Патент USA US2407181код для вставки
Patented Sept. 3, 1946 ' 2,407,181 UNITED STATES ‘PATENT OFFICE 2,401,181 ‘ ' ARTIFICIAL waxes AND GREASES Samuel Le Roy Scott, Wilmington, Del., asslgnor to E. I. du Pont de Nemours 8: Company, Wil mington, Del., a corporation of Delaware , ‘ No Drawing, Application March 30, 1944, Serial No. 528.770 8 Claims. , (Cl. 260—-2) . This invention relates to the reaction of a 2 ' The end of the reaction is indicated by the ces polymerizable aliphatic monoole?nic hydrocar; sation of ethylene absorption. When this point bon with a silicon halide and to novel products is reached, the reaction mixture is allowed to cool, removed fromv the reactor, and the mono meric silicon halide, e. e., silicon tetrachloride, with any added inert organic solvents which may resulting therefrom. This invention has as an object the prepara tion of wax-like polymeric products from a poly merizable aliphatic monoole?nic hydrocarbon have been employed, is removed by distillation. and a silicon halide. preparation of wax-like compounds from ethyl The residue which is an organic material con~ taining silicon and chlorine‘ is greasy to wax-like ene and a siliconhalide. Other objects will ap 10 in character, usually melting between 85° and pear hereinafter. The further object is the , a 110° 0., although lower melting products can be -_ These objects are accomplished by the follow obtained. ‘The reaction products produced by ing invention wherein a polymerizable monoole this reaction have molecular weights of between ?nic aliphatic hydrocarbon of from’ two to four 400‘ and approximately 4000, although slightly carbon atoms is reacted with a silicon halide of 15 higher molecular weight products can be ob— not more than twenty-one carbon atoms, having tained when silicon tetra?uoride is employed. directly attached to silicon at least one halogen The mixtures obtained by this reaction of the atom of atomic weight below 90, i. e., selected silicon halide and the monoethylenically unsatu from the class consisting of ?uorine, chlorine, rated hydrocarbon such as ethylene in the ab ‘and bromine. 2,0 sence of a Friedel-Craf-ts catalyst are not readily The reaction is carried out in the absence'of'a amenable to separation by distillation or other Friedel-‘Crafts reaction catalyst and preferably means into their component parts and the mix ture can be employed per se, since it is probably a mixture of functionally similar compounds. In order that the process may be more fully in the presence of a catalyst which is effective for the polymerization of the monoole?nic hydrocar- ' bon and ine?ective in the Friedel-Crafts reac understood, the following speci?c examples are given by way of illustration. In the examples, the parts given are parts by weight. ' tion. The reaction of the silicon halide with the polymerizable aliphatic ~monoole?nic hydrocar bon, e. g., ethylene, to give wax-like products is carried out in general as follows: A reaction ap Example I I paratus, a pressure reactor capable of being A pressure reactor was charged with 78 parts heated and provided with a means of agitation, is equipped with inlet tubes for admitting a gase of cyclohexane, 30 parts of silicon tetrachloride, one part of hexachloroethane, and one part of ous monoole?nic hydrocarbon such as ethylene, a mercuric chloride. The reactor was flushed with vent connected to a safety rupture disc, and a 35 nitrogen, closed, and pressured to about 150 at-‘ mospheres pressure with ethylene. The tempera pressure gauge. The liquid charge, which con’ ture was then raised to 275° C. with a correspond sists of a silicon halide such as silicon tetrachlo ing increase in pressure within the reactor to - ride, and usually small amounts ofa catalyst (OJ-5%) such as ‘a peroxygen compound, e. g., approximately 900 atmospheres. Over a reac diethyl peroxide, with or without inert organic tionperiod of 16 hours, the pressure was main solvents such as ,cyclohexane, is placed in the tained at 900 atmospheres by occasional injection of ethylene and during‘this period the total pres pressure reactor. The reactor is then ?ushed sure drop was about 175 atmospheres. The re with nitrogen, closed, the contents agitated by a suitable means such as stirring with an internal actor was cooled, ethylene bled off, and the prod stirrer or by agitation of the reaction vessel, and 45 uct which consisted of a solid suspended in the ethylene is admitted. ' The pressure of ethylene cyclohexane was obtained. This solid material for the reaction with silicon tetrachloride is pref was ?ltered and dissolved'in benzene, and the ’ erably between 600 and 1000 atmospheres and benzene solution ?ltered. After ?ltration,‘ the the temperature‘ at which the reaction is usually benzene solution was heated to distill the unre carried out is between 75 and 300° C. Pressures 50 acted silicon tetrachloride'and after about 3A of of from 20 to'1000 or more atmospheres may be the benzene had also been ‘distilled, the‘ re used and the exact pressure and temperature em mainder of the benzene was removed by steam ployed-is dependent upon such factorsv as the distillation and the product ?ltered from the wa speci?c catalyst employed and properties desired in the resulting product. ter. After drying under reduced pressure at‘100" 55 0., the product, consisting of about 16 parts of 2,407,181 ' 3 a soft, tacky wax, was found to contain about“ 0.07% siliconnand had a molecular- weight of about 487 as determined by elevation of the boil ing point of a benzene solution. The waxy prod uct melted at about 85° C. cooled and the ethylene bled oil. The reactor was then warmed and evacuated to remove unreacted dimethylsilicon dichloride. There was obtained seven parts of a waxy product (puri?ed by pre cipitation from xylene/methanol mixture) which contained 0.11% silicon and 1.10% chlorine. The A similar reaction product was obtained when, ’ waxy product melted at 106-l09° C. in place of the hexachloroethane and mercuric The above described reaction, between silicon chloride, 0.4 part of diethyl peroxide was used as halides and an ole?n can be carried out with catalyst under similar conditions. 10 any polymerizable aliphatic monoole?nic hydro Example I! carbon capable of being polymerized when treated with a peroxygen catalyst. Although ethylene A silver lined reaction vessel was charged with undergoes the reaction with silicon tetrachloride 85 parts of silicon tetrachloride, 0.5 part of po readily, other monoole?nic hydrocarbons having tassium chlorate, and 0.1 part of manganese di oxide. The reactor was swept free of air with a 15 from two to four carbon atoms and which pref erably have a CH:=CH— (vinyl group) may be current of nitrogen. closed, and ethylene admitted used. to the tube until a pressure of 150 atmospheres In the process of this reaction there may be em was obtained. The temperature of the tube was ployed any silicon halide having at least one then raised to about 200° C. and additional ethylene added to bring the pressure to 900 at 20 halogen of atomic weight below 90, i. e., ?uorine, chlorine or bromine directly .attached to siliconin mospheres. The reactor was maintained at this temperature for about 14 hours and ethylene was ' cluding (CrHsO) zslClz, C2H5OS1C13, (CH3) 281012, SiCh, SizBro, SiBn, SlF4, SlFzClz, Sl(CI-Ia) C13, occasionally admitted to maintain the pressure _ SiHClc, S1(CH3)F3, SKGH'!) 2C12, CaHsCHaSiCla, at about 900 atmospheres. At the end of this (CuHsCI-Iz) 2S1Cl2, SiHsCl, period, the reactor was cooled and the unreacted 25 Si (CrHs) 2012, (CcHt) aSlF, (CaHt) aSiCl, (C6H5CH2)3S1C1. ethylene removed. The unreacted silicon tetra chloride Was distilled from the reaction vessel by Although the reaction of the present invention attaching the reactor .to a vacuum line and re can occur in the absence of substantial amounts ducing the pressure to about 10 mm. The solid of a catalyst, it is preferred to use a catalyst product left within the reactor was rinsed with 30 which is effective for the polymerization of the water and the water removed by ?ltration. The a oleflnic hydrocarbon and which is ineffective as a solid was dissolved in xylene, ?ltered, and meth-' catalyst for Friedel-Crafts reactions, (1. e., alkyl anol added to give a precipitate, which was then ation or acetylation reactions). By way of ex ?ltered from the xylene/methanol mixture. The ample, the following suitable catalysts may be product after drying in vacuum consisted of 23 35 mentioned as effective for the reaction between parts of a waxy material softening at 87° C. and silicon halides and an ole?nic hydrocarbon such melting at 104° C. when heated on a copper bar. as ethylenezperoxygen compounds‘, e. g., diacyl The product contained 0.55% silicon and 1.22% peroxides such as acetyl peroxide, dibenzoyl per chlorine. oxide, and lauroyl peroxide; dialkyl peroxides Example III 40 such as diethyl peroxide; other peroxides such as When a reaction was run in a manner similar ascaridole, cyclohexanone peroxides; ammonium persulfate, perborate, and percarbonate; molec cular oxygen; amine voxides, for example, tri to that of Example II except that for the potas sium chlorate manganese dioxide mixture, there was substituted about 0.5 part of “Chloramine-T" methylamine oxide; oxygen-containing com Example IV dibenzoylhydrazine, hydrazine dihydrochloride; as catalyst, a product was obtained which softened 45 pounds such as manganese dioxide, perchlorate, etc.; such metal alkyls as tetraethyllead and at 85° C. and melted at 104-110‘ C. when heated tetraphenyllead; ultraviolet light, especially in on a copper block. This product contained 0.91% the presence of such photosensitizers as mercury; silicon and 2.06% chlorine. - 50 N-halomines, e. g., “Chloramine-T"; and tetra chloroethane. Combinations of some of these A stainless steel pressure reactor was charged compounds with other compounds, for example with 80 parts of benzene and 0.3 part of benzoyl with mercuric chloride, are also useful.‘ These peroxide. The reactor was closed; evacuated. and compounds or combinations are effective as cata cooled by “Dry Ice.” There was then added 50 parts of silicon tetra?uoride and the reactor was 55 lysts for the polymerization of ethylene under the pressured to 600 atmospheres with ethylene. The conditions of temperature and pressure that are necessary. In general, these catalysts have been reactor was heated to 80° C. and ethylene injected termed “telomerization catalysts" as described in occasionally to maintain a pressure of 810-960 pending application. Serial Number 438,466. These atmospheres. A pressure drop of 310 atmospheres occurred during a period of about nine hours 60 catalysts are usually employed in amounts varying from about 0.01 to 5.0% by weight as based on after which the reactor was cooled and the ethyl the silicon halide present. When molecular oxy ene and unreacted silicon tetrailuoride were bled gen is employed as a catalyst, its concentration off. There was obtained 25 parts of a solid which should be less than 1000 parts per million as gave a waxy, brittle film. The solid product con 65 based on the polymerizable ole?nic hydrocarbon tained 0.14% silicon and 1.2% ?uorine. Example V _ A stainless steel pressure reactor was charged , with 0.5 part of potassium chlorate, 0.1 part of manganese dioxide. and 25 parts of dimethylsili con dichloride. Ethylene was introduced and maintained at 850-950 atmospheres while the re actor was heated to 198-201° C. At the end of ; nine hours, during which there was a total pres employed. , ' To obtain the polymeric products of this in vention the reaction is to be carried out in the absence of a Friedel-Crafts reaction catalyst such 70 as a halide of an amphoteric metal, e. g., alumi num trichloride, since the reaction in the pres ence of a Friedel-Crafts type catalyst leads .to low molecular weight, non-polymeric compounds containing one unit derived from the silicon hal sure drop of 105 atmospheres. the reactor was 75 ide and one from the oleilne. ' 2,607, 181 5 6 To obtain a sufllcient' concentration of polymerizable oleflnic hydrocarbon. such as ethylene; it is necessary usually to employ superatmospheric . The wax-like polymeric products of this inven tion are useful in the preparation of polishes such as automobile polishes, floor polish, shoe polish, emulsion floor polish, and other places where pressure. Although pressures of 20-1000 atmos pheres can be used for this reaction, the ultimate pressure limit for the reaction is only that which the equipment available will stand and accord ingly pressures higher than 1000 atmospheres camauba or similar waxes have found employ ment. These waxes similarly are useful as modi fiers for lubricating 011. paper coating, and‘im pregnation as for example as a textile ?nish and may be used. Pressure is used principally as a similar applications. The higher molecular‘ means of obtaining su?icient concentration of 10 weight products can be fabricated‘ into self-sup ole?ns at the temperatures desired. - porting illms, etc. ‘ . In a similar manner the temperature for the re The above description and examples are in action of silicon halides‘ with the polymerizable tended to be illustrative only. Any modification aliphatic monoolefi-nic hydrocarbons ' may be thereof or variation therefrom which conforms ‘ varied within wide limits and is dependent usually 16 to the spirit of the invention is‘intended to be upon the catalyst employed. For the majority of cases, temperatures of 50° to 300° C. are employed. For such catalysts as those having directly linked included within the scope of the claims. What is claimed is: 1. Process for the preparation of greasy to ' oxygen atoms such as the peroxy compounds, the waxy, silicon-containing, polymeric materials temperature range is usually 50° to 150° C. For 20 which comprises reacting ethylene with a silicon halide containing not more than twenty-one car molecular oxygen, hexachloroethane, chlorate manganese dioxide mixtures, the temperature re bon atoms and having directly attached to silicon quired for catalytic action is usually between 125° at least one halogen selected from the class con and 300° C. . sisting of ?uorine, chlorine, and bromine, at 50—- ' Inert diluents such as isooctane, cyclohexane, 25 300° C. and a pressure of at least 20 atmospheres, any catalyst present being a polymerization cat benzene or similar aliphatic, cycloaliphatic or aromatic hydrocarbons may be employed. It is alyst ineffective in the Friedel-Crafts reaction. preferred to use low boiling solvents which can 2. Process for the preparation of greasy to waxy, silicon-containing, polymeric materials readily be removed by distillation of the reaction mixture. The reaction should be carried out‘ 30 which comprises reacting ethylene with silicon " under anhydrous conditions to avoid hydrolysis tetrachloride at 50-300° C. at an ethylene pressure , of the silicon halides. The compounds resulting of at least 20 atmospheres, any catalyst present from the polymerization of ethylene with silicon being a polymerization catalyst ineffective in the halides, e. g., silicon tetrachloride, are wax-like Frieder-Crafts reaction. materials having molecular weights between 400 35 may be obtained by adjustments in the propor- ‘ 3. Process for the preparation of greasy to waxy, silicon-containing, polymeric materials which comprises reacting ethylene with silicon tions of silicon halide and catalysts employed, and tetrachloride at 50-300° C. at an ethylene pres- I and 4000 although higher molecular weight values ‘ in choice of temperature and pressure, 1. e., the sure of at least 20 atmospheres, any catalyst pres concentration of olefin employed. In general, the 40 ent being a potassium chlorate-manganese diox ide catalyst. molecular weight .of the polymeric material is increased by increasing the pressure, 1. e., increas 4. A greasy to waxy, silicon- and halogen-con ing the relative concentration of ethylene. The molecular weight is also increasedv by decreasing the reaction temperature and/or decreasing the catalyst concentration. Materials of higher average molecular weights, e. 8-, up to15,000 may ' taining, polymeric product of the reaction, at 50 300° C. and a pressure of at least 20 atmospheres, of a silicon halide containing not more than twenty-one carbon atoms having‘ directly at tached to silicon at least one halogen selected . from the class consisting of ?uorine, chlorine, and be obtained when silicon tetrailuoride is used. .It is probable that small amounts of polymers of bromine, with ethylene, any catalyst present being ethylene are also formed during the silicon halide 60 a polymerization catalyst ineffective in the ethylene reaction. The products obtained by the above described reaction are different from monomericaddition Friedel-Crafts reaction. ' 5. A ‘greasy to waxy polymeric product of the reaction, vat 50—-300° C. and a pressure of at least products of silicon halides with an'ethylenically _ 20 atmospheres, of silicon tetrachloride with eth unsaturated hydrocarbon and also differ in 66 ylene, any catalyst present being a polymeriza molecular weight and other properties from the tion catalyst ineffective in the Friedel-Crafts re polymerizable products of ethylene or other‘ action. a 6. A greasy to waxy polymeric'product of‘the absence of the silicon halide. It is probable that reaction, at 50—300° C. and'a pressure of at least there are produced in this reaction compounds 60 20 atmospheres, of silicon tetrachloride with eth ylene, any catalyst present being potassium of the general formula A<CH2CH2>11B in which n monoole?nic hydrocarbons when prepared in the , is a plural integer and A and B together form a silicon halide. In the case of the reaction em chlorate-manganese dioxide catalyst. 7. Process. which comprises adding ethylene to a reaction charge consisting of silicon tetrachlo ploying ethylene and silicon chloride the product comprises reaction products of the formula 66 ride, potassium chlorate and manganese dioxide at a temperature of about 200° C. and maintain- , Cl(CHzCH2)nSiCla where n is a plural integer. ing a pressure of about 900 atmospheres by the Some of the halogens of such compounds are addition of further ethylene for about fourteen probably removed when the reaction product is hours. ' subjected to mild hydrolysis, for example as dur 8. A waxy material containing silicon and chlo ing puri?cation. ‘This type of reaction is called rine softening about 8'7‘’- C. and melting vabout "telomerization” and has been described inpend 104‘? C. obtained by the process of claim 7. ing application, Serial Number 438,468. . ' SAMUEL LE ROY SCO'I'I‘. Certi?cate of Correction ‘ v Patent No.‘_ 2,407,181. Seiitember a, 1940. SAMUEL LE ROY SCOTT It is hereby certi?ed that error appears in the Yrinted speci?cation of the above numbered atent requiring correction as follows: Co umn 4, line 22, for “(CH|),SiC1," read (0H, )pS’iOlz; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent O?ice. Signed and sealed this 19th day of November, A. D. 1946. ‘ [m] _ LESLIE FRAZER, - _ First Assistant Oommissioner of Patents.