ORGANO SILOXANES, METHOD FOR THE PREPARATION THEREOF AND POLYMERIC COMPOSITIONS CONTAINING SAME

Abstract: Organo siloxanes which, in conjunction with organic per­ oxides, serve as vulcanizing or crosslinking agents for poly­ mers, prepared by reacting a fatty alcohol, water and methyl­ vinyldichlorosilane or a mixture of methylvinyldichlorosilane and dimethyldichlorosilane.

Description: ORGANO SILOXANES, METHOD FOR THE PREPARATION THEREOF AND POLYMERIC COMPOSITIONS CONTAINING SAME SUMMARY OF THE INVENTION This invention relates to organo silosanes, prepared by reacting a mixture containing a vinyldichlorosilane, water and a fatty alcohol. The organo siloxanes of this invention can be used as vulcanizing or crosslinking agents for natural and synthetic polymers, in conjunction with organic peroxides. OF THE Vinyl silanes such as vinyl-tris(2-methoxyethoxy)silane are used as vulcanizing or crosslinking agents for natural and synthetic polymers. As a rule, the compositions are formulated by admixing the ingredients and compounding the resultant mixtures to a blend at elevated temperatures, below the vulcanization temperature or crosslinking temperature of the composition involved. It has been found, however, that vinyl silanes such as vinyl-tris(2-methoxyethoxy)- silane, present in the polymeric compositions, undergo hydrolysis in the compounding step, yielding products which tend to be injurious to humans. Specifically, in the case of vinyl-tris(2-methoxyethoxy)- silane, the silane hydrolyzes to 2-itthoxyethanol, a volatile product which tends to be toxic to human beings. OF THE INVENTION The present invention provides organo siloxanes which do not suffer deficiencies previously discussed. The e organo siloxanes of this invention can be added to polymeric material, such as ethylene polymers and the resultant composition compounded to a blend, at elevated temperatures, without undergoing hydrolysis to a toxic, volatile product. The e organo silceanes of this invention, which contain vinyl groups, can be used to vulcanize or crosslink polymers, as will be shown subsequently in this application. The organo siloxanes of this invention are characterized by Formulas I and II below: (average formulas) FORMULA I EMI2.1 wherein R1 and R2, which can be the same or different, are hydrocarbon radicals, generally having 6 to 18 carbon atoms, preferably 12 to 14 carbon arans, and n is an integer having a value of 4 to 100, preferably 4 to 16. X D: EMI2.2 wherein R1 and R2 are as previously defined and x and y, which can be the same or different, are integers having a value of 2 to 50, preferably 2 to 8. Illustrative of suitable hydrocarbon radicals for R1 and R2 are alkyl radicals such as hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl and the like, unsaturated hydrocarbon radicals e.g. the correspond- ing olefinic radicals, such as 1-octenyl, dodecenyl and the like. Among suitable fatty alcohol reactants fran which the hydrocarbon radicals derive are: hexyl alcohol, heptyl alcohol, octyl alcohol, vinyl alcohol, dodecyl alcohol, cetyl alcohol, stearyl alcohol and the like. It may be said, in general, that the preparation of organo siloxanes falling within the scope of Formula I and Formula II can be effected by reacting methylvinyldichlorosilane or a mixture of methyl- vinyldichlorosilane and dimethyldichlorosilane with water and a fatty alcohol or mixtures of fatty alcohols. The 'rolar ratios of water and alcohol can be varied with respect to each rrole of difunctional chlorosilane such that the following stoichiometric equation holds, wherein for purposes of convenience the reactants are shown to be irethylvinyldichiorosilane, water and dodecyl alcohol. EMI3.1 In preparing silanes falling within the scope of Formula II, the amount of methylvinyldichlorosilane (x) plus the amount of dimethyldichlorosilane (y) will be equal to n, according to the following stoichiometric reaction scheme: EMI4.1 Specifically, the preparation of organo siloxanes falling within the scope of Formula I can be carried out by reacting a mixture of methylvinyldichlorosilane, water and a fatty alcohol, at temperatures below the boiling point of water. It is preferred to conduct the reaction at temperatures below about 15 C in order that the HC1 remain in the reaction mixture and serve as an equilibration catalyst, that is a catalyst which increases the production of linear products. The amount of fatty alcohol and water used is a stoichismetric amount, that is, an arrount sufficient to react with all of the chlorine atans of the silane. Preparation of organo siloxanes falling within the scope of Formula II can be carried out at temperatures described above by reacting mixture of methylvinyldichlorosilane, dimethlydichlorosilane, water and a fatty alcohol wherein the amDInt of water used, in moles, is n-l wherein n is equal to the sum of the moles of dimethyldichlorosilane and vinylmethyldichlorosilane. The number of repeating units of each comonomer can be varied as desired by varying the water to alcohol ratio, with the total water and alcohol content being sufficient to react with all the chlorine altars. The reaction itself can be conducted under atmospheric, subatmospheric or superatmospheric pressure, although atmospheric pressure is preferred. At the completion of the reaction in about 3 hours, hydrogen chloride, which is in the reacted mixture, can be removed by a nitrogen gas sparge at elevated temperatures on the order of about 80 C to about 90 C. In order to insure removal of hydrogen chloride fran the liquid product formed, it is convenient to treat the product with a base such as sodium bicarbonate to form sodiun chloride, water and carbon dioxide. Sodium chloride is conveniently reeved fran the product by filtration. As previously stated, the organo siloxanes of this invention can be used as vulcanization or crosslinking agents for polymers. As will be appreciated fran the following discussion and examples, a wide variety of polymers such as rubbers, both natural and synthetic, can be vulcanized by the organo siloxane of this invention. Illustrative of such rubbers are the natural rubbers; balata, caoutchouc, caucho gutta percha, gutta-siak, juleting, kickxia, manihot, latex from the Hevea brasiliensis; synthetic diene polymers, such as horto polymers of hydrocarbons containing two unsaturated bonds such as butadiene-l,3; isoprene, 2,3-dimethyl butadiene-l, 3 and the like, or copolymers of these with one or more copolymerizable mono-olefinic compounds. Copolymerizable mono-olefinic compounds are organic compounds which contain a single olefinic double bond: EMI6.1 and which are copolymerizable with butadiene-1,3 hydrocarons. Such compounds are usually low molecular weight compounds of less than 10 carbon atoms which contain at least two hydrogen atoms and at least one radical other than hydrogen attached to the unsaturated double bond carbon atoms, as in the structure: EMI6.2 where at least one of the disconnected valences is attached to a group other than hydrogen, such as chlorine, alkyl, alkoxy, acyl, cyano or aryl. Examples of such compounds include styrene, p-methyl styrene, alpha-methyl styrene, p-chloro styrene, vinyl naphthalene and similar aryl olefins and substituted aryl olefins, isobutylene and similar copolymerizable olefinic hydrocarbons, acrylic and substituted acrylic acids and their esters, nitriles and amides such as acrylic acid, acrylonitrile, methacrylonitrile, alphy-chloroacrylonitrile, methyl acrylate, methyl methacrylate, ethyl methacrylate, methyl alpha-chloro acrylate, acrylamide, methacrylamide and the like; vinyl methyl ketone, vinyl methyl ether, vinylidene chloride, Nvinyl carbazole, N-vinyl pyrrolidbne and similar copolymerizable compounds containing a single olefinic double bond. Any rubbery copolymer prepared by the ccpolymerization of a butadiene-1,3 hydrocarbon and a copolymerizable mono-olefinic compound can be vulcanized by the organo siloxanes of this invention. The rubbery copolymers which are ordinarily emplcyed are copolymers of butadiene-l, 3 with a lesser amount of styrene, acrylonitrile or an acrylic ester, or the copolymers of butadiene-1,3 and isobutylene. Such copolymers are known commercially under such nans of "Ameripol", "Hycar", "Perbunan", "Buna S", "GR-S", "Chemingum", "Butyl", and "Flexon". Among other suitable polymeric material which can be crosslinked by the organo siloxanes are ethylene polymers such as normally solid hopopolymers of ethylene, copolymers of ethylene andoC-olefins and copolymers of ethylene0C-olefins and diene monomers. Exemplary of suitable copolyrerizable monomers are OC-olefins such as propylene, butene-l, hexene-l, and the like; diene monomers such as butadiene, isoprene and the like; wherein the polymers contain at least about 70 percent by weight ethylene. Preferred copolymers are ethylene-propylene copolymers, ethylene-butene copolymers and the like. These copolymers can be produced under low pressure of about 150 to about 300 psi, using a chromium oxide catalyst modified with titanium as disclosed in U.S. Patent 4,011,382 granted March 8, 1977. The amount of organo silane plus the amount of organic peroxide used, in formulating the polymeric compositions are sufficient to vulcanize or crosslink the polymers to cross linked products. As a general rule, the organo siloxanes are used in amounts of about 0.1 to about 5 percent by weight, preferably about 0.5 to about 2 percent by weight based on the weight of the polymer, with the organic peroxide being present in an anoint of about 1 to about 3 percent z nt by weight, preferably in an arrount of about 1.5 to about 2 percent by weight, based on the weight of the polymer. It is to be understood that additives commonly added to polymeric compositions such as fillers such as clay, carbon black, antioxidant4 and the like can be added to the compositions of this invention, if so desired. The following examples further illustrate the present invention and are not intended to limit the scope thereof. EXAMPLE 1 Siloxane-l - characterized by gel peureation chromatography and nuclear magnetic resonance specto5copy as having the average formula: EMI8.1 was prepared as follows: Into a two liter, 3-necked flask equipped with an addition funnel, mechanical stirrer, thermometer and distillation head, with receiver protected by a nitrogen gas by-pass, was added 846.0 g (6.0 moles) of methylvinyldichlorosilane. From the addition funnel, there was added 294.7 g (1.5 moles) of dodecanol to the flask at a rroderate rate with stirring. The temperature of the flask decreased to < 100C due to evolution of HC1. After the dodecanol had been added, 89.7 g (5.0 moles or 958 of the stoichiometric amount) of water were slowly charged fran the addition funnel while maintaining the contents of the flask at a temperature of 10 + 5 C with an external ice bath. After the water was added, the mixture was held at 15 + 5 C for an additional 3 hours with stirring (the HC1 equilibration step). The addition funnel was replaced by a N2-sparge tube and the contents of the flask were slowly heated to 90 C, continuously removing HC1 fran the flask. After 30 minutes, a sample fran the flask was analyzed and found to contain 0.11 meq clT/g sample. The remaining amount of water (4.5 g, 0.25 mole) was added as a saturated Na2C03 solution. Heating was resumed for an additional 30 minutes at 80 C, continuing the N2-sparge throughout. The remaining acid chloride was neutralized with damp NaHCO3. The resultant product was filtered, yielding 759.0 g (theory 792.5 g) 96% of theory of a clear, colorless fluid of 16.5 cstk viscosity (at 25qC), having a chloride content of 0.01 meg/g (0.04%). The source of dodecanol used in preparing the siloxanes noted herein was a Procter & Gamble product CC-1214 Fatty Alcohol, a brand name for a mixture containing dodecanol and a small amount of C14 alcohol. EXAMPLE 2 - SILOXANE-2 Siloxane-2 - characterized by gel permeation chromatography and nuclear magnetic resonance be spectroscopy as having the average formula: EMI10.1 was prepared as follows: Into a 1 liter, 3-necked flask, equipped with an addition funnel, condenser, mechanical stirred, thermometer, and protected with a nitrogen gas by-pass, was added 282.0 g (2.0 moles) of methylvinyldichlorosilane. From the addition funnel, there was added 98.25 g (0.5 mole) of dodecanol, slowly with stirring, while maintaining the temperature between 10-15 C. After the dodecanol had been added, 28.4 g (1.59 mules, 90% of required stoichiometry of 1.75 moles) of water were added with stirring, maintaining a temperature between 10-15 C on the reaction vessel by means of an ice bath. The contents of the flask were stirred for 3 hours at a temperature between 10-15 C. The addition funnel was replaced by a tube inserted into the liquid reaction mixture and nitrogen was passed through the mixture while heating to a temperature of 90 C with stirring to remove hydrogen chloride fran the flask. After 0.5 hour at a temperature of 900C, the remaining stoichiometric quantity of water (3.1 g) was added as saturated Na2C03. All residual hydrogen chloride was then neutralized as described for the preparation of Sil3xane-l. After filtration 250 g of a clear, colorless fluid of 18.4 cstk (25 C) viscosity were obtained. EXAMPLE 3 - SILOXANE-3 Siloxane-3 - characterized by gel permeation chromatography and nuclear magnetic resonance spectroscopy as having the average formula: EMI11.1 was prepared following the procedure described with respect to Siloxanel, by reacting 282.0 g (2 moles) methylvinyldichlorosilane, 46.6 g (0.25 rrole) dodecanol and 33.75 g (1.875 moles) H20 to produce 178.5 g of a clear, colorless fluid. EXAMPLE 4 Silkoxane-4 - characterized by gel permeation chromatography and nuclear magnetic resonance spectroscopy as having the average formula: EMI11.2 was prepared by following the procedure described with respect to Siloxane-1, by reacting 141.09 (1.0 mole) methyldichlorosilane, 129.1 g (1.0 mole) dimethyldichlorosilane, 93 29 (0.5 rrole) dodecanol and 31.5 g (1.75 moles) water to produce 193.5 g of a clear, colorless fluid. The following examples illustrate the ability of the siloxanes to vulcanize rubbet. Composition were formulated by admixing the components, with the exception of the peroxide, in a Banbury mixer at a temperature and for a period of time to insure thorough mixing. The compositions were -sheeted on a tWD roll mill wherein the peroxides were added. Each composition was then molded into test plagues according to the proceure described in ASTM test D-15-72 and then vulcanized in a heated press under pressure for 20 minutes at a temperature of 340 F. Tests to which the seecMrris were subjected and results thereof are set forth in Table 1. These results establish the improvement in physical properties of the compositions of this invention which contain the claimed siloxanes TABLE I Example 5 Example 6 Example 7 Example 8 Control 1 Control 2 Ethylene-Propylene Copolymer (Vistalon 404-Sold by Exxon Company) 100 100 100 100 100 100 Siloxane-1 0.5 1.0 0.5 1.0 --- -- Poly-2,2,4-trimethyl-1,2-dihydroxyquinoline (antioxidant) 1.5 1.5 1.5 1.5 1.5 1.5 Zinc Oxide 5 5 5 5 5 5 Carbon Black 2 2 2 2 2 2 Vulcup-R &alpha;,&alpha; ;'-bis-(t-butylperoxy) disopropylbenzene 2 2 2 2 2 2 Clay-(Translink 37-Sold by Freeport Kaolin Company) 110 110 --- --- 110 -- Clay-(Burgess KE-Sold by Burgess Pigment Company) --- --- 110 110 --- 110 Hardness, Shore A ASTM-D-2240-68 62 62 62 62 61 61 Elongation, Percent ASTM-D-412-68 540 460 390 360 610 430 300 Percent Modulus, psi ASTM-D-412-68 780 920 970 1040 710 830 Tensile Strength, psi ASTM-D-412-68 910 1030 1040 1080 860 950 Set at Brak, Percent ASTM-D-412-68 52 15 15 15 35 20

Claims: WHAT IS CLAIMED IS: 1. An organo siloxane having the average formula: EMI14.1 wherein R1 and R2 are hydrocarbon radicals having 6 tQ 18 carbon atoms and n is an integer having a value of 2 to 50; or having the average formula: EMI14.2 wherein R1 and R2 are as previously defined and x and y are integers each having a value of 2 to 50. 2. An organo siloxane having the average formula: EMI14.3 3. An organo siloxane having the average formula: EMI14.4 4. An organo siloxane having the average formula: EMI15.1 5 An organo siloxane having the average formula: EMI15.2 6. A polymeric composition oontaining an organic peroxide and an organo siloxane and facultatively filler, as defined in claim 1. 7. A polymeric composition as defined in claim 6 wherein the filler is clay. 8. A method of producing an organo siloxane as defined in one or more of the claims 1 - 7 which comprises reacting a mixture containing water, a fatty alcohol and methylvinyldichlorosilane or a mixture of methylvinyldichloro silane and dimethyldichlorosilane. 9 A method as defined in claim 8, conduced at teMperatures below about 150C.

Inventors: PETTY, HERBERT EUELL
Applicants: UNION CARBIDE CORPORATION
Application year: 1983
Main classification: C08G77
IPC codes: C08G77, C07F7, C08K5, C08K3, C08L83