Organosilicon compounds containing alkenyl groups

Details Organosilicon compounds containing alkenyl groups Organosilicon compounds containing alkenyl groups

1999-03-03

2001-06-26

Shaver, Paul F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

Reexamination Certificate

active

06252101

ABSTRACT:

BACKGROUND OF THE INVENTION
In Polym. Repr. 33 (1), 1078, Wagener and Smith describe ring-closure reactions of olefinic Si compounds in which ethylene is eliminated. For example, 1,3-diallyldisiloxanes are cyclized to form unsaturated 7-membered rings and siloxanes containing relatively long 1-alkenyl radicals are polymerized.
Similar coupling reactions are known from J. Organomet. Chem. 447 (1993) 2, 163-166 (Marciniec) and Appl. Organomet. Chem. 1997, 11 (8), 667-671 (Marciniec). Here, silanes having terminal double bonds, e.g. Si-bonded vinyl groups, are reacted with other olefins. The products obtained are not reactive in hydrosilylation reactions.
According to Angew. Chem. 1997, 109 (3), 257-259 (Schneider et al.) or the corresponding Chemical Abstract 12 237970, allyltrimethylsilane is used as ring-opening reagent for cycloolefins, forming silanes having a terminal C═C group.
U.S. Pat. No. 5,264,606 (Union Carbide Chemicals & Plastics Technology Corporation, issued on Nov. 23, 1993) describes a process for preparing monomeric polyvinyl compounds and their oligomers by heterogeneously catalyzed cross-metathesis of norbornene or substituted norbornenes such as 5-triethoxysilyl-2-norbornene with ethylene in the presence of activated rhenium oxide fixed-bed catalysts.
DISCLOSURE OF THE INVENTION
It is an object of the invention to provide organosilicon compounds containing alkenyl groups which can be prepared in a simple process which uses readily available starting materials and allows two terminal alkenyl groups to be introduced on one Si atom. These and other objects are achieved by the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention provides organosilicon compounds containing alkenyl groups and comprising units of the formula
A
a
⁢
R
b
⁡
(
R
1
⁢
O
)
c
⁢
SiO
4
-
(
a
+
b
+
c
)
2
,
(
I
)
where R are identical or different and are each a monovalent hydrocarbon radical which is free of aliphatic carbon-carbon multiple bonds, has from 1 to 20 carbon atom(s) per radical and may contain from 1 to 4 oxygen atom(s),
R
1
are identical or different and are each a monovalent hydrocarbon radical which is free of aliphatic carbon-carbon multiple bonds and has from 1 to 8 carbon atom(s) per radical,
a is 0 or 1,
b is 0, 1, 2 or 3,
c is 0, 1, 2 or 3, preferably 0, where the sum a+b+c<3,
A is a radical of the formula
—(R
2
)
d
—Y(—CH═CHR
3
)
2
where R
2
is a divalent hydrocarbon radical which is free of aliphatic carbon-carbon multiple bonds and has from 1 to 6 carbon atom(s),
R
3
are identical or different and are each a hydrogen atom or are as defined for R,
Y is a trivalent hydrocarbon radical which has from 2 to 20 carbon atoms and may contain from 1 to 4 oxygen atom(s) and d is 0 or 1,
with the proviso that the organosilicon compounds have at least two units of the formula (I) and at least one radical A per molecule.
The invention further provides a process for preparing organosilicon compounds containing alkenyl groups, which comprises reacting organosilicon compounds (1) comprising units of the formula
B
a
⁢
R
b
⁡
(
R
1
⁢
O
)
c
⁢
SiO
4
-
(
a
+
b
+
c
)
2
,
(
II
)
where R, R
1
a, b and c are as defined above,
B is a radical of the formula
R
2
, Y and d are as defined above,
with the proviso that the organosilicon compounds have at least two units of the formula (II) and at least one radical B per molecule,
with &agr;-olefins (2) of the formula R
3
—CH═CH
2
in the presence of metathesis catalysts (3) selected from the group consisting of transition metal compounds or complexes of transition groups IV to VIII of the Periodic Table.
The novel organosilicon compounds containing alkenyl groups preferably have a viscosity of from 1 to 10,000 at 25° C., more preferably from 1 to 500 at 25° C. and particularly preferably from 1 to 50 at 25° C.
The novel organosilicon compounds containing alkenyl groups preferably contain at least two radicals A, more preferably from 2 to 5 radicals A and particularly preferably from 2 to 3 radicals A.
The novel organosilicon compounds containing alkenyl groups are preferably oligomeric and polymeric organopolysiloxanes.
Examples of radicals R are alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical and octadecyl radicals such as the n-octadecyl radical; cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radicals, alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals such as the benzyl radical, the &agr;- and the &bgr;-phenylethyl radicals. Preference is given to the methyl radical.
Examples of radicals R
1
are alkyl radicals having from 1 to 8 carbon atom(s), e.g. the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl and tert-butyl radicals. Preference is given to the methyl and ethyl radicals. Examples of alkyl radicals R
1
which are substituted by an oxygen atom are the methoxyethyl and ethoxyethyl radicals.
Examples of radicals R
2
are those of the formulae —H
2
—,
with preference being given to radicals of the formulae
R
3
is preferably a hydrogen atom.
Examples of radicals Y are the
1,2,4-butanetriyl radical,
1,3,6-hexanetriyl radical,
1,2,4-cyclopentanetriyl radical and the 2-methylenyl-3,5-bicyclo[2.2. 1]heptanediyl radical of the formula
Examples of radicals A are the
4-(1 ,7-octadienyl),
5-(1 ,9-decadienyl),
2-(2,4-divinylcyclopentyl)ethyl,
2,4-divinylcyclopentyl and
2(4)-vinyl-4(2)-l-octenyl radicals.
Examples of radicals B are the
3-cyclohexenyl,
4-cyclooctenyl,
5-norbornenyl,
2-(5-norbornenyl)ethyl and 2(3)-dicyclopentadienyl radicals.
Examples of &agr;-olefms (2) are ethylene, 1-octene, 1-pentene, 1-hexene, 1-dodecene, preference being given to ethylene.
Methods of preparing the organosilicon compounds (1) are known to those skilled in the art. 2-(norbornenyl)ethylsiloxanes are obtainable, for example, by hydrosilylation of 5-vinylnorbornene using organo(poly)siloxanes containing Si-bonded hydrogen, and 5-norbornenylsiloxanes are obtainable by analogous reactions from norbornadiene, as described in DE-A 41 28 932 (Wacker-Chemie GmbH, published on Mar. 4, 1993).
In the process of the invention, the ratio of &agr;-olefins (2) to radicals B in organosilicon compound (1) is preferably from 1:1 to 20:1.
The metathesis catalysts (3) used in the process of the invention can be the same catalysts as have hitherto proven useful in metathesis reactions.
Examples of transition metal catalysts are compounds of titanium, tungsten, molybdenum and ruthenium, with particular preference being given to those of ruthenium.
The process of the invention can be carried out in the presence of homogenous or heterogeneous catalysts. It is preferably carried out in the presence of homogeneous catalysts.
In the case of the homogeneous systems, a distinction is made between single-component and multicomponent catalysts. The multicomponent catalysts preferably comprise transition metal compounds or complexes of transition groups IV to VII of the Periodic Table and a cocatalyst, and if desired, an oxygen-containing promoter. The complexes can contain halogen atoms and/or carbonyl groups and/or nitrosilyl groups. Examples are:
WCl
6
/SnMe
2
Et
2
O,
W(CO)
5
(PPh
3
)/0
2
/EtAlCl
2
and
MoCl (NO) (CO)
2
(PPh
3
)/EtAlCl
2
(Me=methyl, Ph=phenyl).
Further examples of multicomponent catalysts are transition metal complexes with diazoalkane cocatalysts:
L=NCMe
2
NCPh, PPh
3
, P(OiPr)
3
, P(Cy)
3
, 3-Me-pyridine
(Me=methyl, Ph=phenyl, iP

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