Patented Octlgz, 1946 2,409,948 UNITED STATES PATENT OFFICE 2,409,948 POLYMERIC MATERIALS Elmore Louis Martin, Wilmington, Del., assignor to E. I. du Pont de Nemours 8: Company, Wil mington, Del., a corporation of Delaware No‘ Drawing. Application March 1, 1945, Serial No. 580,491 6 Claims. ' (Cl. 260-86) 2 1 phate. The reactor is closed, evacuated, cooled This invention relates to polymeric materials and more particularly to polymers obtained from in a solid carbon dioxide/methanol mixture, and is further charged with 10 parts of vinyl chloride, 60 parts of vinyl ?uoride and 30 parts of tetra ?uoroethylene. The reactor is agitated and halogenated ethylenes. This invention has an an object new and use ful compositions of matter. A further object is the preparation of valuable high molecular heated to 75° C. while maintainng an internal pressure within the range of 3,000-32,000 lb./sq. weight polymers comprising ?uorinated ethylenes. in. by periodic injection into the reactor of deoxy A still further object is the preparation of poly genated water. The sum of the individual pres mers comprising tetra?uoroethylene and vinyl ?uoride having greater solubility in organic sol 10 sure drops during the heating period of 9.1 hours is 5400 lb. /sq. in. The'reactor. is cooled to room vents and improved workability. Other objects temperature, the unreacted portion of the gaseous will appear hereinafter. monomers bled o?, and the contents of the re These objects are accomplished by polymerizing action tube are discharged. There is obtained 42 ture of a perhaloethylene containing at least two 15 parts of a copolymer which contains 43.4% ?uo rine and 8.67% chlorine which corresponds to a ?uorine atoms, vinyl ?uoride, and a hydrogen tetra?uoroethylene/vinyl ?uoride/vinyl chloride containing halogenated ethylene other than the copolymer having a tetra?uoroethylene content vinyl ?uoride. of 25%, and a vinyl ?uoride content of 60% and a I have found that polymers can be obtained from the above mentioned ingredients which are 20 vinyl chloride content of 15%, or a mole ratio of tetra?uoroethylene/vinyl ?uoride/vinyl chloride of particular value in many industrial applications of 1:5.4:1. Films cast from an acetone solution by reason of their clarity and solubility in con in the manner more fully described below a mix (25% copolymer), have tensile strengths of 4850 junction with high tensile strength, non?am lb./sq. in. at an elongation of 460%, a modulus of mability, and other desirable properties The invention is most advantageously carried 25 elasticity of 0.136>< 10° lb./sq. in., a tack tempera ture (the temperature at which the ?lm shows out when the mixture of copolymer ingredients is a tendency to stick to a highly polished surface) composed of tetra?uoroethylene, vinyl ?uoride, of 115-120° C. and a temperature of zero tenacity and vinyl chloride. The tetra?uoroethylene can, of 135° C. The copolymer is non?ammable and however, be replaced by other perhaloethylenes, that is by other completely halogenated ethylene's 30 is soluble in acetone, methyl ethyl ketone, ethyl acetate and halogenated hydrocarbons. It is in which at least two of the halogen atoms are insoluble in alcohols, ethers, and aliphatic and The vinyl chloride can be replaced by various hydrogen-containing halogenated ethyl enes other than vinyl ?uoride. The vinyl ?uo ride is speci?cally a necessary component in the 35 aromatic hydrocarbons. Exmu2 , present copolymers. A stainless steel pressure reactor is charged with 200 parts of deoxygenated water and 0.3 part of benzoyl peroxide. The reactor is closed, evacu ties of stiffness, melting point, tensile strength, ated, cooled in a solid carbon dioxide/methanol solubility and clarity, and sacri?c of one or more 40 mixture, and is then further charged with 25 of these properties, each of the mentioned copoly parts of vinyl ?uoride, 45 parts of tetra?uoro mer ingredients must be present in the composi ethylene, and 30 parts of vinylidene ?uoride. The tion to the extent of at least 5%. The polymer reactor is then agitated and heated to 80° 0., the ization reaction is conducted under superatmos , pressure being maintained in the range of 2400 pheric pressure, generally autogenous pressure, 2600 lb./sq. in. by the periodic injection of de and elevated temperature in the presence of a oxygenated water. After heating for 10.2 hours In order to obtain the'desired balance between preservation to the greatest extent of the proper small amount of a peroxy compound as catalyst; the sum of the individual pressure drops is 1600 lb./sq. in. The reactor is then cooled and dis charged. There is obtained 34 parts of a copoly 50 mer of tetra?uoroethylene/vinyl ?uoride/vinyli .‘EXAMPLE 1 dene ?uoride which is soluble in acetone to the extent of 23%. Films cast from an acetone solu Av stainless steel high-pressure reactor is ‘tion have vtensile strengths of 5000 lbJsq. in. at charged with 50 parts of tert.-butyl alcohol, 150 The invention is illustrated by the following examples wherein parts are by weight. ‘ parts of deoxygenated water, 0.3 part of benzoyl peroxide and 0.3 part of hydrated disodium phos ' an elongation of 440%, a modulus of elasticity of 55 0.101 x10a lbJsq. in.,,a tack temperature of 160 2,409,948 4 165° C., and a temperature of zero tenacity of 178° C. The copolymer is nan?ammable and is soluble used, the products are in general characterized by lower molecular weights. 'The catalysts used in the practice of this in vention are peroxy compounds, 1. e., those com in acetone, methyl ethyl ketone, ethyl acetate, and , halogenated hydrocarbons. It is insoluble in al cohol, ether and aliphatic and aromatic-hydro 5 pounds which contain an -O—0_ linkage. Ex carbons. - amples of such catalysts are diacyl peroxides, such as benzoyl peroxide and lauroyl peroxide, polymers for a particular use is facilitated by dialkyl peroxides, such as diethyi peroxide, and the table inserted herein which shows the physi inorganic peroxy compounds such as ammonium cal properties of a number of these copolymers: l0 persulfate, potassium persulfate, potassium per Tame ' The ready selection of the most desirable co Tetra‘ ?uoro~ ethylene Per cent 5‘ 7 7 9 11 14 20 vm 1 ?uor dc Vin 1 chlor de Tack temp. Temp- Modulus of often zero elssticltyX10‘ 69 22 35 68 52 54 51 26 71 58 23 37 32 29 ° 0. 45-50 40-45 35 70-75 40-45 50-55 35-40 ° 0. 68 82 Lba/sq. in. 0. 062 0. 260 50 124 61 78 88 0. 219 0. 098 "‘. 032 0. 097 0. 134 21 48 31 60-65 ...... _. 0. 030 23 25 33 36 36 55 60 40 37 43 22 15 180 135 . 100 90 , 126 0. 145 0. 136 0. 002 0. 094 0. 147 55 25 27 21 20 85-90 115-120 50-55 40-45 80-85 130-135 172 2 38 70-75 126 60 . 27 Yield Point Ten. Lbalaq. in. Liza/sq. in. 1, 850 2, 000 3, 120 ' 3, 120 3, 420 2, 860 1, 720 2, 660 . 3, 550 3, 420 2, 900 1, B00 2, 700 3, 600 Elong. Per cent 150 10 10 220 / 10 80 60 . Excellent. Hazy. Good. Excellent. Fair. Excellent. Good. 1, 840 . 2, 550 380 3, 800 3, 800 1, 400 2, 640 3, 880 3, 850 4, 850 3, 410 2, 870 4, 710 10 460 420 350 400 0. 112 3, 480 7, 250 465 Fair. 0. 090 3, 160 3, 720 410 Good. ' _ Clarity of films Fair. D0. Good. Excellent. ' Suitable perhaloethylenes in addition to tetra carbonate, potassium perphosphate, sodium per ?uoroethylene which contain at least two ?uorine 30 borate and hydrogen peroxide. atoms include chlorotri?uoroethylene, bromotri The polymerization is conducted generally at ?uoroethylene, 1,1-dichloro-2,2-di?uoroethylene temperatures within the range of 40-200° C., de and 1,2-dichloro-l,2-di?uoroethylene. Hydrogen pending upon the type of catalysts used. With containing halogenated ethylenes in addition to diacyl peroxide catalysts, temperatures ranging vinyl chloride and vinylidene ?uoride include from 80-120° C., with persulfate catalysts 20-100° vinyl bromide, vinylidene chloride, l-chloro-l C., and with dialkyl peroxide catalysts 100-l50° C. ?uoroethylene, 1,1-di?uor0-2-chloroethylene and tri?uoroethylene. ' , are generally used. The polymerization can ‘be carried out at pressures above atmospheric, gen erally within the range of 500—5000 lb./sq. in. and The copolymers having the most valuable prop erties are those obtained from mixtures consist 40 preferably within the range of 1500-4000 lb./sq. ing of 20% to 50% tetra?uoroethylene, 25% to in. 75% vinyl ?uoride, and 5% to 30% of the hy The products of this invention are character drogen-containing halogenated ethylene other ized by good solubility and excellent clarity. They than the vinyl ?uoride. Within this range the , are further characterized by having the valuable proportions best for particular purposes will vary 45 combination of ‘properties which include good somewhat. Thus where stiffness is a considera tensile strength, relatively high softening tem tion the preferred compositions contain 20%-45% tetra?uoroethylene, 50%-75% vinyl ?uoride, and 5% .to 30% of the other hydrogen-containing a perature, high modulus of elasticity, low water ab sorption' and non?amma-bility. Copolymers of this invention are therefore particularly suitable halogenated ethylene. For applications where tack temperature is of ?rst importance, the best 50 for use as a base for photographic and X-ray ?lms and in coating compositions, wrapping ?lms results are obtained with compositions contain and industrial ?bers. They can be molded into ing 20%-50% tetra?uoroethylene, 25%-75% various shaped articles and can be extruded in vinyl ?uoride and 5%-20% of the .other hydroe the form of ?bers, ?lms, etc. These copolymers gen-containing halogenated ethylene. Where the tensile strength is of primary importance, com 55 are also valuable for coating wire in the manu facture of electrically insulated conductors. For positions containing 20%-50% of the tetra?uoro many of these purposes the polymer may be com ethylene, 45 %-70% of vinyl ?uoride and 5%-.25% bined with or prepared in the presence of plasti of the hydrogen-containing halogenated ethylene‘ are the preferred. For applications where tack cizers, stabilizers, ?llers, pigments, dyes, softeners, 60 natural resins or synthetic resins. ‘ , temperature, stiffness and tenacity are of ?rst im-. portance, compositions containing 20%-45% .of 5 ' , As many widely different embodiments of this tetra?uoroethylene, 50%-70% of vinyl ?uoride, and 5%-2o% vof the hydrogen-containing halo invention may be- made without departing from . the spirit and scope thereof, it is to be understood , genated ethylene are used because these composi- 65 that this invention is not to be limited to the speci?c embodiments thereof, except as de?ned in the appended claims. ture and tenacity values. Iclaim: .Although the examples illustrate the polymerlQ 1. A composition of matter comprising the co zation of a monomeric mixture in the presence’ of water, it is possible to carry out the reaction in , polymerization product of a mixture of a per an organic solvent instead of water. In general, 70 haloethylene containing at least two ?uorine tions possess the higher stiffness, tack tempera - _ it is preferred to carry out the polymerization in the presence of water or water-organic solvent , mixtures inasmuch as better results can be ob atoms, vinyl ?uoride, and a hydrogen-containing halogenated ethylene other than vinyl ?uoride, 'said mixture containing each of said nerhalo ethylene, vinyl ?uoride and hydrogen-containing . tained. since when organic solvents‘ alone are 75 halogenated ethylene other than vinyl ?uoride in 2,409, 948 ‘ 5 a an amount of at least 5% by weight, the halogen contained in said perhaloethylene and in said hy drogen-containing halogenated ethylene being ,_ selected from the group consisting of chlorine, bromine, and ?uorine. . 2. A composition of matter comprising the co polymerization product of a mixture of tetra 6 said perhaloethylene, vinyl ?uoride and hydro gen-containing halogenated ethylene other than vinyl ?uoride in an amount of at least 5% by weight, the halogen contained in said perhalo ethylene and in said hydrogen-containing halo c genated ethylene being selected from the group consisting of chlorine, bromine, and ?uorine. ?uoroethylene, vinyl ?uoride, and a hydrogen 5. A process for obtaining copolymers which containing halogenated ethylene other than vinyl comprises heating in the presence of a peroxy ?uoride, said mixture containing each of said 10 catalyst at 40° C. to 200° C. under autogenous tetra?uoroethylene, vinyl ?uoride and hydrogen pressure a mixture of tetra?uoroethylene, vinyl containing halogenated ethylene other than vinyl ?uoride, and a hydrogen-containing halogenated ?uoride i an amount of at, least 5% by weight, ethylene other than vinyl ?uoride, said mixture the halogen contained in said perhaloethylene containing each of said tetra?uoroethylene, vinyl and in said hydrogen-containing halogenated ?uoride, and hydrogen-containing halogenated ' ethylene being selected from the group consist ethylene other than vinyl ?uoride in amount of at least 5% by weight, the halogen contained in ing of chlorine, bromine, and ?uorine. , 3. A composition of matter comprising the co polymerization product of a mixture of tetra said perhaloethylene and in said hydrogen-con taining halogenated ethylenebeing" selected from ?uoroethylene, vinyl ?uoride, and vinyl chloride, 20 the group consisting of chlorine, bromine, and said mixture containing each of said tetra?uoro ?uorine. ethylene, vinyl ?uoride, and vinyl chloride in 6. A process for obtaining copolymers which , comprises heating in the presence of a peroxy 4. A process for obtaining copolymers which catalyst at 40° C. to 200° C. under autogenous comprises heating at 40°-200° C. under autoge 25 pressure a mixture of tetra?uoroethylene, vinyl nous pressure in the presence of a peroxy catalyst ?uoride, and vinyl chloride, said mixture con a mixture of a perhaloethylene containing at least taining each of said tetra?uoroethylene, vinyl two ?uorine atoms, vinyl ?uoride, and a hydro ?uoride, and vinyl chloride in amount of at least amount of at least 5% by weight. gen-containing halogenated ethylene other than vinyl ?uoride,-said mixture containing each of 5% by weight. EIMORE LOUIS MARTIN.