses of material by vaporization. At thev con- ' addition to improved heat stability, the chlor clusion of the reaction the reaction mixture may inated resinous materials are characterized'by increased solubility in the common lacquer sol 35 be blown with ‘air to free it fromhydrogen chlo ride and chlorine, and the chlorinated copoly-I vents such as aromatic hydrocarbons, and by ‘ meric material precipitated by'the addition of increased softening temperature. The copoly a precipitating agent such as methanol. It is mers of vinyl chloride and trichlorethylene, as' described in my copending application, gen- ' then recovered by ?ltration and dried in the . erally have softening temperatures within the 40 usual manner. As examples of my process for preparing new range 70 to 80° 0., whereas by the incorpora and valuable polymeric materials of increased tion of additional chlorine to yield a resinous chlorine content, the following are illustrative. product of 64% or over chlorine content the sof tening temperature is increased to one in the Example I range 109 to 120° 0. Improved heat stability, 45 higher softening temperature, and greater solu bility in common solvents are all properties of A copolymer of vinyl chloride and trichlor-‘ ethylene, the trichlorethylene constituting 1.5% considerable value and importance where the. of the monomeric material copolymerized, was heat stability, and increased solubility in the 50° 0., there being-present, as polymerization prepared by following the procedure described resin is employed as a coating material. Accordingly. it is one of the objects of this 60 in Example 1 of my copending application,» Serial No. 488,213 filed May 24, 1943. 'This involved invention to prepare resins of the vinyl chloride trichlorethylene copolymer type which resins will > subjecting the monomeric mixture to copolymer izatlon at a temperature within the range 40 to exhibit elevated softening temperature, improved ' common lacquer solvents.‘ Another obiect of this 55 catalyst, ammonium persulfate and sodium bi 2,408,609 4 3 The copolymerization was complete Example 11 The copolymer of Example 2 of my previously referred t‘o-copending application was prepared, after somewhat over three hours, whereupon the copolymer of vinyl chloride containing 1.5% tri chlorethylene was recovered from the autoclave in which the copolymerization was carriedv out. 400 parts of this copolymeric material and Yutilizing as monomeric material a mixture oi vinyl chloride and trichlorethylene containing. 3% of trichlorethylene. _ This was copolymerized 5,314 parts by weight of carbontetrachloride for four- hours and twenty minutes at an elevated were then placed in a suitable glass-lined vessel temperature. . equipped with a stirrer, a re?ux condenser, a , The copolymer thus resulting was chlorinated thermometer well and thermometer, a light well, 10 after suspension in carbon tetrachloride by the and an inlet tube for introducing chlorine._ Ac introduction of chlorine gas, following the proce tinic radiation was supplied by the light of an dure described in Example 1, until a chlorinated ordinary tungsten ?lament lamp placed in the copolymer containing 64.5% of chlorine was so light well. . v cured. This material was readily soluble at room The contents of the reaction vessel were then 16 temperature to the extent of, 33%, without amp, heated to approximately 60° C. in order to initiate culty, in mixed solvents such as one comprising the reaction. Chlorine was introduced into the‘ 60% of methyl ethyl ketone and 40% toluene.‘ stirred suspension of copolymer, and chlorination Films deposited on a‘ steel plate from this solution continued until a total of 111 parts by weight of were characterized by the desirable properties hydrogen chloride has been evolved. The reac 20 enumerated in Example I. ' tion mixture was then blown with air until sub The products obtained in accordance with this. stantially free from hydrogen chloride and chlo invention are useful for many purposes in the rine. lacquer industry, and may be generally employed The chlorinated coplymer was then isolated by for impregnating and insulating purposes. "they the addition of methanol as a precipitant to the may be employed either alone or ‘in combination reaction mixture. This resulted in the formation with other resinous products. ‘ of a ?ne, easily ?ltered powder which was recov As various changes may be made in the pre- ' ered from the methanol-carbon tetrachloride ferred procedure as described without departing mixture by ?ltration. In this way there were re from the scope of my invention, it is intended covered 485 parts by weight of a chlorinated co 80 that it shall be construed in accordance with the polymer of vinyl chloride and trichlorethylene, this chlorinated material analyzing 65.9% chlo _ appended claims.‘ I claim: 1. ' _ rine. . l, A polymeric product obtained by the chlo Moldings of this chlorinated copolymeric mate rination of a copolymer of vinyl chloride and tri rial were prepared- at 165° C. and compared with 85 chlorethylene prepared by copolymerization of a moldings of the 'unchlorinated copolymer pre monomeric mixture containing between 1% and ~ pared at the same temperature. Moldings of the 5% by weight of trichlorethylene and the re chlorinated polymer containing 65.9% chlorine mainder of said mixture being vinyl ‘chloride, were light yellow in color, while moldings of the said polymeric product, as a result of said chlo unchlorinated copolymer were jet black in color. rination, having an increased percentage content Moreover, in . the latter case, the chromium of chlorine and an increased resistance to dark plated surfaces of the molding equipment had ening at elevated temperatures. been severely attacked by the copolymer, while 2. A polymeric product obtained by'the chlo no evidence of attack was noticeable in the case rination of a copolymer of vinyl chloride and tri of the chlorinated resin containing 65.9% chlo 45 chlorethylene prepared by copolymerlzation of a rine; The solubility and ease of solution of the monomeric mixture containing between 1% and chlorinated copolymer in various solvents were 5% by ‘weight of trichlorethylene and the re clearly superior to those of the unchlorinated co mainder of said mixture being vinyl chloride, polymer. Moreover, coatings of the chlorinated said polymeric product, as a result or said chlo 50 copolymer deposited upon steel strips were of im rination having a chlorine content of between - proved character, both as regards flexibility and 64% and 66%, and having an increased resistance adherence, as well as in regard to resistivity to to darkening at elevated temperatures. 1 ' the action of moisture. acids and alkalies. OLIVER W. CASS.