PATENT OFFICE WALTER, BOCK and EDUARD TSCHUNKUR, of COLOGENE-MULHELM, GERMANY, As THE-MAIN,Signors to GERMANY I

Patented Feb. 21, 1933 1,898,522

UNITED STATES

------f------PATENT OFFICE WALTER, BOCK AND EDUARD TSCHUNKUR, OF COLOGENE-MULHELM, GERMANY, As THE-MAIN,SIGNORs To GERMANY I. G. FARBENINDUSTRIE AKTIENGESELLSCHAFT, or FRANKFORT-os PoLYMERIZATION PRODUCT OF BUTADIENE-1.3 HYDROCARBONs AND PROCESs OF MAKNG SAME No Drawing. Application filed January 5, 1931, Serial No. 506,833, and in Germany January 15, 1930. The present invention relates to a process pound, for example 0.5–2% by weight (cal of polymerizing butadiene (1.8) hydrocar culated on the amount of hydrocarbon ap bons or mixtures thereof with each other or lied). The effect in question is not con with olefine benzenes in emulsion with water ned to a definite condition of solubility of 5 and an agent possessing emulsifying proper the chlorine compound employed in the re- 55 ties, in the presence of chlorinated aliphatic spective hydrocarbon or in the aqueous phase compounds. The invention furthermore re and is also to a large extent independent of lates to the polymerizates obtainable by the the nature of the emulsifying agent. Thus, process specified above. for example, a pronounced effect not only The process of manufacture of the inven takes place in the case of chlorinated com tion is by emulsifying the hydrocarbon to be pounds of the type specified, which are in polymerized, such as butadiene-(1.8), iso soluble in water and miscible with the hy prene, 1.3-dimethyl-butadiene (1.3), 2.3-di. drocarbon to be polymerized (carbon tetra methylbutadiene- (1.3), etc. with water and chloride, for example), but also in the case 15 an emulsifying agent or a protein, adding a of chlorinated compounds, which are solu 65 chlorinated aliphatic compound containing ble in water and which are soluble with diffi at least two chlorine atoms attached to one culty or insoluble in the said hydrocarbons, and the same carbon atom, and causing poly (for example, chloral hydrate, the sodium merization to perform at normal or elevated salt of trichloro acetic acid and the like). 0 temperature, for example, at a temperature All the substances indicated are capable in 70 between about 30-100°C. Shaking or stir conjunction with the most varied substances ring of the emulsion during polymerization exerting an emulsifying action, such as for will be of advantage. Among the chlorin example, emulsion forming salts of the type 5 ated aliphatic compounds we prefer those of soaps, alkylated naphthalene sulfonic as contain three or more chlorine atoms, of acid salts, salts of sulfonated oils or salts of 75 which at least three are attached to one and organic bases with inorganic or organic the same carbon atom, such as for example, acids, hydrotropic agents of the most vari hexachloroethane, chloralhydrate, trichloro ous kind, as far as they exert emulsifying acetic acid, trichloroacetic acid amide, carbon action, albuminous substances, sulfite waste 89 tetrachloride and the like. Other chlorin liquor, salts of humic acid, saponins and the 80 ated aliphatic compounds of the type speci like, of increasing quite considerably the fied above, such as asymmetric dichloroethyl yield of polymerizates from the hydrocar ene, symmetric tetrachloroethylene, di bons and of rendering the process substan choloroacetic acid, dichloromalonic acid, tially quantitative in a comparatively short higher chlorinated aliphatic aldehydes, ace time. tals-alcohols and the like will be likewise 85 operable. Generally, the effect of the chlorin Either pure butadiene hydrocarbons or ated aliphatic compounds will be the great mixtures of the same with each other or with er, the more chlorine atoms they contain at olefine benzenes, such as styrol, cy-methylsty tached to one and the same carbon atom. rol, divinylbenzenes, etc., may be employed By the addition of the aliphatic chlorine as starting materials. 90 compounds in emulsion-polymerization proc The addition of the aliphatic chlorine esses the yield of polymerizates is consider compounds in the emulsion-polymerization ably increased and the time of polymeriza of butadiene hydrocarbons moreover influ 43 tion is shortened. This apparently catalytic ences the properties of the polymerization effect is in many cases, for example, in case products to a greater or less extent. Thus, of aliphatic compounds containing three or the plasticity of the artificial rubber-like four chlorine atoms attached to one and the masses, obtainable in accordance with the same carbon atom, brought about by even improved emulsion process is in many cases very small quantities of the chlorine com betterduced thanaccording that toof therubber-like same process masses but pro in '' 2 1,898,522 the absence of chlorinated aliphatic com ly increased even by prolonging the duration pounds. Accordingly, while the present of the polymerization process. process by an appropriate combination of the Eacample 2-150 kgs. of butadiene and 1.5 chlorine compounds and emulsifying agents kgs of dichloro malonic acid are polymer 5 renders possible the production o plastic ized in emulsion with a solution of 7 kgs. of saponin in 150 kgs. of water at about 55° C. rubber-like masses (especially, in case of After 5-6 days a yield of about 80% of a mixed polymerization products), possessing polymerization product is obtained, while valuable soft rubber properties, there can be without the addition of chlorine compounds obtained, especially when employing highly 5 10 chlorinated organic compounds, peculiarly the yield under the above conditions of work altered polymerization products, differing ing amounts to only about 45%. When em. from the hitherto known artificial rubber ploying trichloroacetic acid instead of the like masses. Some of these altered polymer above chlorine compounds the yield is in izates are especially suitable for hard rubber creased to about 90%. purposes, as guttapercha substitutes and for Eacample 3-100 kgs. of butadiene and 10 80 adhesive or solvent purposes and the like. kgS. of carbon tetrachloride are polymerized As mentioned above the chlorinated ali at about 60° C. in emulsion with a solution phatic compounds can be applied in rather of 10 kgs. of saponin in 100 kgs. of water. small amounts (0.5-2% by weight calculated After about 4 days the yield of polymeriza 20 on the hydrocarbon to be polymerized), but tion product amounts to 75%, while without in some cases, especially in case that com the presence of carbon tetrachloride scarcely pounds of rather small chlorine content are any such rubber formation takes place with applied, or in case that it is desired to pro in the said period. duce polymerizates of strongly altered prop Eacample 4-150 kgs. of isoprene and 15 25 erties in comparison to the polymerizates kgS. of carbon tetrachloride are polymerized obtainable in the absence of chlorinated ali at about 55° C. in emulsion with a solution of phatic compounds, it will be of advantage to 15 kgs. of casein and 5 grams of acetic acid in 150 kgs. of water for about 14 days. After apply the latter in larger amounts, say up working up a very plastic rubber is obtained to 10% (calculated on the hydrocarbon ap 5 30 in a yield of about 75%, while without the plied)The aliphaticor even more. compounds containingto chlo presence of carbon tetrachloride only 25% of rine above indicated can also be used in con polymerization product is obtained. When junction with other substances known to be carrying out the process in neutral solution operative in emulsion-polymerization proc: the yield is still better. 35 esses, such as for example, electrolytes of Eacample 5-A mixture of 100 kgs. of CO yarious nature, oils and other plasticizing butadiene and 50 kgs. of styrol with the addi tion of 10 kgs, of carbon tetrachloride is poly agents.Accordingly, the process offers a simple" merized with a solution of 15 kgs. of saponin means by which in addition to a pronounced in 150 kgs. of water with agitation at about 40 increase in the yield of polymerization prod 60° C. for about 8 days. A plastic polymeri ucts and in the speed of the polymerization zation product is obtained in a yield of 100%, process the possibility is also provided of which does not possess the valuable soft rub regulating to a far-reaching extent the qual ber properties of the styrol-butadiene-emul ity of the polymerization products for any sion-rubbers, but which is suitable for other 45 technical purposes. 10 desiredThe following application. examples illustrate the ine Eaample 6. A mixture of 50 kgs. of buta vention without in any way restricting the diene and 50 kgs. of 2.3-dimethylbutadiene same to the proportions given, nor to the par (1.3) with the addition of 5 kgs. of carbon ticular manner of working. tetrachloride is polymerized at about 50° C. Eacample 1-150 kgs. of butadiene and 15 in emulsion with a solution of 5 kgs. of glue kgs. of hexachloroethane (ClC-CCls) are and 5 kgs. of sodium isobutyl-naphthalene emulsified with a solution of 15 kgs. of sodi sulfonate in 100 kgs. of water. After about um stearate in 150 kgs. of water and poly 6 days a 100% yield of a strong, plastic mixed merized at ordinary or slightly increased rubberis obtained which possesses the highly temperature for 5 days. After the addition valuable properties of soft rubber. 3. of acetone a substantially quantitative yield Eacample .-A mixture of 100 kgs. of buta of a polymerization product is obtained, dif diene and 50 kgs. of styrol with the addition fering in its properties from normal buta of 1 kg. of carbon tetrachloride is polymer diene rubber and which, when rolled out into ized at about 55° C. in emulsion with a solu 60 plates, is transparent in thin layers, has a tion of 7.5 kgs. of glue and 7.5 kgs. of sodium guttapercha-like appearance and can be isobutyl-naphthalene-sulfonate in 150 kgs. of kneaded like paraffin wax. Without the use water. After 5 days a 100% yield of a of hexachloroethane the yield under, the strong, plastic mixed rubber is obtained, above conditions of working amounts to only which possesses the highly valuable proper about 45% of rubber and cannot be essential ties of soft rubber, without the presence of 30 1,898,522 3. carbon tetrachloride only a yield of about a mixture of a compound of the probable 35% of rubber is obtained within the same formula period and this yield is not essentially in CsC-O=CH creased by prolonging the duration of the ! ! Pyterianacample 8-A process. mixture of 100 kgs. of bu wherein a means hydrogen or methyl, and 70 tadiene and 50 kgs. of styrol with the addi of an olefine benzene, in emulsion with water tion of 5 kgs. of chloralhydrate is polymer and an agent possessing emulsifying proper ized in emulsion at about 50-60° C. with a so ties, in the presence of a chlorinated aliphatic O lution of 7.5 kgs. of glue and 7.5 kgs, of sodi compound containing at least two chlorine um isobutyl-naphthalene-sulfonate in 150 atoms attached to one and the same carbon kgs. of water for 5 days. A 100% yield of a atom4. Process which- comprises polymerizing plastic, mixed rubber is obtained possessing a mixture of a compound of the probable 5 the highly valuable properties of soft rubber. formula Without the presence of chloral hydrate the 80 yield of styrol-butadiene-emulsion-rubber ch- - -CH amounts to only about 30-40% within the at a same period, which yield is not essentially in wherein a means hydrogen or methyl, and of 20 creasedpolymerization by prolonging process. the duration of the styrol, in emulsion with water and an agent Eacample 9-5 kgs. of sodium trichloroace possessing emulsifying properties, in the 85 tate are employed instead of the chloral hy presence of a chlorinated aliphatic com drate in the polymerization mixture given in pound containing at least two chlorine atoms Example 8 and the polymerization process is attached to one and the same carbon atom. 25 5. Process which comprises polymerizing carried out under otherwise the same condi 90 tions. A quantitative yield of a plastic a hydrocarbon of the butadiene series in mixed rubber is obtained after 4 days pos emulsion with water and an agent possessing sessing the highly valuable properties of soft emulsifying properties, in the presence of rubber. 0.5-10% by weight (calculated on the amount 30 When employing sodium acetate free from of hydrocarbon applied) of a chlorinated ali chlorine instead of the salt containing chlo phatic compound containing at least two rine, a yield of only about 25-28% is obtained chlorine atoms attached to one and the same within the same period. carbon atom. Eacample 10-1 kg. of trichloroacetic acid 6. Process which comprises polymerizing a 35 is employed instead of the chloral hydrate compound of the probable formula - given in the polymerization mixture in Ex CH---ch, 00 ample 8, and the polymerization process is carried out under otherwise the same condi wherein a means hydrogen or methyl, in tions. A yield of approximately 75% of a emulsion with water and an agent possessing 40 plastic mixed rubber is obtained after only 4 emulsifying properties, in the presence of days, which possesses the highly valuable 0.5-10% by weight (calculated on the amount 05 properties of soft rubber. By employing of hydrocarbon applied) of a chlorinated ali acetic acid free from chlorine instead of the phatic compound containing at least two acid containing chlorine the yield is only chlorine atoms attached to one and the same 4. 5 small within the same period. carbon atom. We claim: 7. Process which comprises polymerizing 10 1. Process which comprises polymerizing a a mixture of a compound of the probable hydrocarbon of the butadiene series in emul formula sion with water and an agent possessing 5 ch:---CH, emulsifying properties, in the presence of a at a 5 chlorinated aliphatic compound containing wherein a means hydrogen or methyl, and at least two chlorine atoms attached to one of an olefine benzene, in emulsion with water and the same carbon atom. and an agent possessing emulsifying prop 2. Process which comprises polymerizing t 5 erties, in the presence of 0.5-10% by weight a compound of the probable formula (calculated on the mixture of hydrocarbons 20 CH---CH, applied) of a chlorinated aliphatic com 2 at pound containing at least two chlorine atoms wherein a means hydrogen or methyl, in attached to one and the same carbon atom. emulsion with water and an agent possessing 8. Process which comprises polymerizing emulsifying properties, in the presence of a a mixture of a compound of the probable 25 chlorinated aliphatic compound containing formula at least two chlorine atoms attached to one and the same carbon atom. oil---OH,at a 3. Process which comprises polymerizing wherein a means hydrogen or methyl, and 30 4. 1,898,522 emulsion with water and an agent possessing ofagent styrol, possessing in emulsion emulsifying with waterproperties, and anin emulsifying properties, in the presence of the presence of 0.5-10% by weight (calcu 0.5-10% by weight (calculated on the amount lated on the mixture of hydrocarbons ap fydrocarbon applied) of trichloroacetic 70 5 plied) of a chlorinated aliphatic compound CIO. containing at least two chlorine atoms at 14. Process which comprises polymerizing tached to one and the same carbon atom. a compound of the probable formula 9. Process which comprises polymerizing C Hi- --CH, a compound of the probable formula 5 0 oil---CH, wherein a means hydrogen or methyl, in 2 emulsion with water and an agent possessing wherein a means hydrogen or methyl, in emulsifying properties, in the presence of 0.5-10% by weight (calculated on the amount ennulsion with water and an agent possessing 80 5 emulsifying properties, in the presence of of hydrocarbon applied) of tetrachlorome 0.5-10% by weight (calculated on the amount thane. of hydrocarbon applied) of a chlorinated 15. The polymerizates obtainable in ac aliphatic compound containing at least three cordance with the process claimed in claim 1. chlorine atoms, of which at least three are 16. The polymerizates obtainable in ac attached to one and the same carbon atom. cordance with the process claimed in claim 3. 20 10. Process which comprises polymeriz 17. The polymerizates obtainable in ac cordance with the process claimed in claim 5. ing a mixture of a compound of the probable 18. The polymerizates obtainable in ac formula cordance with the process claimed in claim 7. cil---CH: 90 2. a in testimony whereof, we affix our signa tures. wherein a means hydrogen or methyl, and of WALTER BOCK. andan olefinean agent benzene, possessing in emulsion emulsifying with proper Water EDUARD TSCHUNKUR. ties in the presence of 0.5-10% by weight 30 (calculated on the amount of hydrocarbons applied) of a chlorinated aliphatic com pound containing at least three chlorine atoms, of which at least three are attached to one and the same carbon atom. 35 11. Process which comprises polymerizing a mixture of a compound of the probable formula CII---CI. 2 105 40 wherein a means hydrogen or methyl, and of styrol, in emulsion with water and an agent possessing emulsifying properties in the presence of 0.5-10% by weight (calculated on the amount of hydrocarbons applied) of a 0. 45 chlorinated aliphatic compound containing at least three chlorine atoms, of which at least three are attached to one and the same carbon atom. 12. Process which comprises polymerizing 50 a compound of the probable formula

CH---ch,at at wherein a means hydrogen or methyl, in 20 55 emulsion with water and an agent possessing emulsifying properties, in the presence of 0.5-10% by weight (calculated on the amount of hydrocarbon applied) of hexachloro ethane 125 60 13. Process which comprises polymerizing a compound of the probable formula CH---ch, 2 65 wherein a means hydrogen or methyl, in 30