Патент USA US2405971код для вставки
2,4053% > Patented Aug. 20, 1946 f'fU'N-prgp STATES PATENT OFFICE ' 2,405,971 1 HAIDGENATED roLxEmLENE’ , S Ambrose McAlevy, Kennett Square, Pa., assignor' ‘ ‘_ to _E. I. du Pont de Nemours & Company, Wil ' mington, vDeL, a corporation of Delaware . . hlo Drawing- Application March 23, 1943. . ‘Serial No. 480,211 f “1 Claim. (01. 260-94), This invention relates to an improved process used in the description and claims to reierto the for the halogenation of; polymers from organic compounds containing “mono‘ole?nic unsatura polymers , from ethylene alone and also to the tion, and is more-particularly,related'to an im telomers of the above kind. , ' In accord with this invention the polymers are modified ethylene ‘polymers, interpolymers and Proved processyfor the chlorination ofpolymers from ethylene -An object of dissolved or suspended in‘ an organic solvent, pref erably one which is substantially inertjand then treated with an oxychloride of carbon ‘or sulfur, in the presenceof light, with or without‘ the aid the presentginventlonis to provide‘ I _ _ an improved process for the halog'enation of ‘poly; mers, derivedfrom ‘organic compounds having monoole?nic unsaturation _ and which contain at least one replaceable hydrogen-per structuralunit 10 of a catalyst, re. 2., a heterocyclic compound con taining- annular nitrogen. Alternatively, the 're-' and molecular weights in excess of‘ 300. Another object is to provide-aprocess tor the chlorination -.action may be catalyzed by the use, in lieu‘ of ‘light, . of .monoole?nqpolymers; which , have, molecular - oyl peroxide. The amount of catalyst either used ' of a peroxide catalyst such, for example, as benz weights in excess o_f1'_300.“_ (Still another object is, 15 withlight or employed in the alternatereaction to provide an improved process forchlorinating can vary from 0.01 to 10% on the weight of the oxychloride, generally the amount which has been polymers » from, ethylene, ‘which- have I molecular weightsinexcess of,--300.§,1,0ther' objectsand 'ad- ‘ found to give satisfactorily ‘good results is from vantages of, the invention lwil'llhereinafter appear. The polymers from ethylene which are halogen ated in accord , with, this . invention include the about 0.10 to 2%. ,. 20 In carrying out the invention by one practical method, a solution or suspension ,of'the desired solid to’ semi-solid ;high_,_mQ1ccular weight sub stances ofa polymelic naturewhich are obtained polymer and, if desired, acatalytic amount of a heterocyclic compound containing annular nitro (1),, by the. polymerizationtof l ethylene alone as . gen, e. g., pyridine, is‘ charged into a ?ask ?tted described in U. S. Patents 2,153,553 andv 2,188,465, 25 withv a re?ux condenser, a stirrer with a suitable (2). by the polymerization of ethylene with other seal to prevent escape of solvent, a thermometer, polymerizable organic compounds, as described in U.-S. 2,200,429, (3) bycontacting ethylene alone and an oxychloride inlet. The reaction mixture or in admixture with anotherpolymerizable or C., with agitation, exposed‘ to a source of actinlc is then heated,‘ preferably to between 50 and 130°. ganic compound with molecular oxygen, a pcr-oxy, 30 light, and they oxychloride added portion-wise. compound, a hydrazine or hydraziniumcompound After completion of the reaction the chlorinated or an amine oxide anda normally liquid, substan polymervis isolated by means well known to the tially inert reaction mediumI at a temperature in art. , , . ‘ ' The oxychlorides of carbon or sulfur ‘that may therange of ,40f't0 400‘? C. andat a pressure in excess of atmosphericxpreferably in‘ the range of 35 be used include phosgene, (C0012); oxalyl chlo 50 to 3000 atmospheres, or, (4,), ,by. reacting ethyl ride, (C_0Cl)z; sulfuryl chloride, (SOzClz); and, thionyl chloride, SOC12. In general, at least half ene with a telogen to give, telomers; as described a mole of the oxychloride is used for each hydro in Jthecopending application Of Hanford 8: Joyce, gen tov be replaced in the polymer. As a rule, S.‘ N. 438,466, ?ledhprllllo, 1942,,an'd in, the co pending application of; Hanford ,8: Roland, S. N. 40 however, it is advantageous to increase the 471,028, ?led January 1:1943. I e - The polymers of ethylene alone are either semi amount of the oxychloride to one mole. _ As a sourceof actinic, light there can be used a high wattage tungsten ?lament light, a mercury solid or solidat normal temperatures, correspond vapor light, sunlight, carbon arc, ultraviolet lamp, in composition substantially to (CI-12):, and have molecular weights in excess of 1000. The proper-, 45 infrared lamp, or monochromatic light. The apparatus may be of glass, enameled ves ties of the polymers of ethylene with other‘ poly sels, or corrosion resistant alloys. merizablev organic. : compounds . vary depending ‘If desired the process may be carried out as a > upon the nature oirethe polymerizable organic compound and the composition of the polymer, ‘ continuous operation, for example,‘ vby injecting The properties .of thetelorners depend inter alia 50 the oxychloride into a hot solution of the polymer upon such factors as the nature of the telogen and its reactivity, relative concentrations or telogen and ethylene, temperature employed in the telom erization, and nature of the catalyst. ?owing through an illuminated tube. Suitable solvents include carbon tetrachloride, tetrachloroethylene, tetrachloroethane, hexa chloroethane, and the like. In place of these The expression “polymers from ethylene” is” chlorinated aliphatic hydrocarbons there can be 9,400,071 3 4 used benzene, nitrobenzene, etc. If a low boiling solvent is used it is desirable to conduct the chic rination under pressure for this raises the boiling point of the solvent and maintains the product in solution. The peroxide catalyst that may be used in ac cord with the alternate procedure includes hydro gen peroxide, persucclnic acid, lauroyl peroxide, tetralin peroxide, urea peroxide, butyryl peroxide, acetyl peroxide, diethyl peroxide, the alkali metal l0 and alkaline earth metal peroxides, or mixtures . thereof. Generally the products obtained from the poly . sulfuryl chloride and 40.5 parts of chlorine are added and the mixture heated under re?ux, in the light of a 800-watt tungsten ?lament, electric lamp, at approximately"l'l° ‘C, for 60 minutes. The reaction mixture is drawn on, drowned in 1500 parts of methanol to precipitate the chlori nated polymer and after .decantation and ?ltra tion the methanol is removed by treatment with steam. The product analyses 47% chlorine and 0.56% sulfur. . The melt viscosity herein described is deter mined by the following procedure. An aluminum cylinder of %" internal diameter open at the top is ?tted at the bottom with an 8 mm. steel disk mers of ethylene alone are rubbery, flexible, and tough with higher tensile strengths than the orig 15 containing at its center a 2.1 mm. ori?ce. The cylinder and disk are heated to a temperature of inal polymers. At 20 to 25% chlorine content the 190° C. and the product to be tested introduced materials are tacky. The tensile strength of the and heated to the same temperature. Above the products increases very rapidly with increase in surface of the product a piston heated to 190° C. chlorine content. Above 30% chlorine, the sof tening points reach the range of those of the 20 and ?'“ in diameter is superimposed and upon it a weight is placed giving a. combined weight of original polymers. The chlorinated polymers from ethylene are in most cases soluble in arc 2.16 kilograms. The weight of product ?owing matic hydrocarbons, in chlorinated aliphatic hy drocarbons and in organic esters at ordinary tem from the orifice in grams per minute is the meas ure of the melt viscosity. peratures. 25 Variation in the chlorine and the sulfur content of the halogenated polymer is possible. It has been foundv that if sulfur dioxide is introduced Example 2.-25 parts of solid ethylenepolymer having a melt viscosity of 0.1, is added to 500 parts of carbon tetrachloride and the ‘resulting mixture heated and stirred to effect solution. 57 parts of sulfuryl chloride and 0.2 part of benzcyl peroxide » throughout the reaction sulfur content of the re sulting chlorinated polymer can be increased up 30 are added and the resulting mixture heated under re?ux at a temperature of approximately 77° C. to from 5 to 10%. It is likewise possible to aug for 90 minutes. The carbon tetrachloride, sul ment the chlorine content of the chlorinated poly furyl chloride, and hydrochloric acid are steam mer by introducing chlorine throughout the re distilled from the reaction mixture, the reaction action. Furthermore, both gases may be intro duced if an increase in the sulfur and chlorine 35 product is separated. dried on a rubber mill and is analysed. It contains 30.9% of chlorine with content over that obtained by a given concentra tion of the oxychloride is desired. Variation in . substantially no sulfur. Example 3.—Fifty parts of a polymer of ethyl the sulfur content of the product is also obtained ene, having a melt viscosity of 0.1, is dissolved in by the use of suitable reaction temperatures. In general, the sulfur content of the product varies d0 1000 parts of carbon tetrachloride and to the solu tion there is added 120 grams of sulfuryl chloride. inversely, with reaction temperature over the The resulting mixture is heated under re?ux and range 10° to 80° C. It is often convenient to lower irradiated during the reaction with a type H-4 the reaction temperature when the reaction is only partly complete, for in the intermediate ranges of chlorine content (10 to 35%) the resin is su?lciently soluble, in carbon tetrachloride, to permit lowering the temperature without precipi 100-watt mercury vapor lamp. After 140 minutes - the product is steam distilled, and milled. It con tains 34.4% of chlorine. Example 4.—Eight parts ofan ethylene polymer (average molecular weight 25,000-30,000) is dis solved in 480 parts of boiling carbon tetrachlo When phosgene is employed as the oxychloride the reaction is partly one of chlorination, but in 60 ride, and one-half part of pyridine is added to the solution. As the re?uxing solution is stirred runs of 24 hours’ duration introduction of small and is illuminated, 99 parts of sulfuryl chloride is amounts of carbonyl groups into the resin occurs, added drop-wise over a period of 70 minutes. The and an infusible, insoluble product results. tation occurring. ' mixture is stirred for 2 additional hours. The When the product of reaction between an oxy chloride and an oleilne polymer‘is soluble in the 55 product precipitates out as a soft tally-like co agulate. The carbon tetrachloride is decanted oil’, reaction mixture, the. following procedure may and occluded solvent, sulfuryl chloride, and hy drogen chloride are removed from the product by chloride and hydrogen chloride present after the hot-water wash on a rubber mill. The dried prod reaction may be removed by simple steam distilla tion and the product, subsequently washed and 60 uct is ?exible and tough and is soluble at ordinary temperatures in hydrocarbons and organic esters. ' dried on a mill, such as is used in compounding It softens at 115° C, to 118° C. and contains 44.1% rubber, or contrariwise the product dissolved in be used for isolating it. y The solvent, excess oxy benzene, carbon tetrachloride, dichloro di?uoro of chlorine and 2.6% of sulfur. Example 5.—Ten parts of the ethylene polymer described in Example 3 is dissolved in 486 parts of hot tetrachioroethylene, and one-half part of pyridine is added. As the solution is stirred and is maintained at 100° to 110° C., it is exposed to actinic light, and 117 parts of sulfuryl chloride is added slowly over a period of 90 minutes.‘ Stir ring is continued-for 45 additional minutes. No weight. precipitate separates out, and the solution is Example 1.—Twenty-i1ve parts of a polymer of steam distilled to remove solvent, sulfuryl chlo ethylene, having a melt viscosity of 0.1, is dis ride, and hydrogen chloride.v The chlorinated solved with heating in 500 parts of carbon tetra chloride. Into the resulting mixture 15 parts of 7s polymer is washed and dried on a mill. It is ethane, methylene chloride or other suitable sol vent is precipitated therefrom by an aliphatic alcohol or other liquid miscible with the reaction medium employed but which is a non-solvent for the chlorinated polythene produced. The following examples illustrate preferred em bodiments of the invention in which parts are by 70 2,405,971 5 tough, ?exible, and soluble at ordinary tempera tures in hydrocarbons and organic esters. It softens at 115° to 117° C. and contains 53.4% of Example 10.-A solution of 15 grams of solid ethylene polymer and 3 grams benzoyl peroxide break. The original ethylene polymer is insoluble The resulting resin. is somewhat similar to the in 300 cc. benzene is kept saturated with phos= gene at a temperature close to the'boiling point chlorine and 0.7% of sulfur. A solvent-cast ?lm 3 mils thick has a tensile strength of 4,600 pounds 5 of the solvent. This mixture is irradiated with per square inch and an elongation of 276%‘ at a 300 watt tungsten ?lament lamp for 24 hours. in cold solvents, and a solvent-cast ?lm 4 mils ethylene polymer in appearance, but is infusible and insoluble. thick has a tensile strength of 1,580 pounds per 10 square inch and an elongation of 8% of break. In place of the polymer set forth in the above Example 6.—Ten parts of the ethylene poly examples there can be used any polymer derived mer of Example 3 is dissolved in 405 parts of hot from an organic compound containing monoole~ tetrachloroethylene and one-half part of pyridine ?nic unsaturation and which contains at least one is added. During the reaction the solution is il replaceable hydrogen per structural unit, said luminated with actinic light and is stirred vigor 15 polymer being further characterized by having a ously at 100° to 105° C. Fifty parts of sulfuryl molecular weight of at least 300. ‘ Speci?c exam chloride is added over a period of 80 minutes. ples of polymers which can be used in the prac The solution is steam-distilled to remove the sol tice of this invention include vinyl acetate, poly vent and impurities. The product is washed and vinyl chloride, polystyrene, polymethylacrylate, dried on a rubber mill. It is a soft rubbery ma terial, containing 21% chlorine and only a trace of sulfur, and soluble in hydrocarbons at room 20 polymethyl methacrylate, etc., the polymers of vinyl chloride with either vinyl acetate, fumaric esters, maleic esters, or vinylidene chloride; the ‘ polymers of ethylene with amylene, styrene, stil . Example 7 .—Twenty parts of the ethylene poly bene, vinyl acetate, methacrylic esters, ethyl mer of Example 1 is dissolved in 960 parts of 25 itaconate, diethyl citraconate, diethyl maleate, di= boiling carbon tetrachloride, and 1 part of pyr ethyl fumarate, acrylic esters, vinyl chloride, vinyl idine is added. The re?uxing solution is illum ?uoride, chlorotri?uoroethylene, vinylidene ?uo inated with actinic light, and 109 parts of sulfuryl ride, vinylidene chloride, tetra?uoroethylene, chloride is added slowly over a period of 90 min maleic anhydride, vinyl butyl ether, eta; poly utes. Stirring is continued for 30 minutes. The 30 mers of vinylidene chloride with acrylonitrile, ' temperature and in warm butyl acetate. coagulated precipitate is placed in boiling water vto remove solvent and impurities. After drying in the air overnight the product is dissolved in methylene chloride and the solution shaken vig orously with powdered sodium bicarbonate to re move last traces of hydrogen chloride. The so methacrylic esters, tetra?uoroethylene, vinyl chloride, etc., and methyl methacrylate, styrene, or vinylidene chloride. The products may be removed from the reac- tion mixture and puri?ed by means already de scribed or the reaction mixture may be injected dium bicarbonate is removed by centrifugation at the bottom of a vessel containing boiling water, and decantation. Clear, colorless, transparent whereupon the solvent and impurities will ?ash ?lms may be cast from the resulting solution. A off or dissolve and the puri?ed polymer may be ?lm 1.’! mils thick has a tensile strength of 3549 40 skimmed off the top of the water. If the prod pounds per square inch and an elongation of uct is still in solution it may be precipitated from 308% at break. The product contains 41.4% solution with alcohol or any liquid miscible with chlorine and 3%’ of sulfur. the solvent but not itself a solvent for the poly Example 8.—To 5 parts of a liquid propylene mer. The polymer may then be redissolved in polymer having a. molecular weight of 318 is a suitable solvent and similarly reprecipitated any added approximately 0.’! part of pyridine, the desired number of times. Drying may be' carried mixture is stirred and irradiated with a 500 watt out in the air or in a vacuum oven at a slightly Mazda lamp while adding 5 parts of sulfuryl chlo ride during a period of 15 minutes. The irra elevated temperature. diation is continued for an additional 45 minutes and the reaction mixture is then poured into 500 parts of a 30% aqueous sodium hydroxide solu tion. The product is extracted with ether and dried over magnesium sulfate. The solvent is re in wrapping ?lms, in coating and waterproo?ng moved at reduced pressure, and the product is, obtained as a yellow liquid. Upon analysis it is found to contain 18.4% chlorine and no sulfur. Example 9.—To a solution of 30 grams chloro polythene (having a chlorine content of 30.3%) in 500 cc. 0614, 30 grams oxalyl chloride is added, and the mixture irradiated for three days at ‘17° A process of chlorinating a polymer from eth ylene having a molecular weight of at least 300 The chlorinated products are applicable for use fabrics, as protective liners for acid or base con tainers, in lacquers for wood, cement, or metal, as gaskets and washers, etc. I claim: 1 ' obtained by polymerizing ethylene at a tempera ture between 40 and 400° C. under pressures be tween 350 and 3000 atmospheres and in the pres ence of a catalyst selected from the group con sisting of oxygen and peroxy compounds which by means oi’ a mercury vapor lamp. The prod comprises reacting the said polymer in solution uct, which is’isolated by steam distillation of the in carbon tetrachloride with sulfuryl chloride in the presence of benzoyl peroxide and at a tem solvent, contained 34.3% 01, 56.77% C, and 8.86% B. This analysis shows that the predominating 65 Denture between 50 and 130° C. 1 reaction which occurred was chlorination. AMBROSE McALEVY.