Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2000-03-06
2001-10-30
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C528S015000, C528S017000, C528S025000, C528S026000, C528S027000, C528S031000, C528S033000, C525S474000, C556S413000, C556S418000, C556S419000, C556S420000, C556S425000
Reexamination Certificate
active
06310169
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel radical-polymerizable silicone and a production process for the same, specifically to polymerizable terminal group-containing polyorganosiloxane having a polyoxyalkylene segment between a polymerizable terminal group and a polysiloxane segment and a production process for the same.
2. Description of the Related Art
Subjecting cyclotrisiloxane to ring-opening polymerization with an organic lithium compound or lithium silanolate used as a polymerization initiator and then terminating the reaction with an end-capture having a radical-polymerizable functional group has so far produced a radical-polymerizable silicone. A production process disclosed in Japanese Patent Application Laid-Open No. 78236/1984 in which hexamethylcyclotrisiloxane is subjected to ring-opening polymerization with lithium trimethylsilanolate used as a polymerization initiator and then sealed with 3-(2-methacryloyloxyethoxy)propyldimethylchlorosilane can be given as an example of a production process for dialkylpolysiloxane having an acryl or methacryl group at a single terminal. Further, a production process disclosed in Japanese Patent Application Laid-Open No. 110303/1985 in which hexamethylcyclotrisiloxane is subjected to ring-opening polymerization with lithium trimethylsilanolate used as a polymerization initiator and then sealed with p-vinylphenyldimethylchlorosilane can be given as a production example for dialkylpolysiloxane having a styryl group at a single terminal.
The radical-polymerizable silicone described above can produce graft polymers by copolymerizing with various monomers. These graft polymers are used for high molecular products such as various films, plastics, rubber and waxes, surface treating agents for glass and paper and, modifiers for shampoos, rinses and hair setting agents. Thus, these products are provided with functions such as water repellency, a stain resistance, a non-adhesive property, a heat resistance, an abrasion resistance and a biocompatibility. These graft polymers have dialkylpolysiloxane bonds on side chains and do not have such problem that dialkylpolysiloxane bleeds out unlike conventional compounds obtained by merely blending dialkylpolysiloxanes.
Applications of such graft polymers having radical-polymerizable silicone include hair care products, skin care products, make-up cosmetics, water-in-oil type emulsion cosmetics, oil-in-water type emulsion cosmetics, contact lenses, glazing agents for floor, synthetic leathers, coating agents for an optical magnetic storage, magnetic paints, adhesives, water repellent finishing paints, aqueous resin emulsions, surface modifiers for a high molecular material, resin compositions for electrodeposition paint, subaqueous stain preventives for ship bottom paint and water-repellent and oil-repellent agents.
However, conventional polymerizable terminal group-containing silicones have an ester bond between a radical-polymerizable group and a polysiloxane segment and therefore are susceptible to hydrolysis, so that it is difficult to use them for a long period of time in moist atmosphere.
On the other hand, in order to solve such problem, amide bond (not ester bond) type single radical-polymerizable terminal group-containing silicones are disclosed in Japanese Patent Application Laid-Open No. 017577/1993.
However, conventional single radical-polymerizable terminal group-containing silicones including amide bond type single radical-polymerizable terminal group-containing silicones described above do not fall in a homogeneously mixed state in a certain case, and therefore it has been difficult to graft silicone depending on monomers to be copolymerized. Further, when carrying out emulsion polymerization, it has been difficult since silicone has an inferior dispersibility into water.
SUMMARY OF THE INVENTION
A subject to be solved by the present invention is to solve these problems on conventional techniques and to provide polymerizable terminal group-containing polyorganosiloxane which is less susceptible to hydrolysis.
Intensive researches repeated by the present inventors in order to solve the problems on the conventional techniques described above have resulted in finding that polymerizable terminal group-containing polyorganosiloxane which has a high compatibility with various polar solvents and monomers and which is less susceptible to hydrolysis can be obtained by introducing a polyoxyalkylene segment between a polymerizable terminal group and a polysiloxane segment, and thus they have completed the present invention based on this finding.
The polymerizable terminal group-containing polyorganosiloxane of the present invention is represented by the following items 1 to 2.
1. Polymerizable terminal group-containing polyorganosiloxane having a number average molecular weight of 500 to 100000 represented by Formula (1):
wherein R
1
, R
2
, R
3
, R
4
and R
5
each represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl-containing group having 6 to 10 carbon atoms; R
6
represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl-containing group having 6 to 10 carbon atoms; n represents 1 or more and m represents 0 or more, in which n+m represents an average polymerization degree and is 4 to 1100; X represents an alkylene group having 2 to 20 carbon atoms; Y represents —OCH
2
CH
2
—, —OCH(CH
3
)CH
2
— or —OCH
2
CH(CH
3
)—; p represents 3 or more; and Z represents an alkylene group having 1 to 20 carbon atoms.
2. The polymerizable terminal group-containing polyorganosiloxane as described in the preceding item 1, wherein R
1
, R
3
, R
4
and R
5
are methyl; R
2
is n-butyl; and Z is ethylene.
A production process for the polymerizable terminal group-containing polyorganosiloxane of the present invention is represented by the following items 3 to 4.
3. A production process for polymerizable terminal group-containing polyorganosiloxane represented by Formula (1), comprising the steps of:
subjecting polyorganosiloxane represented by Formula (4) having an SiH group at a single terminal to hydrosilation with polyoxyalkylene represented by Formula (6) having a hydroxyl group and an alkenyl group at terminal according to the following reaction equation (a) to thereby produce a hydroxyl single terminal group-containing polyoxyalkylene.polysiloxane block copolymer represented by Formula (2), and then
subjecting the block copolymer (2) obtained by the reaction described above to addition reaction with an isocyanate compound represented by Formula (3) according to the following reaction equation (b);
wherein R
1
, R
2
, R
3
, R
4
and R
5
each represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl-containing group having 6 to 10 carbon atoms; R
6
represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl-containing group having 6 to 10 carbon atoms; n represents 1 or more and m represents 0 or more, in which n+m represents an average polymerization degree and is 4 to 1100; X represents an alkylene group having 2 to 20 carbon atoms; Y represents —OCH
2
CH
2
—, —OCH(CH
3
)CH
2
— or —OCH
2
CH(CH
3
)—; p represents 3 or more; and Z represents an alkylene group having 1 to 20 carbon atoms.
4. A production process for polymerizable terminal group-containing polyorganosiloxane represented by Formula (1) characterized by reacting a single terminal-hydroxyl polyoxyalkylene.polysiloxane block copolymer represented by Formula (2) with an isocyanate compound represented by Formula (3) according to the following reaction equation (b) in the presence or absence of a catalyst:
wherein R
1
, R
2
, R
3
, R
4
and R
5
each represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl-containing group having 6 to 10 carbon atoms; R
6
represents a hydrogen atom
Kawabata Kiichi
Kimae Youichi
Chisso Corporation
Dawson Robert
McDermott & Will & Emery
Robertson Jeffrey B.
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