Ethyl Corporation

Albemarle Corporation

Gunner E. Nelson

Kaung-far Lin

Carroll W. Lanier

Gunner E Nelson

John G Loop

Tillmon H Pearson

Carroll W Lanier

Charles R Everly

Kaung-Far Lin

Arcelio J Malcolm

Michael J Dagani

Isaac L Smith

Novel methods for producing alpha-alkenylalkylsilanes by reacting alkenylhalosilanes and organoalkalimetalaluminates have been discovered. For example, vinyltrichlorosilane and sodium tetraheylaluminate can be reacted to produce alpha-alkenyltrihexylsilane.

Methods of producing alpha-alkenylalkylsilanes

New methods of producing phenylalkylsilanes having a desired ration of phenyldialkylsilanes to phenyltrialkylsilanes using effective control of temperature in the reaction of sodium trialkylaluminum and phenyltrihalosilanes are disclosed.

Method of preparation of phenylalkylsilanes

Improved silahydrocarbon mixtures comprising phenyltrialkylsilanes wherein the alkyl groups independently are hydrocarbon chains having from about 4 to about 20 carbon atoms, preferably each independent alkyl group differing from the other by no more than about 2 carbon atoms, are produced having unexpectedly good resistance to oxidation and having use in lubrication compositions.

Phenyltrialkylsilane lubricating compositions

Novel methods for the preparation of sodium aluminum tetraalkyls have been discovered comprising the reaction of sodium aluminum tri-isobutyl hydride and olefins. The methods avoid the use of sodium aluminum hydrides and permit in one step both the substitution of isobutyl groups and additions at hydride hydrogens to produce sodium aluminum tetraalkyls.

Preparation of sodium aluminum alkyls

Olefins and metal aluminum tetraalkyls react with alkylhalosilanes to yield mixtures of tetraalkyl silanes which may be employed as functional fluids. For example, decene-1 and sodium aluminum tetraoctyl, NaAl(C.sub.8 H.sub.17).sub.4, react with dialkyldichlorosilane. The mole ratio of sodium aluminum tetraalkyl to halosilane in from about 0.5:1.0 to about 1:1, and the ratio of olefin to the metal aluminate is selected to confer in the product mixture, the desired concentration of alkyl radicals derived from the olefin.

Preparation of alkyl silanes

A silahydrocarbon functional fliud comprising a mixture of silahydrocarbons of the formula RSiR'.sub.3, wherein the R' radicals may be alike or different, is prepared by a three step process. In the first step in a preferred embodiment, sodium, aluminum, hydrogen, and olefin (corresponding to the radical R') are reacted in the presence of a triorganoaluminum catalyst. In a second step, fresh catalyst is added and reaction is continued. In a third step, the product of the second step is reacted with a trihaloalkylsilane to produce the RSiR'.sub.3 product. Such a product satisfied the U.S. Air Force specification for silahydrocarbon base stock.

Vinyl-olefins are converted to vinylidene olefin dimers at a selectivity of at least 85 mole percent by reacting a mixture of dry vinyl-olefin containing 0.001-0.04 moles of trialkyl aluminum per mole of initial vinyl-olefin at a temperature in the range of about 100.degree.-140.degree. C. for a time sufficient to convert at least 80 mole percent of the initial vinyl-olefin to a different material.

Vinylidene dimer process

Olefins and metal aluminum tetralkyls react with alkylhalosilanes to yield mixtures of tetraalkyls silanes which may be employed as functional fluids. For example, decene-1 and sodium aluminum tetraoctyl, NaAl(C.sub.8 H.sub.17).sub.4, react with methyltrichlorosilane. The mole ratio of sodium aluminum tetraalkyl to halosilane is from about 0.75:1.0, to about 1:1, and the ratio of olefin to the metal aluminate is selected to confer in the product mixture, the desired concentration of alkyl radicals derived from the olefin.

Silahydrocarbons having the formula RSiR'.sub.3 are prepared by a three step process. In the first step in a preferred embodiment, sodium, aluminum, hydrogen and olefin (corresponding to the radical R') are reacted in the presence of a triorganoaluminum catalyst. In a second step, fresh catalyst is added and reaction continued. In a third step, the product of the second step is reacted with a trihaloalkylsilane to produce the RSiR'.sub.3 product. Such products are useful as functional fluids.

A process for the preparation of a phosphinic acid, ##STR1## said process comprising reacting a phosphorus oxyhalide, POX.sub.3, with an alkali metal tetraalkyl aluminate, MAlR.sub.4, wherein X is halogen, M is an alkali metal, and R is an alkyl radical.

Preparation of phosphinic acids

In the direct synthesis process for producing NaAlH.sub.4 (pressure hydrogenation of Na and Al in a liquid phase reaction medium at an elevated temperature) advantages are realized by insuring that the initial reaction mixture contains a small amount of water and/or an alcohol. In particular, the induction period is shortened. And, the time, trouble and expense of purifying and pre-drying the reaction medium are avoided.

Synthesis of sodium aluminum hydride

Mixtures of silahydrocarbons which comprise a product RSiR'.sub.3, wherein R is an alkyl of 1-4 carbons, and R' is an alkyl of 8-14 carbons are produced by reacting a silicon tetrahalide, SiX.sub.4, a trialkylaluminum, R.sub.3 Al, and an alkali metal aluminate NaAlR'.sub.4. An alkali metal salt increases the relative amount of RSiR'.sub.3 in the product. The trialkylaluminum can be replaced with an olefin or with an organoaluminum sesquihalide. The products are useful as functional fluids.

Alkali metal aluminates, NaAlR'.sub.4, react with alkyl trihalosilanes, RSiX.sub.3, in accordance with the following equation:

Alkali metal aluminum tetraalkyls can alkylate tetraalkyl silicates and alkyltrialkoxysilanes, Si(OR).sub.4 and RSi(OR).sub.3, respectively. The product in each case is predominately the dialkylate. With tetraalkyl silicates, both of the alkyl groups bonded to silicon in the dialkylate product are derived from the metal tetraalkyl. With alkyltrialkoxysilanes, the silicon atom in the dialkylate product is (a) bonded to one alkyl group detained from the metal tetraalkyl, and (b) is also bonded to an alkyl group--that was bonded to silicon--in the silicon-containing starting material. Thus, the alkyl groups in the dialkylate product that are bonded to silicon can be alike or different. The dialkyldialkoxysilane products produced by this invention can be reduced to the corresponding silanes; e.g., R.sub.2 SiH.sub.2, by using an alkyl aluminum tetrahydride as the reducing agent. The dialkyldialkoxysilanes as well as the dialkylsilanes produced are useful as chemical intermediates.

Preparation of dialkyldialkoxysilanes and related compounds

Silane and monoalkylsilanes can be alkylated using an alkali metal aluminate, MAlR.sub.4, wherein M is Li, Na, or K and each R is a straight chain, alkyl radical solely composed of carbon and hydrogen containing from about 4 to about 18 carbon atoms. The aluminate can be used as a reactant, optionally in the presence of a straight chain alpha-olefin corresponding to the alkyl group in the aluminate. Alternatively, the aluminate can be used as a catalyst for the reaction of the olefin and the silane reactant, in which case from about 5 to about 10 mole percent of the aluminate (based on the silane reactant) is employed. The catalytic reaction is promoted by a smaller amount of a lithium salt such as lithium chloride. Both embodiments are conducted at somewhat elevated temperatures, approximately 160.degree.-210.degree. C., and at autogenous pressures, using reaction times of 8-20 hours. The products are useful as functional fluids or as intermediates.

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Baton Rouge, LA, United States of America

Gunner E Nelson