JPH1025322A - Method for producing silicone composite polymer - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a method for producing an industrially usable silicone composite polymer. SOLUTION: The method for producing a silicone composite polymer includes:
The method includes a step of polymerizing a polymerizable solution containing the hydrosilyl group-containing organopolysiloxane and the polymerizable double bond-containing monomer using a radical polymerization initiator. Here, the polymerizable solution contains, for example, at least 20% by weight or more of a hydrosilyl group-containing organopolysiloxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polymer,
In particular, it relates to a method for producing a silicone composite polymer.

[0002]

2. Description of the Related Art Resins used for various coating materials such as resins for paints, resins for molding materials, resins for medical materials and resins for cosmetic materials, and surface modifiers such as defoamers and flow agents. In organic polymers such as resins used as a, if necessary, to improve various properties such as heat resistance, weather resistance, mold release, moldability, thermal shock resistance, etc., heat resistance and weather resistance Is considered to be complexed with a good silicone compound.

As a method for combining an organic polymer and a silicone compound used in the above-mentioned various applications, Japanese Patent Application Laid-Open No.
No. 126478 discloses a method for synthesizing a silicone / vinyl graft polymer. This method is a method of obtaining a graft polymer by copolymerizing a silicone macromonomer obtained by living polymerization, but it is difficult to industrialize living polymerization itself,
It is not easy to industrialize.

Japanese Patent Application Laid-Open No. 1-254719 discloses a method for synthesizing a silicone / vinyl block polymer. This method is a method for synthesizing a block polymer by a two-stage polymerization method using a polymer initiator, but has a low blocking efficiency and is difficult to industrialize.

An object of the present invention is to realize a method for producing a silicone composite polymer which can be industrialized.

[0006]

According to the present invention, there is provided a method for producing a silicone composite polymer, comprising the steps of: preparing a polymerizable solution containing a hydrosilyl group-containing organopolysiloxane and a polymerizable double bond-containing monomer with a radical polymerization initiator; And a step of causing a polymerization reaction.

The radical polymerization initiator used here is:
For example, a peroxide-based radical polymerization initiator,
Specifically, those selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and benzoyl peroxide can be exemplified.

Further, the hydrosilyl group-containing organopolysiloxane is, for example, represented by the following average composition formula (1):
It is at least one selected from the group consisting of (2), (3) and (4).

[0009]

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Wherein R is an alkyl group, allyl group, aryl group, aralkyl group, epoxy group, hydroxyl group, carboxyl group, amino group, alkoxysilyl group or polyether group, a is 0 to 200, b is 0 ~ 200, c is 1 ~
200, d is 3-10, and e is 1-4. )

In the above-mentioned organopolysiloxane containing a hydrosilyl group used in the present invention, for example, the average number of hydrosilyl groups contained in one molecule is at least 15.

On the other hand, polymerizable double bond-containing monomers include, for example, styrene monomers, alkyl acrylates, alkyl methacrylates, hydroxyl-containing polymerizable double bond-containing monomers, carboxylic acid-containing polymerizable double bond-containing monomers. , Alkoxysilyl group-containing polymerizable double bond-containing monomer, fluorine-containing polymerizable double bond-containing monomer, bifunctional polymerizable double bond-containing monomer, epoxy group-containing polymerizable double bond-containing monomer, amide group-containing polymerizable Double bond-containing monomer, amino group-containing polymerizable double bond-containing monomer, sulfone group-containing polymerizable double bond-containing monomer, polyether group-containing polymerizable double bond-containing monomer, and phosphate group-containing polymerizable double bond-containing It is at least one selected from the group consisting of monomers.

The hydrosilyl group-containing organopolysiloxane is contained, for example, in a polymerizable solution by at least 20% by weight.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The hydrosilyl group-containing organopolysiloxane used in the present invention is not particularly limited as long as it has at least one hydrosilyl group (SiH group) in one molecule. Usually, the main chain is a repeating siloxane bond represented by the following general formula (A), and the side chain is an alkyl group such as a methyl group, an ethyl group and a propyl group, and an aryl group such as an allyl group, a vinyl group and a phenyl group. Aralkyl groups such as phenylethyl group and phenylisopropyl group, epoxy groups, hydroxyl groups, carboxyl groups, amino groups, methoxysilyl groups, alkoxysilyl groups such as ethoxysilyl groups, and polyether groups such as polyethylene oxide and polypropylene oxide. A polymer having at least one And it has a hydrosilyl group.

[0015]

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Specific examples of such a hydrosilyl group-containing organopolysiloxane include those represented by the following average composition formulas (1), (2), (3) and (4).

[0017]

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In each average composition formula, R represents the above-mentioned alkyl group, allyl group, aryl group, aralkyl group, epoxy group, hydroxyl group, carboxyl group, amino group, alkoxysilyl group or polyether group. A is 0 to 2
00, b is 0 to 200, c is 1 to 200, d is 3-1
0 and e are 1-4. Note that R in each average composition formula may be two or more.

It is preferable that such a hydrosilyl group-containing organopolysiloxane has an average number of hydrosilyl groups of at least 15 per molecule. When the average number of hydrosilyl groups is less than 15, the reaction efficiency between the hydrosilyl group-containing organopolysiloxane and the polymerizable double bond-containing monomer decreases, and the organic compound obtained from the organopolysiloxane and the polymerizable double bond-containing monomer is reduced. In some cases, it is difficult to obtain a polymer having a high efficiency of complexing with a polymer.

Polymerizable Double Bond-Containing Monomer The polymerizable double bond-containing monomer used in the present invention is not particularly limited as long as it has a polymerizable double bond. Examples thereof include a styrene monomer and an alkyl acrylate. Methacrylic acid alkyl ester, hydroxyl group-containing polymerizable double bond-containing monomer, carboxylic acid-containing polymerizable double bond-containing monomer, alkoxysilyl group-containing polymerizable double bond-containing monomer, fluorine-containing polymerizable double bond-containing monomer, Functional polymerizable double bond containing monomer, epoxy group containing polymerizable double bond containing monomer, amide group containing polymerizable double bond containing monomer, amino group containing polymerizable double bond containing monomer, sulfone group containing polymerizable double Bond-containing monomer, polyether group-containing polymerizable double bond-containing monomer and phosphate group-containing polymerizable double Or the like can be mentioned a case containing monomer.

Here, examples of the styrene-based monomer include styrene and α-methylstyrene. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and cyclohexyl acrylate. Examples of the alkyl methacrylate include methyl methacrylate,
Examples thereof include ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and cyclohexyl methacrylate. Examples of the hydroxyl group-containing polymerizable double bond-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-methacrylic acid. -Hydroxybutyl and the like. Examples of the carboxylic acid-containing polymerizable double bond-containing monomer include acrylic acid, methacrylic acid, and maleic anhydride. Examples of the alkoxysilyl group-containing polymerizable double bond-containing monomer include 3-trimethoxysilylpropyl acrylate, methacrylic acid 3
-Trimethoxysilylpropyl, 3-triethoxysilylpropyl acrylate, 3-triethoxysilylpropyl methacrylate and the like. Examples of the fluorine-containing polymerizable double bond-containing monomer include trifluoroethyl acrylate and trifluoroethyl methacrylate. Examples of the bifunctional polymerizable double bond-containing monomer include allyl acrylate, allyl methacrylate, 3-methyl-3-butenyl acrylate, and 3-methyl-3-butenyl methacrylate. Furthermore, examples of the epoxy group-containing polymerizable double bond-containing monomer include glycidyl acrylate and glycidyl methacrylate.

The amide group-containing polymerizable double bond-containing monomer includes acrylamide, methacrylamide,
Examples include methylenebisacrylamide, methylenebismethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and the like. Examples of the amino group-containing polymerizable double bond-containing monomer include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, and dimethylaminopropyl acrylamide. Can be. Examples of the sulfone group-containing polymerizable double bond-containing monomer include acrylic sulfonic acid, methacrylsulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, and 2-acrylamide-
Examples thereof include 2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, and alkali salts, ammonium salts and amine salts thereof. Examples of the polyether group-containing polymerizable double bond-containing monomer include acrylate having ethylene oxide added to about 2 to 50, methacrylate to which ethylene oxide is added to about 2 to 50, and propylene oxide having 2 to 50.
An acrylate to which about 50 has been added and a methacrylate to which about 2 to 50 propylene oxide has been added can be exemplified. Further, as the phosphoric acid group-containing polymerizable double bond-containing monomer, 2-acid phosphooxyethyl methacrylate, 2-acid phosphoxyethyl acrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, 3-chloro-2- Acid phosphoxypropyl acrylate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate and dibutyl-2
-Acryloyloxyethyl phosphate.

The above-mentioned monomers containing a polymerizable double bond may be used in combination of two or more.

In the present invention, as the polymerizable double bond-containing monomer, 2,4-formula represented by the following general formula (5) is used.
Diphenyl-4-methyl-1-pentene can also be used.

[0025]

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Radical polymerization initiator In the present invention, a peroxide polymerization initiator or an azo polymerization initiator is used as the radical polymerization initiator. Here, as the peroxide-based radical polymerization initiator, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-hexyl peroxy-2
-Ethylhexanoate, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, 1,1-bis (tert-butyl peroxy) cyclohexane and the like can be exemplified. On the other hand, as the azo radical polymerization initiator, 2,
2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-
2,4-dimethylvaleronitrile, dimethyl-2,2 '
-Azobisisobutyrate, 4,4'-azobis-4-
Cyanovaleric acid, 2,2′-azobis (2-
Methyl-N- (2-hydroxyethyl)) propionamide and the like can be illustrated.

The above radical polymerization initiator is preferably a peroxide-based radical polymerization initiator, particularly, dicumyl peroxide, ditertiary peroxide, because hydrogen atoms are easily extracted from the hydrosilyl group of the hydrosilyl group-containing organopolysiloxane. Preference is given to using butyl peroxide, tert-butyl peroxybenzoate or benzoyl peroxide.

Polymerization Reaction The method for producing a silicone composite polymer according to the present invention comprises the steps of: preparing a polymerizable solution containing the aforementioned hydrosilyl group-containing organopolysiloxane and the aforementioned polymerizable double bond-containing monomer;
And a step of performing a polymerization reaction using a radical polymerization initiator. Here, a hydrogen abstraction reaction from the hydrosilyl group of the hydrosilyl group-containing organopolysiloxane,
The polymerization reaction of the polymerizable double bond-containing monomer proceeds competitively. Specifically, a Si radical is generated on the hydrosilyl group-containing organopolysiloxane side, and the Si radical serves as a starting point to polymerize the polymerizable double bond-containing monomer,
The organic polymer in which the polymerizable double bond-containing monomer is polymerized with the hydrosilyl group-containing organopolysiloxane. Thereby, the desired silicone composite polymer can be obtained.

In carrying out such a polymerization reaction, the above-mentioned polymerizable solution may or may not contain a solvent.

The above-mentioned polymerizable solution is used, regardless of the use of a solvent, in order to increase the efficiency of combining the hydrosilyl group-containing organopolysiloxane and the organic polymer with the polymerizable double bond-containing monomer. Preferably, the concentration of siloxane is adjusted to be at least 20% by weight.

The temperature condition during the polymerization reaction is not particularly limited, but it is usually carried out in a temperature range from room temperature to 200 ° C, preferably in a temperature range from 100 to 200 ° C.

Further, the polymerization reaction can be carried out under a molecular weight modifier. As molecular weight regulators, mercaptans such as dodecyl mercaptan and thioglycol,
Allyl compounds such as allyl alcohol, allyl acetate and allyl carbonate; halides such as carbon tetrachloride and dibromoethane; 2,4-diphenyl-4-methyl-1-pentene; and 2,4-dicarboxymethyl-4-methyl- Examples thereof include α-vinyl monomer dimers such as 1-pentene.

The silicone composite polymer produced by the method of the present invention can be used as a resin for various coating materials such as a resin for paints, a resin for molding materials, a resin for medical materials, a resin for cosmetics materials, or a defoaming agent. When used as a surface conditioner such as a flow agent, good heat resistance, weather resistance, mold release,
Various properties such as moldability and thermal shock resistance can be achieved.

[0034]

EXAMPLE 1 A pressure-resistant reactor equipped with a condenser, a stirrer, a nitrogen inlet tube and a temperature controller was prepared, and 25 g of xylene was added thereto.
And 75 g of an organopolysiloxane represented by the following structural formula (6) were charged and heated to 150 ° C. After heating,
A mixed solution of 100 g of tert-butyl methacrylate and 10 g of di-tert-butyl peroxide was added dropwise over 3 hours, and the temperature was further maintained for 3 hours. The polymer solution thus obtained was heated to 140 ° C. to remove the solvent, whereby polymer A was obtained.

[0035]

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The obtained polymer A was applied to a UV detector (25
When analyzed using high performance liquid chromatography equipped with 4 nm), two peaks were observed. Separate each peak part and measure its infrared absorption spectrum (IR)
As a result, it was found that the two peaks were due to an organopolysiloxane in which unreacted organopolysiloxane and poly (tert-butyl methacrylate) were composited (grafted). From the area ratio of the two peaks, the composite efficiency (ratio of organopolysiloxane in which tertiary butyl methacrylate is composited)
Was about 39%.

Example 2 Xylene 10 was placed in the same reaction vessel as used in Example 1.
0 g and 75 g of the organopolysiloxane represented by the above structural formula (6) were charged and heated to 150 ° C. After heating,
A mixed solution of 100 g of tert-butyl methacrylate and 10 g of di-tert-butyl peroxide was added dropwise over 3 hours, and the temperature was further kept for 3 hours. The polymer solution thus obtained was heated to 140 ° C. to remove the solvent, whereby polymer B was obtained.

When the obtained polymer B was analyzed using high performance liquid chromatography in the same manner as in Example 1,
Two peaks were observed. Each peak portion was collected and subjected to IR measurement. As a result, two peaks were due to an organopolysiloxane in which unreacted organopolysiloxane and tert-butyl polymethacrylate were composited (grafted). I understand. Further, when the composite efficiency (the ratio of organopolysiloxane in which tertiary butyl methacrylate was composited) was examined from the area ratio of the two peaks, it was about 20%.

Example 3 25 g of xylene was placed in the same reaction vessel as used in Example 1.
And 75 g of an organopolysiloxane represented by the above structural formula (6) were charged and heated to 130 ° C. After heating, 100 g of tert-butyl methacrylate and dimethyl-2,2
A mixed solution of 10 g of 2'-azobisisobutyrate was added to 3
The solution was added dropwise over a period of time, and the temperature was further kept for 3 hours. The polymer solution thus obtained was heated to 140 ° C. to remove the solvent, whereby polymer C was obtained.

When the obtained polymer C was analyzed using high performance liquid chromatography in the same manner as in Example 1,
Two peaks were observed. Each peak portion was collected and subjected to IR measurement. As a result, two peaks were due to an organopolysiloxane in which unreacted organopolysiloxane and tert-butyl polymethacrylate were composited (grafted). I understand. Further, when the composite efficiency (the ratio of organopolysiloxane in which tertiary butyl methacrylate was composited) was determined from the area ratio of the two peaks, it was about 10%.

Example 4 Xylene 25 was placed in a reaction vessel similar to that used in Example 1.
g and 75 g of an organopolysiloxane represented by the following structural formula (7) were charged and heated to 150 ° C. After heating,
A mixed solution of 100 g of tert-butyl methacrylate and 10 g of di-tert-butyl peroxide was added dropwise over 3 hours, and the temperature was further maintained for 3 hours. The polymer solution thus obtained was heated to 140 ° C. to remove the solvent, whereby polymer D was obtained.

[0042]

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When the obtained polymer D was analyzed using high performance liquid chromatography in the same manner as in Example 1,
Two peaks were observed. Each peak portion was collected and subjected to IR measurement. As a result, two peaks were due to an organopolysiloxane in which unreacted organopolysiloxane and tert-butyl polymethacrylate were composited (grafted). I understand. Further, the composition efficiency (the ratio of organopolysiloxane in which tertiary butyl methacrylate was combined) was determined from the area ratio of the two peaks, and was found to be about 15%.

[0044] Xylene 25 In the same reaction vessel as that used in Comparative Example 1
g and 75 g of an organopolysiloxane represented by the following structural formula (8) were charged and heated to 150 ° C. After heating,
A mixed solution of 100 g of tert-butyl methacrylate and 10 g of di-tert-butyl peroxide was added dropwise over 3 hours, and the temperature was further maintained for 3 hours. The polymer solution thus obtained was heated to 140 ° C. to remove the solvent, whereby polymer E was obtained.

[0045]

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When the obtained polymer E was analyzed using high performance liquid chromatography in the same manner as in Example 1,
Only one peak was observed. The peak was collected and subjected to IR measurement, and it was found that the peak was unreacted organopolysiloxane. From these results, it was found that the organopolysiloxane containing no hydrosilyl group did not complex with the organic polymer obtained from the polymerizable double bond-containing monomer in the presence of the radical initiator.

[0047]

In the method for producing a silicone composite polymer according to the present invention, a polymerizable solution containing a hydrosilyl group-containing organopolysiloxane and a polymerizable double bond-containing monomer is polymerized using a radical polymerization initiator. Therefore, the silicone composite polymer which has been difficult to produce industrially can be industrially easily produced.

Claims (7)

[Claims] 1. A method for producing a silicone composite polymer, comprising the step of polymerizing a polymerizable solution containing a hydrosilyl group-containing organopolysiloxane and a polymerizable double bond-containing monomer using a radical polymerization initiator. 2. The method for producing a silicone composite polymer according to claim 1, wherein the radical polymerization initiator is a peroxide-based radical polymerization initiator. 3. The peroxide-based radical polymerization initiator is selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and benzoyl peroxide. 3. The method for producing a silicone composite polymer according to item 2. 4. The hydrosilyl group-containing organopolysiloxane is at least one selected from the group consisting of the following average composition formulas (1), (2), (3) and (4). 4. The method for producing a silicone composite polymer according to 2 or 3. Embedded image (Wherein, R represents an alkyl group, an allyl group, an aryl group, an aralkyl group, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group or a polyether group, a
Is 0 to 200, b is 0 to 200, c is 1 to 200, d is 3 to 10, and e is 1 to 4. ) 5. The silicone composite polymer according to claim 1, wherein said hydrosilyl group-containing organopolysiloxane has an average number of hydrosilyl groups in one molecule of at least 15. Production method. 6. The polymerizable double bond-containing monomer includes a styrene monomer, an alkyl acrylate, an alkyl methacrylate, a polymerizable double bond-containing monomer, a carboxylic acid-containing polymerizable double bond-containing monomer, Alkoxysilyl group-containing polymerizable double bond-containing monomer, fluorine-containing polymerizable double bond-containing monomer, difunctional polymerizable double bond-containing monomer, epoxy group-containing polymerizable double bond-containing monomer, amide group-containing polymerizable monomer A heavy bond-containing monomer, an amino group-containing polymerizable double bond-containing monomer,
The polymerizable double bond-containing monomer containing a sulfone group, the polymerizable double bond-containing monomer containing a polyether group, and the phosphate-containing polymerizable double bond-containing monomer are at least one member selected from the group consisting of: 6. The method for producing a silicone composite polymer according to 2, 3, 4, or 5. 7. The silicone composite polymer according to claim 1, wherein said hydrosilyl group-containing organopolysiloxane is contained in said polymerizable solution in an amount of at least 20% by weight. Production method.