Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-08-09
2002-07-16
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C525S100000, C525S101000, C528S015000, C528S025000, C528S026000, C528S031000, C528S032000, C528S033000, C528S035000, C556S431000, C556S434000, C556S435000, C556S479000
Reexamination Certificate
active
06420504
ABSTRACT:
FIELD OF THE INVENTION
This invention concerns a novel branched siloxane-silalkylene copolymer which contains one radical-polymerizable organic group per molecule, a silicone-containing organic polymer made by polymerizing the copolymer and a process for producing the same.
BACKGROUND OF THE INVENTION
Organopolysiloxanes which contain one radical-polymerizable organic group per molecule, such as an acryloxy group or methacryloxy group are known, for example straight-chain dimethylpolysiloxanes of which only one end is blocked with methacryloxypropyl group, and branched methylpolysiloxanes represented by the formula:
are known (see Japanese Patent Application Laid-open Nos. Hei 7-196975, Hei 1-319518 and Hei 1-254719). However, previous branched organpoolysiloxanes were limited to those having one branching point per molecule, and multiple branched organopolysiloxanes containing radical-polymerizable organic groups that have two or more branching points were not known.
Further, methods for improving the surface properties of organic polymers by copolymerizing a linear or branched organopolysiloxane containing 1 such radical-polymerizable organic group per molecule as a macro-monomer and a radical-polymerizable organic monomer are known (see Japanese Patent Application Laid-open Nos. Hei 7-196975, Hei 1-319518 and Hei 1-254719). However, there were problems with the silicone-containing organic polymers obtained in this way, in that compatibility with non-silicone-containing organic resins was low, and mechanical strength was low. Further, in order to obtain adequate surface-improvement properties by means of the silicone, it was necessary to copolymerize the aforesaid organopolysiloxane in comparatively large amounts and as a result the aforesaid problems became more pronounced.
Consequently, a purpose of the present invention is to provide a novel, muitiple branched siloxane-silalkylene copolymer which contains 1 radical-polymerizable organic group per molecule, and has a highly branched structure.
Further, a purpose of the present invention is to provide a silicone-containing organic polymer of high mechanical strength, good compatibility with organic resins, and having excellent surface-improvement properties, and a method for the production thereof.
DETAILED DESCRIPTION OF THE INVENTION
Firstly, the branched siloxane-silalkylene copolymer of the present invention is explained.
The branched siloxane-silalkylene copolymer of the present invention is represented by the general formula:
In the above formula, R
1
is 1-10 carbon alkyl or aryl, with the alkyl group being exemplified by methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl and cyclohexyl, and the aryl group being exemplified by phenyl and naphthyl. Among these, methyl and phenyl are preferable, and methyl is especially preferable. X
1
is a silyl-alkyl group represented by the following formula in the case when i=1.
In the formula, R
2
is 2-10 carbon alkylene, and is exemplified by straight-chain alkylene such as ethylene, propylene, butylene and hexylene and by branched alkylene such as methylmethylene, methylethylene, 1-methyl pentylene and 1,4-dimethylbutylene. Among these, ethylene, methylmethylene, methylethylene, hexylene, 1-methyl pentylene and 1,4-dimethylbutylene are preferable. R
3
is 1-10 carbon alkyl, and is exemplified by methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl and cyclohexyl. Among these, methyl is preferable. R
1
is the same as aforesaid. X
i+1
is a group selected from the group comprising a hydrogen atom, 1-10 carbon alkyl, aryl and the aforesaid silylalkyl group. a
i
is an integer from 0 to 3, and the mean total number of a
i
in 1 molecule is preferably 1.5
i
×3 or less. i is an integer from 1 to 10, and this indicates the generation number of the said silylalkyl group, i.e. the number of repetitions of this silylalkyl group. Hence, if the generation number is 1, the branched siloxane-silalkylene copolymer of the present invention is represented by the general formula:
(in the formula, Y is as defined below, R
1
, R
2
and R
3
are the same as aforesaid, and R
9
is a hydrogen atom or the same as the aforesaid R
1
, and a
1
is the same as the aforesaid a
i
), and if the generation number is 2, the branched siloxane-silalkylene copolymer of the present invention is represented by the general formula:
(in the formula, Y is as defined below, R
1
, R
2
, R
3
and R
9
are the same as aforesaid, and a
1
and a
2
are the same as the aforesaid a
i
), and if the generation number is 3, the branched siloxane-silalkylene copolymer of the present invention is represented by the general formula:
(in the formula, Y is as defined below, R
1
, R
2
, R
3
and R
9
are the same as aforesaid, and a
1
, a
2
and a
3
are the same as the aforesaid a
i
), Y is a radical-polymerizable organic group, and specifically, a (meth)-acryl group-containing organic group represented by the general formula:
a styryl group-containing organic group represented by the general formula:
or 2-10 carbon alkenyl are mentioned. In the above formulae, R
4
and R
6
are a hydrogen atom or methyl. R
5
and R
8
are 1-10 carbon alkylene, exemplified by straight-chain alkylene such as methylene, ethylene, propylene, butylene, and hexylene and by branched alkylene such as methylmethylene, methylethylene, 1-methyl pentylene, and 1,4-dimethylbutylene, R
7
is 1-10 carbon alkyl, b is an integer from 0 to 4, and c is 0 or 1. As this radical-polymerizable group, for example acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl, 3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinyl -phenyl)ethyl, 2-(3-vinylphenyl)ethyl, vinyl, allyl, methallyl and 5-hexenyl are mentioned.
Such branched siloxane-silalkylene copolymers of the present invention are exemplified by the polymers represented by the following average molecular formulae:
As a method for the production of such branched siloxane-silalkylene copolymers of the present invention, for example a method in which a silicon compound containing a silicon-bonded hydrogen atom represented by the general formula:
(in the formula, R
1
and Y are the same as aforesaid) and an alkenyl group-containing organo-silicon compound are subjected to a hydrosilylation reaction is mentioned. As the silicon compound represented by the above formula, for example, 3-methacryloxypropyltris-(dimethylsiloxy)silane, 3-acryloxypropyltris(dimethylsiloxy)silane, 4-vinylphenyltris-(dimethylsiloxy)-silane, 4-vinyltris(dimethylsiloxy)silane and 5-hexenyltris(dimethylsiloxy) -silane are used. As the alkenyl group-containing organosilicon compound, for example, vinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane and 5-hexenyltris -(trimethylsiloxy)silane are used. This hydrosilylation reaction is preferably performed in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum-olefin complex. Further, as regards the compounding ratio of the two, in order to prevent the carbon-carbon double bonds in the silicon-bonded hydrogen atom-containing silicon compound represented by the above formula from undergoing the hydrosilylation reaction, it is preferable to use more than the stoichiometric amount of the alkylene group-containing organosilicon compound.
Further, the branched siloxane-silalkylene copolymer of the present invention can also be produced by a method in which a silicon-bonded alkoxy group-containing organosilicon compound and a tetraalkyldisiloxane compound are reacted in the presence of an acidic aqueous solution and the major part of the alkoxy groups in the reaction product obtained are replaced by dialkylsiloxy groups. Moreover, by subjecting an alkylene group-containing organosilicon compound to a hydrosilylation reaction, in the same way as aforesaid, with the resulting branched siloxane-silalkylene copolymer of the present invention, the number of repetitions of the silylalkyl groups can be increased. Further, the silicon-bonded alkoxy
Furukawa Haruhiko
Morita Yoshitsugu
Yoshitake Makoto
Dawson Robert
Dow Corning Toray Silicone Co. Ltd.
Morris LLP Duane
Robertson Jeffrey B.
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