JP3518098B2 - Method for producing silicone-vinyl block copolymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a silicone-vinyl block copolymer.

[0002]

2. Description of the Related Art A block copolymer of a vinyl polymer and an organopolysiloxane is one in which various excellent properties of a silicone resin are imparted to a vinyl polymer, and a plastic, a coating agent, a release agent, an adhesive agent. , Is expected to be used in applications such as gas permeable films and processing aids.

As a method for relatively easily producing such a silicone-vinyl block copolymer, a method using an azo group-containing polysiloxane amide exhibiting radical polymerization activity is disclosed in Japanese Patent Publication No. 2-33053. Has been done. The azo group-containing polysiloxane amide is a compound having a repeating unit in which a dicarboxylic acid having an azo group and a diamine having a siloxane segment are amide-bonded, and a radical is easily generated by heat or light, and the compound is vinyl-based. A silicone-vinyl block copolymer is produced by using it as a polymerization initiator of a monomer.

[0004]

However, since the azo group-containing polymer as described above is an initiator which itself is a polymer, its form is a highly viscous oil or rubber. For this reason, there is a problem in that it is extremely difficult to carry out the transfer, the charging to the polymerization container and the like with the azo group-containing polymer alone.

Since the above-mentioned azo group-containing polymer is soluble in an organic solvent, it can be handled in a solution state, but a large amount of solvent is required in order to avoid problems in handling. . However, when the polymerization is carried out in an aqueous system, the presence of an organic solvent is not preferable because it adversely affects the polymerization, the post-treatment step and the properties of the resulting polymer. For example, in suspension polymerization, when an organic solvent is present, aggregation of particles is likely to occur during polymerization, scale and blocking increase, the proportion of polymer obtained in particles decreases, and productivity decreases. Alternatively, since the solvent remains in the obtained polymer, there are problems that 1) an offensive odor occurs, and 2) there is a risk of explosion during drying.

Therefore, when the polymerization is carried out in an aqueous system such as suspension polymerization, it is easy to transfer the azo group-containing polymer or to charge it into a polymerization vessel or the like, which causes a problem in the polymerization step, the quality of the obtained product and the like. There has been a demand for a method for producing a silicone-vinyl chloride block copolymer that is free from the above.

It is an object of the present invention to provide a useful production method for producing a silicone-vinyl block copolymer, which enables production in an aqueous medium on an industrial scale.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has dissolved an azo group-containing polymer such as the above-mentioned azo group-containing polysiloxane amide in a solvent to form a polymerization container. By introducing a step of removing the solvent to the outside of the can after charging into a can, the effect of the solvent on the polymerization step, the post-treatment step and the performance of the resulting silicone-vinyl block copolymer is obtained. The inventors have found that the production amount can be extremely reduced and the production can be performed on an industrial scale, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0010]

[Chemical 3]

(In the formula, each R ¹ may be the same or different and represents a hydrogen atom, a nitrile group or a lower alkyl group, and each R ² may be the same or different, and is a divalent hydrocarbon. Group and m is 0 or 1) and a constituent component having an azo group represented by the following general formula (2)

[0012]

[Chemical 4]

(In the formula, each R ³ may be the same or different and represents a hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group or a phenyl group, and each R ⁴ is the same or different. Also, a divalent hydrocarbon group or a divalent hydrocarbon group having an ether bond is shown, and n is 0 to 5
Indicates an integer of 00. And an organopolysiloxane represented by the formula (1), an azo group-containing polymer having a unit bonded through an amide bond, an ester bond or a urethane bond is dissolved in a solvent and charged into a can. The present invention relates to a method for producing a silicone-vinyl block copolymer, which comprises removing a vinyl monomer from a can and then polymerizing the vinyl monomer in a polymerization can using water as a dispersion medium.

In the azo group-containing polymer used in the present invention, the azo group-containing constituent represented by the general formula (1) and the organopolysiloxane represented by the general formula (2) are amide groups. It is a polymer having units linked through a bond, an ester bond, and a urethane bond. In the constituent having an azo group represented by the general formula (1), each substituent R ¹ may be the same or different and represents a hydrogen atom, a nitrile group or a lower alkyl group. Examples of the lower alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group,
Examples thereof include a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Also,
Each substituent R ² may or may not be present and, if present, represents a divalent hydrocarbon group. As the divalent hydrocarbon group, a linear, branched or cyclic divalent hydrocarbon group having 1 to 24 carbon atoms can be mentioned, and examples thereof include a methylene group, an ethylene group, a trimethylene group and a tetramethylene group. ,
Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, ethylidene group, propylene group,
Divalent aliphatic hydrocarbon groups such as isopropylidene group, butylene group, isobutylene group, pentylene group; phenylene group, tolylene group, naphthylene group, acenaphthenylene group,
Examples thereof include a divalent aromatic hydrocarbon group such as a phenanthrylene group or a hydrocarbon group having 1 to 24 carbon atoms in which the above aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded.

In the component having the organopolysiloxane represented by the general formula (2) of the azo group-containing polymer used in the present invention, each substituent R ³ may be the same or different, and a hydrogen atom or a halogen atom may be used. An atom-substituted or unsubstituted alkyl group or phenyl group is shown. Examples of the alkyl group include a linear or branched alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-group. Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
A decyl group, an undecyl group, a dodecyl group, etc. can be mentioned. Examples of the halogen atom-substituted alkyl group include those in which the above alkyl group is halogenated with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., for example, a chloromethyl group, a bromomethyl group, a trifluoromethyl group. , 2-chloroethyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 1,1,2,2-tetrahydroperfluorooctyl group and the like. Further, the respective substituents R ⁴ may be the same or different and each represents a divalent hydrocarbon group or a divalent hydrocarbon group having an ether bond. The divalent hydrocarbon group has 1 to 2 carbon atoms.
4, a linear, branched or cyclic divalent hydrocarbon group may be mentioned, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group and an octane group. Methylene group,
Divalent aliphatic hydrocarbon groups such as ethylidene group, propylene group, isopropylidene group, butylene group, isobutylene group and pentylene group; phenylene group, tolylene group, naphthylene group, acenaphthenylene group, phenanthrylene group and the like 2
Examples thereof include a valent aromatic hydrocarbon group or a hydrocarbon group having 7 to 24 carbon atoms in which the above aliphatic hydrocarbon group and aromatic hydrocarbon group are bonded. Examples of the divalent hydrocarbon group having an ether bond include a linear or branched divalent hydrocarbon group having 1 to 10 ether bonds and having 2 to 24 carbon atoms in the chain. The bond may be present at any part of the divalent hydrocarbon radical. n is preferably 0 to 500 in order to exhibit the characteristics of the silicone-vinyl block copolymer as a block copolymer.

The azo group-containing polymer used in the present invention is
As described above, the component having an azo group represented by the general formula (1) and the component having an organopolysiloxane represented by the general formula (2) have an amide bond, an ester bond,
Examples of such a compound include a polymer having a unit bonded through a urethane bond, and examples of such a compound include a polycondensate of azobiscarboxylic acid and a diamine having a siloxane segment, and a diol having an azobiscarboxylic acid and a siloxane segment. And a polycondensate of azobis alcohol and a dicarboxylic acid having a siloxane segment, a polycondensate of a diol having an azobis alcohol and a siloxane segment and a dicarboxylic acid, and a diamine having an azobis alcohol and a siloxane segment. Examples thereof include polycondensates with dicarboxylic acids, polyaddition products of diols having an azobis alcohol and a siloxane segment and diisocyanates, polyaddition products of diamines having an azobis alcohol and a siloxane segment, and diisocyanates.

Here, as an azobiscarboxylic acid which gives a constituent having an azo group represented by the general formula (1),
For example, 2,2'-azobis (2-cyanopropanoic acid),
3,3'-azobis (3-cyanobutanoic acid), 4,4 '
-Azobis (4-cyanopentanoic acid), 5,5'-azobis (5-cyanohexanoic acid), 6,6'-azobis (6-cyanoheptanoic acid) and the like, and examples of the azobis alcohol include 1 , 1'-Azobis (1-cyanoethanol), 2,2'-azobis (2-cyanopropanol), 3,3'-azobis (3-cyanobutanol), 4,4'-azobis (4-cyanopentanol) )
Etc.

Examples of the dicarboxylic acid include malonic acid,
Aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.

Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexane diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate). Kind;
Aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate are mentioned.

The method for synthesizing the azo group-containing polymer used in the present invention includes azo compounds, silicone compounds, a method in which the carboxylic acid group of a dicarboxylic acid is converted into an acid halide and then reacted with a hydroxyl group or an amino group, and a carboxylic acid group. With hydroxyl group or amino group using a condensing agent such as tosyl chloride, carbonyldiimidazole, methylchloropyridinium iodide, dicyclohexylcarbodiimide, etc., reacting azobis alcohol with a silicone compound having a hydroxyl group or amino group and diisocyanate And the like.

The vinyl-based monomer used in the method for producing the silicone-vinyl-based block copolymer of the present invention can be used without particular limitation as long as it is a monomer which is polymerized by a radical reaction. Examples of such a monomer include ethylene, propylene, butene,
Isobutene, butadiene, isoprene, chloroprene,
Acrylic esters such as styrene, α-methylstyrene, acrylonitrile, vinylidene cyanide, acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate. , Methacrylic acid esters such as glycidyl methacrylate and 2-ethylhexyl methacrylate, methacrylamide, maleic anhydride, dimethyl maleate, maleic acid esters such as diethyl maleate, fumaric acid such as dimethyl fumarate and diethyl fumarate N-substituted maleimides such as esters, maleimides, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, vinyl acetate, vinyl propionate and vinyl benzoate Esters, vinyl ethers such as methyl vinyl ether, phenyl vinyl ether, vinyl chloride, vinylidene chloride, tetrafluoroethylene,
Vinyl pyridine, N-vinyl pyrrolidone, etc. can be mentioned, and these 1 type (s) or 2 or more types can be used.

In the production method of the present invention, the azo group-containing polymer is dissolved in a solvent for easy handling,
It is introduced into a can as an azo group-containing polymer solution. And
The solvent introduced as the solution is 1) the productivity of the silicone-vinyl block copolymer decreases before the polymerization reaction of the vinyl monomer, and 2) the silicone-vinyl block copolymer obtained is It is necessary to remove from the polymerization system in order to avoid problems such as generation of offensive odor, 3) risk of explosion when dried, and the like.

The can used in the present invention is a container for removing the solvent from the azo group-containing polymer solution. Examples of such a can include a polymerization can or a pretreatment can provided separately. Etc. can be mentioned.

Here, when a pretreatment can is installed, the solvent is removed in the pretreatment can, the azo group-containing polymer is dissolved in the vinyl monomer, and then the polymer is transferred to the polymerization can.
At this time, the period from the mixing of the azo group-containing polymer and the vinyl-based monomer to the start of polymerization is preferably within 1 day from the viewpoint of stability of both.

In the production method of the present invention, the method for removing the solvent of the azo group-containing polymer solution from the can is as follows:
Any method can be used as long as the solvent can be removed. As such a method, the method of removing by solvent or the method of removing by distilling with water is particularly preferable because the solvent can be removed efficiently and the decomposition of the azo group-containing polymer can be suppressed.

As the solvent used for facilitating the handling of the azo group-containing polymer in the present invention, any solvent can be used as long as it dissolves the azo group-containing polymer used in the present invention. . And, since the solvent can be removed efficiently and the decomposition of the azo group-containing polymer can be suppressed, the temperature at which the azo group-containing polymer is dissolved and the azo group in the azo group-containing polymer hardly decomposes It is preferable that the solvent is a solvent that can be removed by distillation or that is soluble in water.

The amount of the solvent used in the present invention is appropriately determined in consideration of the viscosity of the azo group-containing polymer solution, that is, the fluidity, etc., and is not particularly limited, but usually 100 parts by weight of the azo group-containing polymer is used. It is preferable to use 20 to 500 parts by weight of the solvent.

The azo group-containing polymer used in the method of distilling off the solvent which is mentioned as one of the preferred production methods of the present invention is dissolved, and the azo group in the azo group-containing polymer is decomposed. A solvent that can be distilled off at a temperature at which almost no reaction occurs is usually preferable to distill the solvent at a temperature of 40 ° C. or lower in order to suppress the decomposition of the azo group at the time of distillation. It is preferable that the vapor pressure is 50 mmHg or more and the boiling point at normal pressure is 0 ° C. or higher and 120 ° C. or lower. And as such a solvent, for example, hydrocarbons such as pentane, hexane, heptane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, benzene, toluene; dichloromethane, chloroform, Halogenated hydrocarbons such as 1,2-dichloroethane and 1,1,1-trichloroethane; ethers such as diethyl ether, dipropyl ether, tetrahydrofuran and 1,4-dioxane; ethyl formate, methyl acetate, ethyl acetate, acetic acid Carboxylic acid esters such as isopropyl; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and isopropanol.
These may be used alone or in combination of two or more.

In the method for distilling off the solvent, which is mentioned as one of the preferred production methods in the present invention,
The method for distilling the solvent is carried out under normal pressure or reduced pressure. The temperature at that time is preferably about 0 to 40 ° C. in order to suppress the decomposition of the azo group and improve the distillation efficiency.

Further, as the solvent for dissolving the azo group-containing polymer used in the method for extracting and removing the solvent into water, which is mentioned as another preferred production method of the present invention, and as a solvent soluble in water, , Ethers such as tetrahydrofuran and 1,4-dioxane; carboxylic acid esters such as ethyl formate, methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and isopropanol; N, Examples thereof include N-dimethylformamide and dimethyl sulfoxide, which can be used alone or in combination of two or more kinds.

Another preferred production method of the present invention is to remove the solvent by extracting it with water.
The azo group-containing polymer solution and water are mixed and stirred, and then the solvent-water solution is discharged from the can. At this time, the amount of water used for extracting and removing the solvent is appropriately determined based on the amount of the solvent used, the solubility of the solvent in water, and the like.
The temperature at the time of extracting the solvent needs to be a temperature at which the azo group in the azo group-containing polymer is not decomposed, and such a temperature is preferably 5 to 40 ° C.

In the production of the silicone-vinyl block copolymer in the present invention, the solvent of the azo group-containing polymer solution is removed, and then the suspension polymerization, which is generally known as an aqueous polymerization method, It is carried out by fine suspension polymerization or the like.
As the dispersion stabilizer when the dispersion stabilizer is used at the time of polymerization, known dispersion stabilizers can be used. For example, water-soluble polymers such as partially saponified polyvinyl acetate, cellulose derivatives and polyacrylic acids; Amphoteric surfactants having an anion portion such as acid salt, sulfate ester salt, sulfonate salt, and phosphate ester and cation portion such as amine salt and ammonium salt; sulfate ester of higher alcohol, alkylbenzene sulfonate, aliphatic sulfonate Examples thereof include anionic surfactants such as salts; nonionic surfactants such as alkyl esters of polyethylene glycol and alkyl ethers of polyethylene glycol.
Further, the use ratio of the vinyl monomer and the azo group-containing polymer in the polymerization of the vinyl monomer of the present invention, the use ratio of the vinyl monomer and water, the polymerization temperature, the polymerization time, etc.
The conditions can be the same as in the case where no solvent is used, and the conditions are appropriately determined from the methods disclosed in JP-B-2-33053, JP-A-7-2914, JP-A-7-70210 and the like. However, it is usually preferable to carry out under the following conditions. The vinyl-based monomer and the azo group-containing polymer are used in an amount of 0.5 to 1000 parts by weight of the vinyl-based monomer and 1 part by weight of the azo-group-containing polymer.
1 to 2.5 parts by weight of water to 50 parts by weight, the polymerization temperature is 50 to
The polymerization time is preferably 120 ° C. and 2 to 24 hours, and the conditions are appropriately determined in consideration of the properties of the silicone-vinyl block copolymer to be obtained, the polymerization rate, and the like.

Separation of the silicone-vinyl block copolymer after polymerization and water in the present invention can be carried out by a generally known method, for example, filtration, centrifugation,
It is performed by decantation or the like. Further, the silicone-vinyl block copolymer can also be dried by a commonly known method, for example, heat drying while standing,
It is performed by fluidized drying, reduced pressure drying, or the like.

[0034]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The measurement and evaluation methods in the examples will be described below.

The compounds were identified by IR measurement (manufactured by Shimadzu Corporation, trade name IR-460) and NMR measurement (manufactured by JEOL Ltd., trade name JNM-GX400).

The molecular weight is gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, trade name HLC-8).
02A) was used and the value was calculated in terms of polystyrene.

The amount of solvent in the polymer particles is determined by gas chromatography (GC) (manufactured by Shimadzu Corporation, trade name GC-9).
It was measured using A).

The average particle size of the polymer particles was measured using a laser diffraction type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., trade name Microtrac II).

Synthesis Example 1 (Synthesis Example of Azo Group-Containing Polymer) 4,4'-azobis (4-
(Cyanopentanoic acid) (280 g) and dichloromethane (10 l) were charged and dispersed, and then 357 g of 1,1′-carbonyldiimidazole was added thereto, and the mixture was stirred at room temperature for 1 hour, and then polydimethylsiloxane modified at both ends with amino groups. (Shin-Etsu Chemical Co., Ltd., trade name KF8008, number average molecular weight 11500) 12075 g, dichloromethane 15
1 was added, and the mixture was reacted at room temperature for 10 hours.

After the reaction, the following operations were carried out in order to purify the obtained azo group-containing polymer.

Methanol 12 in a 200 l autoclave
0 l was charged and the above reaction solution was added while stirring. The mixture was stirred at room temperature for 1 hour, allowed to stand for a while, and the supernatant was discharged to the outside of the autoclave. Again, 120 l of methanol
Was added, the mixture was stirred and allowed to stand, and the supernatant was discharged. This operation was repeated once more to obtain an azo group-containing polymer containing methanol (white starch syrup).

When methanol was distilled off under reduced pressure at room temperature,
The product, an azo group-containing polymer, was a rubber-like elastic body, and it was difficult to recover it as it was. Then, charge ethyl acetate 42.5kg, 54.5kg
The azo group-containing polymer was recovered as an ethyl acetate solution of.
The non-volatile content in this solution is 22.0%, 12.0k
It contained g of an azo group-containing polymer.

From the IR spectrum and ¹ H-NMR spectrum, it was confirmed that the obtained azo group-containing polymer was an azo group-containing polydimethylsiloxane amide. The molecular weight determined by GPC is the weight average molecular weight (M
w) = 234000, number average molecular weight (Mn) = 9400
It was 0.

Finally, the same operation was repeated 4 times to obtain 218 kg of an azo group-containing polymer in ethyl acetate.

Synthesis Example 2 (Synthesis Example of Polymer Containing Azo Group) After charging 839 g of toluenesulfonic acid chloride and 10 l of dichloromethane in a 50 l autoclave, 1 liter of pyridine was added, and the mixture was stirred at room temperature for 15 minutes, and then dimethylformamide was added. Add 500 ml and add another 15
Stir for minutes.

Then, 560 g of 4,4'-azobis (4-cyanopentanoic acid) and 2 l of dichloromethane were added, and the mixture was stirred at room temperature. After 30 minutes, polydimethylsiloxane having both ends modified with a phenolic hydroxyl group (Shin-Etsu Chemical Co., Ltd., trade name X-22-165E, number average molecular weight 800)
0) 16000 g and dichloromethane 2l were added, and the mixture was reacted at room temperature for 5 hours.

After completion of the reaction, the reaction solution was diluted with dichloromethane and the insoluble matter in the solution was removed by a centrifuge. Thereafter, this filtrate was introduced into a 200 l autoclave, the solvent was distilled off under reduced pressure at room temperature, and the whole was concentrated to 40 l. To this, 120 l of methanol was added, and the mixture was stirred at room temperature for 1 hour and allowed to stand for a while, and then the supernatant was discharged out of the autoclave. Again, 120 l of methanol was added, the mixture was stirred and left to stand, and the supernatant was discharged. This operation was repeated once more to obtain an azo group-containing polymer containing methanol (white starch syrup).

Then, in order to recover this, 17.5 kg of methyl ethyl ketone was added, and a azo group-containing polymer was recovered as a solution of 37.5 kg of methyl ethyl ketone-methanol. The nonvolatile content in this solution is 40%,
It contained 15.0 kg of azo group-containing polymer.

The obtained azo group-containing polymer was confirmed to be an azo group-containing polydimethylsiloxane ester by IR spectrum and ¹ H-NMR spectrum.
The average molecular weight determined by GPC is Mw = 1090.
00 and Mn = 58000.

Finally, the same operation was repeated three times to obtain 113 kg of a methyl ethyl ketone-methanol solution.

Example 1 After charging 136.4 g of an ethyl acetate solution of the azo group-containing polysiloxane amide obtained in Synthesis Example 1 into a 1 l autoclave, the pressure inside the autoclave was reduced to remove ethyl acetate out of the autoclave. (Temperature 25 ℃
The pressure reduction degree is gradually increased with 2 minutes after reaching 1 mmHg).

Thereafter, 11.3 g of a 3 wt% aqueous solution of partially saponified polyvinyl acetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gohsenol GH-23) and 489 g of water were added to the autoclave, and the atmosphere was replaced with deaerated nitrogen, followed by chlorination. 250 g of vinyl was added and the azo group-containing polysiloxane amide was dissolved in vinyl chloride by stirring at room temperature for 1 hour. And
The temperature was raised to 67 ° C. to initiate polymerization. After polymerizing for 5 hours,
The polymerization system was cooled to stop the polymerization. The obtained polymer slurry was filtered, and the collected particles were dried at 60 ° C. for 10 hours under normal pressure to obtain 225 g of silicone-vinyl chloride block copolymer particles. The amount of the polymer attached to the wall of the polymerization vessel, the stirring blade, etc. was 5 g.

The average particle size of the obtained polymer particles is 150 μm.
m, and the amount of ethyl acetate in the polymer particles was 1 ppm or less. The molecular weight of the obtained polymer determined by GPC was Mw = 109000, Mn = 51000.
And the silicone content determined from the ¹ H-NMR spectrum was 11.9% by weight.

Example 2 A 1l autoclave was charged with 62.5 g of a methyl ethyl ketone-methanol solution of the azo group-containing polysiloxane ester obtained in Synthesis Example 2, and the solvent was distilled off in the same manner as in Example 1. Further, polymerization and post-treatment were carried out in the same manner as in Example 1 except that the stirring time for dissolving the azo group-containing polysiloxane ester in vinyl chloride was 5 minutes and the polymerization time was 6 hours, and 216 g of silicone- Vinyl chloride block copolymer particles were obtained. The amount of the polymer attached to the wall of the polymerization vessel, the stirring blade, etc. was 7 g.

The average particle size of the obtained polymer particles is 150 μm.
and the amount of methyl ethyl ketone in the polymer particles is 1 p
It was pm or less. The molecular weight of the obtained polymer determined by GPC was Mw = 107,000, Mn = 5.
The content was 1000 and the silicone content determined from the ¹ H-NMR spectrum was 9.7% by weight.

Example 3 A 1 l autoclave was charged with 113.6 g of an ethyl acetate solution of the azo group-containing polysiloxane amide obtained in Synthesis Example 1, and the solvent was distilled off in the same manner as in Example 1. Then, 250 g of methyl methacrylate and 0.5 g of dodecanethiol were added to the autoclave, and the mixture was stirred at room temperature for 1 hour to dissolve the azo group-containing polysiloxane amide. Furthermore, 3% by weight of partially saponified polyvinyl acetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gohsenol KH-20)
16.7 g of an aqueous solution and 483 g of water were added to the autoclave, the atmosphere was replaced with degassed nitrogen, and the temperature was raised to 80 ° C. to initiate polymerization. After polymerization for 6 hours, the polymerization system was cooled to terminate the polymerization. The obtained polymer slurry was filtered, and the collected particles were vacuum dried at 80 ° C. for 24 hours to obtain 238 g of a silicone-methyl methacrylate block copolymer. Also,
The amount of the polymer attached to the wall of the polymerization vessel and the stirring blade was 11 g.

The average particle size of the obtained polymer particles is 180 μm.
m, and the amount of ethyl acetate in the polymer particles was 1 ppm or less. The molecular weight of the obtained polymer determined by GPC was Mw = 180,000 and Mn = 84,000.
And the silicone content determined from the ¹ H-NMR spectrum was 9.1% by weight.

Example 4 136.4 g of an ethyl acetate solution of the azo group-containing polysiloxane amide obtained in Synthesis Example 1 was placed in a 1 l autoclave.
Water (560 g) was added, and the mixture was stirred at room temperature for 15 minutes. After standing still for a while, an aqueous solution of ethyl acetate was discharged from the autoclave. At this time, the concentration of ethyl acetate in the aqueous solution was 6.8% by weight, and the amount of the discharged aqueous solution was 600 g.
Met. The same operation was performed twice more to remove ethyl acetate by extraction. The ethyl acetate concentration in the aqueous solution of the second extraction operation was 6.6% by weight, the discharge amount was 600 g, the ethyl acetate concentration in the aqueous solution of the third extraction operation was 4.0% by weight,
The discharge amount was 580 g. Therefore, 103.6 g (97.4 wt% of the charged amount) of ethyl acetate was removed by these three extraction operations.

Then, 11.3 g of a 3% by weight aqueous solution of partially saponified polyvinyl acetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gohsenol GH-23) and 489 g of water were added to the autoclave, and after degassing with nitrogen, vinyl chloride was added. 250 g was added, and the azo group-containing polysiloxane amide was dissolved in vinyl chloride by stirring at room temperature for 1 hour. And 6
The temperature was raised to 7 ° C. to initiate polymerization. After polymerization for 5 hours, the polymerization system was cooled to terminate the polymerization. The obtained polymer slurry was filtered, and the collected particles were dried at 60 ° C. for 10 hours under normal pressure to obtain 224 g of silicone-vinyl chloride block copolymer particles. In addition, the amount of the polymer attached to the wall of the polymerization vessel and the stirring blade was 6 g.

The average particle size of the obtained polymer particles is 150 μm.
m, and the amount of ethyl acetate in the polymer particles was 20 ppm. The molecular weight of the obtained polymer determined by GPC was Mw = 108000, Mn = 51000, and the silicone content determined from the ¹ H-NMR spectrum was 11.8% by weight.

Example 5 A 1 l autoclave was charged with 62.5 g of a methyl ethyl ketone-methanol solution of the azo group-containing polysiloxane ester obtained in Synthesis Example 2, and the stirring time for dissolving the azo group-containing polysiloxane ester in vinyl chloride was added. Example 5 except that the polymerization time was 5 minutes and the polymerization time was 6 hours.
The same operation as above was performed to obtain 215 g of silicone-vinyl chloride block copolymer particles. In addition, the amount of the polymer attached to the wall of the polymerization vessel and the stirring blade was 9 g.

The average particle size of the obtained polymer particles is 150 μm.
and the amount of methyl ethyl ketone in the polymer particles is 5 p
pm and methanol were 1 ppm or less. The molecular weight of the obtained polymer determined by GPC is Mw =
107,000, Mn = 51000, ¹ H-NMR
Silicone content determined from the spectrum is 9.8% by weight
Met.

Example 6 A 1 l autoclave was charged with 113.6 g of an ethyl acetate solution of the azo group-containing polysiloxane amide obtained in Synthesis Example 1, and the solvent was extracted and removed in the same manner as in Example 4. Then, 250 g of methyl methacrylate and 0.5 g of dodecanethiol were added to the autoclave, and the mixture was stirred at room temperature for 1 hour to dissolve the azo group-containing polysiloxane amide. Furthermore, 3% by weight of partially saponified polyvinyl acetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gohsenol KH-20)
16.7 g of an aqueous solution and 483 g of water were added to the autoclave, the atmosphere was replaced with degassed nitrogen, and the temperature was raised to 80 ° C. to initiate polymerization. After polymerization for 6 hours, the polymerization system was cooled to terminate the polymerization. The obtained polymer slurry was filtered, and the collected particles were vacuum dried at 80 ° C. for 24 hours to obtain 239 g of a silicone-methyl methacrylate block copolymer. Also,
The amount of the polymer attached to the wall of the polymerization vessel, the stirring blade, etc. was 12 g.

The average particle size of the obtained polymer particles is 180 μm.
m, and the amount of ethyl acetate in the polymer particles was 30 ppm. The molecular weight of the obtained polymer determined by GPC measurement was Mw = 180,000 and Mn = 83000, and the silicone content determined from ¹ H-NMR spectrum was 9.2% by weight.

Example 7 200 m of an ethyl acetate solution of the polysiloxane amide containing an azo group obtained in Synthesis Example 1 was placed in a 1.8 m ³ autoclave.
g was charged into the autoclave using a metering pump, and then the pressure inside the autoclave was reduced at room temperature to remove ethyl acetate outside the autoclave.

Then, 18 kg of a 3% by weight aqueous solution of partially saponified polyvinyl acetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gohsenol GH-23) and 800 kg of water were added to the autoclave, and after degassing with nitrogen, 400 kg of vinyl chloride was added. In addition, the azo group-containing polysiloxane amide was dissolved in vinyl chloride by stirring at room temperature for 1 hour. And
The temperature was raised to 67 ° C. to initiate polymerization. After polymerizing for 5 hours,
The polymerization system was cooled to stop the polymerization. The obtained polymer slurry was introduced into a centrifuge to obtain a polymer cake, which was then dried with a fluidized dryer to obtain 375 kg of silicone-
Vinyl chloride block copolymer particles were obtained.

The average particle size of the obtained polymer particles is 140 μm.
m, and the amount of ethyl acetate in the polymer particles was 1 ppm or less. The molecular weight of the obtained polymer determined by GPC was Mw = 109000, Mn = 52000.
And the silicone content determined from the ¹ H-NMR spectrum was 10.6% by weight.

Example 8 Methyl ethyl ketone of the azo group-containing polysiloxane ester obtained in Synthesis Example 2 was placed in a 1.8 m ³ autoclave.
100 kg of methanol solution was charged into the autoclave using a metering pump, 1000 kg of water was added, and the mixture was stirred at room temperature for 15
Stir for minutes. Then, after standing for a while, an aqueous solution of methyl ethyl ketone and methanol was discharged from the autoclave. Again, 1000 kg of water in the autoclave
Was added and the washing operation was performed once more to remove methyl ethyl ketone and methanol.

Then, 18 kg of a 3% by weight aqueous solution of partially saponified polyvinyl acetate (Nippon Gosei Kagaku Kogyo Co., Ltd., trade name Gohsenol GH-23) and 800 kg of water were added to the autoclave, and after degassing with nitrogen, 400 kg of vinyl chloride was added. In addition, the azo group-containing polysiloxane ester was dissolved in vinyl chloride by stirring at room temperature for 15 minutes. Then, the temperature was raised to 67 ° C. to start the polymerization. After polymerization for 5 hours, the polymerization system was cooled to terminate the polymerization. The obtained polymer slurry was introduced into a centrifuge to obtain a polymer cake, which was then dried with a fluid dryer to obtain 360 kg of silicone-vinyl chloride block copolymer particles.

The average particle size of the obtained polymer particles is 150 μm.
and the amount of methyl ethyl ketone in the polymer particles is 3 p
pm and methanol were 1 ppm or less. The molecular weight of the obtained polymer determined by GPC is Mw =
108000, Mn = 51000, ¹ H-NMR
Silicone content determined from the spectrum is 9.7% by weight
Met.

Comparative Example 1 136.4 g of an ethyl acetate solution of the azo group-containing polysiloxane amide obtained in Synthesis Example 1 in a 1-liter autoclave.
Was charged, and the polymerization was performed without performing the subsequent solvent removal operation, the polymerization time was set to 8 hours, and the drying was performed in the same manner as in Example 1, except that the drying was performed in vacuum. 170 g of copolymer particles were obtained.
In addition, the amount of the polymer attached to the wall of the polymerization vessel or the stirring blade is 54
It was g.

All the polymer particles obtained have a particle size of 1 mm.
That was a big thing. The amount of ethyl acetate in the polymer particles was as high as 1500 ppm, which gave off an offensive odor.
The molecular weight of the obtained polymer determined by GPC was Mw = 92000, Mn = 45000, and ¹ H
-Silicone content determined from NMR spectrum is 1
It was 0.6% by weight.

In this polymerization method, the polymer is considerably attached to the wall of the polymerization vessel or the stirring blade, so that the productivity is low, and more organic solvent remains in the polymer, resulting in poor quality. When the polymer was dried with a fluid dryer, there was a risk of explosion.

Comparative Example 2 62.5 g of a methyl ethyl ketone-methanol solution of the azo group-containing polysiloxane ester obtained in Synthesis Example 2 was charged into a 1-liter autoclave, and polymerization was carried out without performing the subsequent solvent removal operation. 186 g of silicone-vinyl chloride block copolymer particles were obtained in the same manner as in Example 2 except that the polymerization time was 8 hours and the drying was vacuum drying. In addition, the amount of the polymer attached to the wall of the polymerization vessel and the stirring blade was 29 g.

The polymer particles thus obtained were aggregated to 1 m.
20 g of particles having a particle size of m or more were present, and the average particle size of the particles excluding the agglomerates was 360 μm. Also,
The amount of methyl ethyl ketone in the polymer particles is 800 ppm,
The amount of methanol was 5 ppm, which gave off a strange odor. Molecular weight determined by GPC measurement of the obtained polymer was Mw = 94000, Mn = 46000, 1 H
-Silicone content determined from NMR spectrum is 9.
It was 5% by weight.

In this polymerization method, since the polymer is considerably attached to the wall of the polymerization vessel, the stirring blade, etc., the productivity is low, and more organic solvent remains in the polymer, resulting in poor quality. When the polymer was dried with a fluid dryer, there was a risk of explosion.

Comparative Example 3 113.6 g of an ethyl acetate solution of the azo group-containing polysiloxane amide obtained in Synthesis Example 1 was placed in a 1 l autoclave.
Was carried out, and the same procedure as in Example 3 was carried out except that the subsequent solvent removal operation was not carried out to obtain 196 g of silicone-methyl methacrylate block copolymer particles. In addition, the amount of polymer adhering to the wall of the polymerization vessel and the stirring blade is 71 g.
Met.

The polymer particles thus obtained were aggregated to 1 m.
There were 26 g of particles having a particle size of m or more, and the average particle size of the particles excluding the agglomerates was 180 μm. Also,
The amount of ethyl acetate in the polymer particles was as large as 1.5% by weight, which gave off a strange odor. Also, the GPC of the obtained polymer
The molecular weight determined by the measurement is Mw = 18,000, Mn
= 82000, and the silicone content determined from the ¹ H-NMR spectrum was 8.9% by weight.

In this polymerization method, the polymer was considerably attached to the wall of the polymerization vessel, the stirring blades, etc., so that the productivity was low, and more organic solvent remained in the polymer, resulting in poor quality. .

[0081]

Industrial Applicability According to the present invention, an azo group-containing polymer can be handled on an industrial scale without adversely affecting polymerization and the like, and a silicone-vinyl block copolymer having excellent quality can be safely produced on an industrial scale. It has become possible to manufacture with.

Claims (3)

(57) [Claims] 1. The following general formula (1): (In the formula, each R ¹ may be the same or different and represents a hydrogen atom, a nitrile group or a lower alkyl group, and each R ² may be the same or different and represents a divalent hydrocarbon group. , M represents 0 or 1.) and a constituent component having an azo group represented by the following general formula (2): (In the formula, each R ³ may be the same or different,
A hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group or a phenyl group, each R ⁴ may be the same or different, and a divalent hydrocarbon group or a divalent hydrocarbon group having an ether bond may be present. It shows and n shows the integer of 0-500. And an organopolysiloxane represented by the formula (1) is used as a polymerization initiator, and an azo group-containing polymer having a unit bonded through an amide bond, an ester bond or a urethane bond is used as a polymerization initiator. In the method for producing a combined product, the azo group-containing polymer is dissolved in a solvent, charged into a can, the solvent is removed to the outside of the can, and then a vinyl-based monomer is polymerized in a polymerization can with water as a dispersion medium. A method for producing a characteristic silicone-vinyl block copolymer. 2. A method in which an azo group-containing polymer is dissolved in a solvent, charged into a can, the solvent is distilled out of the can, and the vinyl monomer is polymerized in a polymerization can using water as a dispersion medium. The method for producing a silicone-vinyl block copolymer according to claim 1, which is characterized in that. 3. An azo group-containing polymer is dissolved in a solvent, charged into a can, the solvent is extracted and removed with water, and then a vinyl monomer is polymerized in the polymerization can using water as a dispersion medium. The method for producing the silicone-vinyl block copolymer according to claim 1.