Organic compounds -- part of the class 532-570 series – Organic compounds – Silicon containing
Reexamination Certificate
2000-03-07
2001-01-16
Shaver, Paul F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Silicon containing
Reexamination Certificate
active
06175031
ABSTRACT:
BACKGROUND OF INVENTION
This invention relates to a method for synthesizing silicon compounds that contain a substituent bonded to silicon through Si—C bond. This method is undertaken for the purposes of property improvement and imparting reactivity and proceeds through the reaction of unsaturated compounds with silane compounds.
The hydrosilylation reaction is a generally applicable method for the chemical modification of organic compounds by silane compounds. This method employs hydrosilylation between SiH-functional silane and an unsaturated bond-bearing organic compound and is applicable to a fairly broad range of SiH-functional compounds and unsaturated bond-bearing organic compounds. Platinum and rhodium catalysts are generally used to run the hydrosilylation reaction in industrial or commercial processes. Since these metals are very expensive, it is crucial that the catalytic efficiency in the hydrosilylation reaction also be very high. In addition, the hydrosilylation reaction is frequently accompanied by competing side reactions and may include reaction pathways that produce a number of isomers. As a consequence, the hydrosilylation reaction is generally accompanied by such catalyst-related issues as product yield, product selectivity, and production of a single isomer. Modification of the catalyst can be carried out in order to address these problems and issues. For example, various ligands can be added and/or chemically bonded to the catalyst, or the catalyst can be immobilized on any of various different supports. However, these chemical and physical modifications are typically problematic, for example, (1) their effects may rapidly disappear and (2) an improved catalytic selectivity is generally accompanied by a lower activity. In addition, since platinum catalysts gradually lose their activity under oxygen-free conditions, implementation of the hydrosilylation reaction in the presence of oxygen becomes unavoidable thereby increasing side reactions and risk of fire.
With regard to the platinum-catalyzed hydrosilylation reaction between SiH-functional silicon compounds and unsaturated group-bearing organic compounds, the object of the present invention is to introduce a reaction method that provides a high catalyst activity and stability and that also provides a high positional selectivity in the hydrosilylation reaction product. An additional object is to achieve these features without the addition of oxygen and thereby reduce the risk of fire and explosion in the hydrosilylation reaction.
SUMMARY OF INVENTION
A method for synthesizing silicon compounds containing a substituent bonded to silicon through a Si—C bond comprising reacting (a) an unsaturated group-functional organic compound or unsaturated group-functional organosilicon compound with (b) a hydrosilyl-functional organosilicon compound described by formula
HSiR
2
n
Z
3-n
under the action of (c) a platinum catalyst and in the presence of (d) a hydro(acyloxy)-functional silicon compound described by formula
HSiR
2
(O(C═O)R
1
)
or in the presence of (e) a carboxylic acid compound and a hydro(alkoxy)silane; where each R is independently selected from the group consisting of organic groups, siloxy groups, and siloxanoxy groups and each R
1
is independently selected from the group consisting of a hydrogen atom and organic groups, each R
2
is an independently selected hydrocarbon group; each Z is independently selected from the group consisting of silamino groups, siloxy groups, and siloxanoxy groups, and n=0, 1, 2, or 3.
DESCRIPTION OF INVENTION
The present invention is a method for synthesizing silicon compounds that contain a substituent bonded to silicon through a the Si—C bond by reacting (a) an unsaturated group-functional organic compound or unsaturated group-functional organosilicon compound with (b) a hydrosilyl-functional organosilicon compound described by formula
HSiR
2
n
Z
3-n
under the action of (c) a platinum catalyst and in the presence of (d) a hydro(acyloxy)-functional silicon compound described by formula
HSiR
2
(O(C═O)R
1
)
or in the presence of (e) a carboxylic acid compound and a hydro(alkoxy)silane; where each R is independently selected from the group consisting of organic groups, siloxy groups, and siloxanoxy groups, each R
1
is independently selected from the group consisting of the hydrogen atom and organic groups, each R
2
is an independently selected hydrocarbon group; each Z is independently selected from the group consisting of silamino groups, siloxy groups, and siloxanoxy groups; and n=0, 1, 2, or 3.
The following compounds (1) through (8) are examples of preferred unsaturated compounds encompassed by component (a):
(1) styrene and styrene derivatives;
(2) vinylsilane compounds;
(3) siloxane compounds containing the vinyl group directly bonded to silicon;
(4) epoxy-functional olefins;
(5) diene compounds;
(6) allyl compounds defined by CH
2
═CHCH
2
X where X=halogen, alkoxy, or acyloxy;
(7) vinyl-functional olefin compounds; and
(8) acetylenic compounds.
While the unsaturated compounds encompassed by component (a) are preferably selected from compounds (1) to (8) as defined above, the unsaturated compound (a) may contain atoms other than carbon and hydrogen in its structure, the other atoms being selected from the group consisting of O, N, F, Cl, Br, Si, and S. However, compound (6) remains as described above.
The styrene and styrene derivatives can be exemplified by styrenic hydrocarbons such as styrene, p-methylstyrene, p-ethylstyrene, p-phenylstyrene, and divinylbenzene; halogenated styrenes such as p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-(chloromethyl)styrene, and m-(chloromethyl)styrene; oxygenated styrene derivatives and silicon-containing styrene derivatives such as p-methoxystyrene and p-trimethylsilylstyrene; nitrogenous styrene derivatives such as p-(diphenylamino)styrene, p-(ditolylamino)styrene, p-(dixylylamino)styrene, and bis(4-vinylphenyl)(4-methylphenyl)amine.
The vinylsilane compounds and siloxane compounds containing the vinyl group directly bonded to silicon can be exemplified by vinyltrialkylsilanes such as vinyltrimethylsilane, vinyltriethylsilane, vinyltripropylsilane, and vinyldimethylethylsilane; vinylalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyldimethylmethoxysilane; vinyl-functional siloxanes such as 1,3-divinyltetramethyldisiloxane, &agr;,&ohgr;-divinylpolydimethylsiloxanes, and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane; and vinyl-functional silazanes such as 1,3-divinyltetramethyldisilazane and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane.
The epoxy-functional olefins can be exemplified by allyl glycidyl ether and vinylcyclohexene oxide. The diene compounds can be exemplified by 1,3-butadiene, isoprene, 1,5-hexadiene, 1,3-octadiene, and 1,3-cyclohexadiene. The allyl compound CH
2
═CHCH
2
X can be exemplified by allyl chloride, allyl acetate, and allyl methacrylate.
The vinyl-functional olefin compounds may be straight chain or branched and may contain an aromatic hydrocarbon group as a substituent. The straight-chain unsaturated olefin compounds can be exemplified by ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 1-octadecene. The branched unsaturated olefin compounds can be exemplified by isobutylene, 3-methyl-1-butene, 3,5-dimethyl-1-hexene, and 4-ethyl-1-octene.
Olefin compounds containing an atom or atoms from the group consisting of O, N, F, Cl, Br, Si, and S are exemplified by oxygenated allyl compounds such as allyl methacrylate; vinyl-functional amine compounds such as N-vinylcarbazole; halogenated olefins such as 4-chloro-1-butene and 6-bromo-1-hexene; Si-functional olefin compounds such as allyloxytrimethylsilane; and sulfur-containing olefin compounds such as allyl mercaptan and allyl sulfide. Allylbenzene and 4-phenyl-1-butene are examples of aromatic hydrocarbon group-containing olefin compound.
The acetylenic compound may contain the terminal ethynyl group (CH≡C—) or m
Boley William F.
Dow Corning Asia Ltd.
Shaver Paul F.
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