Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2000-06-27
2001-10-02
Moore, Margaret G. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C524S284000, C524S157000, C528S023000, C528S025000, C528S031000, C556S412000, C556S450000, C556S479000
Reexamination Certificate
active
06297340
ABSTRACT:
BACKGROUND OF INVENTION
The present invention relates to a method for manufacturing a silicon compound having substituents bonded to silicon atoms via Si-C bonds by reacting an unsaturated compound and a silane compound for the purpose of improving physical properties and imparting reactivity.
The use of a hydrosilylation reaction is generally very effective in the chemical modification of organic compounds with silane compounds. A method that is used in this case involves a hydrosilylation reaction of an Si-H functional silane and an organic compound having unsaturated bonds. This method is applicable to quite a wide range of Si-H compounds and organic compounds having unsaturated bonds. A platinum or rhodium catalyst is generally used in the hydrosilylation reactions conducted industrially, but these metals are prohibitively expensive, and the catalytic efficiency of the hydrosilylation reaction is therefore of the utmost importance. Also, competing side reactions are frequently encountered with hydrosilylation reactions, and the hydrosilylation reaction itself includes reaction paths that produce a number of isomers. Therefore problems related to the catalyst, such as yield of the product, selectivity, and production of a single isomer, are always present in a hydrosilylation reaction. In an effort to reduce these problems modifications of the catalyst have been performed such as chemically bonding or adding various ligands to the catalyst or fixing the catalyst on various different carriers. In general, however, this chemical or physical modification has the problems that (1) the effect thereof is gradually lost and (2) the activity of a catalyst is generally lower the better its selectivity. Besides these problems, platinum catalysts slowly deactivate under oxygen-free conditions, and therefore the hydrosilylation reaction has to be conducted in the presence of oxygen, despite the fact that this leads to side reactions and poses a fire hazard.
It is an object of the present invention to provide a reaction method with which high catalytic activity and stability are realized and the positional selectivity of the hydrosilylation reaction product is enhanced in the hydrosilylation reaction of an organic compound having unsaturated groups and an H-Si functional silicon compound using a platinum catalyst. An objective is also to achieve these effects without adding any oxygen, and to reduce the danger of fire, explosion, and so on in a hydrosilylation reaction.
SUMMARY OF INVENTION
A hydrosilylation reaction method that achieves high catalytic activity and stability and improves the positional selectivity of the hydrosilylation reaction product. The method comprises reacting an unsaturated compound selected from the group consisting of aromatic vinyl compounds and allyl halides with a silicon compound having hydrosilyl groups described by formula HSiR
n
(Z)
3−n
, where n=0, 1, or 2, R is a hydrocarbon group, and Z is selected from the group consisting of a silamino group, siloxy group, and siloxanoxy group in the presence of a carboxylic acid compound, a silyl ester of a sulfonic acid, and a platinum catalyst.
DESCRIPTION OF INVENTION
The present invention is a method for manufacturing a silicon compound having substituents bonded to silicon atoms via Si-C bonds. The method comprises reacting (a) at least one unsaturated compound selected from the group consisting of aromatic vinyl compounds and allyl halides with (b) a silicon compound having hydrosilyl groups described by formula
HSiR
n
(Z)
3−n
(1)
where n is 0, 1, or 2; R is a hydrocarbon group; and Z is selected from the group consisting of silamino group, siloxy group, and siloxanoxy group; in the presence of (c) at least one carboxylic acid compound selected from the group consisting of
(1) carboxylic acids,
(2) carboxylic anhydrides,
(3) silyl ester compounds of carboxylic acids described by formula
(R
2
COO)
4−m
SiR
1
m, (2)
where m is an integer from 0 to 3; each R
1
is independently selected from the group consisting of C
1
to C
6
hydrocarbon groups and C
1
to C
6
alkoxy groups; and each R
2
group is independently selected from the group consisting of a hydrogen atom and C
1
to C
20
saturated or unsaturated hydrocarbon groups which may include at least one atom selected from among oxygen, halogens, sulfur, and silicon;
(d) a silyl ester of a sulfonic acid described by formula
where R
3
is selected from the group consisting of C
1
to C
10
halogenated hydrocarbon groups, C
1
to C
10
alkyl groups, C
6
to C
10
aryl groups, a fluorine atom, a chlorine atom, a group described by formula OR
4
, and a group described by formula OSiR
8
R
9
R
10
; where R
4
is a C
1
to C
6
alkyl group; R
8
, R
9
, and R
10
are each independently selected from the group consisting of C
1
to C
10
hydrocarbon groups, C
1
to C
10
halogenated hydrocarbon groups, a halogen atom, and a hydrogen atom; and R
5
, R
6
, and R
7
are each independently selected from the group consisting of C
1
to C
10
hydrocarbon groups, a group described by formula —OS(O
2
)R
3
where R
3
is as previously described, C
1
to C
10
halogenated hydrocarbon groups, a halogen atom, and a hydrogen atom; and
(e) a platinum catalyst.
The above-mentioned aromatic vinyl compound refers to a compound in which at least one of the carbon atoms on the aromatic ring is bonded to a vinyl group (i.e. —CH═CH
2
). Examples of this aromatic vinyl compound include styrene-based hydrocarbon compounds, such as p-methylstyrene, p-ethylstyrene, p-phenylstyrene, and divinylbenzene; halogen-containing styrenes, such as p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, and p- and m-(chloromethyl)styrene; oxygen- or silicon-containing derivatives, such as p-methoxystyrene and p-trimethylsilylstyrene; and nitrogen-containing derivatives, such as p-(diphenylamino)styrene, p-(ditolylamino)styrene, p-(dixylylamino)styrene, and bis(4-vinylphenyl) (4methylphenyl)amine.
Specific examples of the above-mentioned allyl halides include allyl chloride and allyl bromide.
The above-mentioned silicon compound having hydrosilyl groups is described by formula (1) HSiR
n
(Z)
3−n
. In the formula R represents a hydrocarbon group, and is preferably selected from the group consisting of C
1
to C
10
alkyl groups, aryl groups, and aralkyl groups, such as the methyl group, ethyl group, propyl group, n-hexyl group, n-octyl group, cyclohexyl group, 2-ethylhexyl group, and other such saturated hydrocarbon groups; the phenyl group, tolyl group, xylyl group, and other such aryl groups; and the benzyl group, phenethyl group, and other such aralkyl groups. R is preferably a methyl group.
In the formula (1), Z is selected from the group consisting of silamino group, siloxy group, and siloxanoxy group. Specific examples thereof include —OSiMe
2
H (where Me is a methyl group and the same applies hereinafter), —OSiMe
2
OSiMe
2
H, —OSiMe
2
OSiMe
2
OSiMe
2
H, —OSiMe
3
, —OSiMe
2
OSiMe
3
, —NHSiMe
3
, and —NHSiMe2H. Z may also be divalent rather than univalent and an example thereof is —OSiMeHOSiMeHOSiMeHO—.
The above-mentioned silicon compound having hydrosilyl groups preferably has 2 to 8 silicon atoms, specific examples of which include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, Si(—OSiMe2H)
4
, tetrakis(dimethylsiloxy)silane, and 3,3,5,5-tetrakis(dimethylsiloxy)-1,1,7,7-tetramethyltetrasiloxane.
The above-mentioned carboxylic acid compound is selected from among carboxylic acids described by the following formula 4, carboxylic anhydrides described by the following formula 5, and silyl ester compounds of carboxylic acids described by the following formula 2:
R
2
COOH, (4)
(R
2
CO)
2
O, (5)
(R
2
COO)
4−m
SiR
1
m, (2)
where each R
1
is independently selected from the group consisting of C
1
to C
6
hydrocarbon groups and C
1
to C
6
alkoxy groups; each R
2
is indepen
Dow Corning Asia Ltd.
Moore Margaret G.
Severance Sharon K.
Zimmer Marc S.
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