JPS60123518A - Production of silicone based graft copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having improved water, heat and weather resistance, etc., by copolymerizing an acrylic-modified silicone of a condensate of silicone of a specific formula with an acrylic compound radically with a radically polymerizable monomer. CONSTITUTION:(A) A silicon expressed by formula I (R1 and R2 and 1-10C monofunctional aliphatic hydrocarbon, phenyl or halogenated hydrocarbon; n>=2) is reacted with (B) an acrylic compound expressed by formulas II and/or III[R3 is H or methyl; R4 is methyl, ethyl or phenyl; m is 0 or 1; l is an integer 0-2 when m is 0, l is 1 when m is 1; X is 1-10C alkoxyl, acetoxy or Cl], e.g. (meth)acrylate silane, in a solvent, e.g. diethyl ether, to give an acrylic-modified silicone. The resultant acrylic-modified silicone is then reacted with (B) a radically polymerizable monomer, e.g. ethylene, in the presence of a radical polymerization initiator, e.g. ammonium persulfate, generally at 50-100 deg.C for 3- 100hr to afford the aimed copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a silicone-based graft copolymer.

Conventionally, several methods have been proposed for producing silicone-based graft copolymers, such as Japanese Patent Publication No. 52-689.
Publication No. 6, Japanese Patent Publication No. 47-16199, Japanese Patent Application Publication No. E48
A method of forming an active group by abstracting hydrogen from a lower alkyl group bonded to a silicon atom of silicone and grafting an organic polymer thereto, as described in Publication No. 28389 (hereinafter abbreviated as silicone hydrogen abstraction method)
, Japanese Patent Publication No. 46-9555, Japanese Patent Publication No. 52-1353
As seen in Japanese Patent No. 91, etc., there is a method in which silicone having active groups is prepared in advance and an organic polymer is grafted onto the active group (hereinafter abbreviated as the method using silicone having active groups).

Among these proposed methods for producing silicone-based graft copolymers, in the method based on hydrogen abstraction from silicone, hydrogen abstraction from lower alkyl groups bonded to silicon atoms is an essential condition for producing the graft copolymer. Therefore, a method and conditions suitable for abstracting hydrogen from the lower alkyl group bonded to the silicon atom of silicone are first required.

A commonly used method is to form a silicone and a polymer to be grafted onto the silicone, and then heat the resulting monomer and organic peroxide to react. The type of oxide, amount and reaction temperature must be carefully chosen. For example, with respect to catalysts, azo-based initiators such as azobisisobutyronitrile have a low hydrogen abstraction ability from silicone, resulting in low grafting efficiency (and cannot normally be used).

Generally, a peroxide represented by ROOH or ROOR (R is an organic group) is used, such as benzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. However, the ease with which hydrogen can be abstracted from silicone varies depending on the type of peroxide.

Furthermore, although the reaction temperature is above the decomposition temperature of the organic peroxide used, the ease with which hydrogen can be abstracted from silicone is affected by the temperature, and at the same time, the molecular weight of the organic polymer to be grafted is also affected. It is difficult to control the influence well, and furthermore, the crosslinking reaction may proceed and gelation may occur during the reaction, making it impossible to obtain a graft copolymer with a clear structure. That is, the molecular weight and number of organic polymers grafted per silicone molecule may differ, and unreacted silicone that is not grafted may be included.

On the other hand, in the method using silicone with active groups,
For example, according to the method disclosed in Japanese Patent Publication No. 46-9555, a silicone-based graft copolymer can be obtained by reacting silicone having an active group with a living polymer obtained by anionic polymerization. The manufacturing process used is complicated, it is necessary to select monomers that are resistant to anionic polymerization, and the manufacturing cost is high.
It's never satisfying. - Furthermore, according to the method disclosed in Japanese Patent Publication No. 52-135391, a polysiloxane polyester containing maleic acid in the main chain is synthesized, and an electron-donating monomer that easily forms a charge transfer complex with maleic acid is added to the polysiloxane polyester. A silicone-based graft copolymer can be obtained by mixing and graft polymerizing, but there are restrictions on the monomers that can be used.

The present inventors have arrived at the present invention as a result of intensive research in view of these hitherto proposed methods for producing silicone-based graft copolymers in order to overcome the drawbacks of known methods.

That is, the present invention is characterized in that an acrylic-modified silicone, which is a condensation reaction product of a silicone represented by the following general formula (A) and an acrylic compound represented by the general formula (B), and a radically polymerizable monomer are radically copolymerized. This is a method for producing a silicone-based graft copolymer.

1 (A,) HO(7S 1O-)--HI3 2 However, R1 and R2 are a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group, or a -valent halogenated hydrocarbon group. n is a positive number of 2 or more.

3 (B) CH2=C7C-(XCI(2-1i7(-0
鈷CH2CH2CH,,5i(Ra2X1 and/or R3 CH2=C-C-0(-CH,ei÷0%7CH,CI
]2CH, SiX.

1 However, R3 is a hydrogen atom or a methyl group. R' is a methyl group,
Ethyl group, phenyl group. m is D or 1゜l is m = O
In the case of , it is an integer of 0 to 2, and in the case of m-1, 2°X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom.

Various types of silicones represented by the general formula (A,) used in the present invention are currently readily available, and one suitable for the purpose can be used. Substituent 1' (+ and R2 present on the silicon atom are a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group, or a -valent halogenated hydrocarbon group having 1 to 10 carbon atoms) Examples of monovalent aliphatic hydrocarbon groups include methyl group, ethyl group, decyl group, etc., and examples of -valent halogenated hydrocarbon groups include:
For example, 6°3.3-)lifluoroglovir group, 4,4
, 4-trifluoro-6,6-difluorobutyl group,
Examples include 2-chloroethyl group. Particularly preferred as R1 and R2 is a methyl group.

The molecular weight of the silicone represented by general formula (A) can be selected depending on the purpose. Generally, when an acrylic modified silicone derived from a silicone with a large molecular weight in which n is 100 or more and a radically polymerizable monomer are copolymerized, An oil-like graft copolymer is obtained, and in copolymerization of an acrylic-modified silicone derived from a low molecular weight silicone with n of 100 or less and a radically polymerizable monomer, an oil-like or jelly-like graft copolymer is obtained depending on the type of monomer used. , various types of graft copolymers such as solid ones can be obtained.
If n is too small, the effects of silicone in the resulting silicone graft copolymer, i.e., water repellency, slip properties,
Weather resistance, gas permeability, etc. cannot be obtained, and if the silicone graft copolymer is too large, the obtained silicone graft copolymer becomes oily and difficult to purify. Therefore, n is preferably 2 or more and 500 or less, and 10 or more and 400 or less. More preferred.

The acrylic compound represented by the general formula (B) is an acrylate silane and/or a methacrylate silane (hereinafter collectively referred to as (meth)acrylate silane), and specifically, r-(meth)acryloyl Oxypropyltrimethoxysilane, γ-(meth)acryloyloxyglobyltrichlorosilane, γ-(meth)acryloyloxyglopyldimethylmethoxysilane, γ-
(meth)acryloyloxyglobildimethylchlorosilane, 3-(2-(meth)acryloyloxyethoxy)propyltrimethoxysilane, 6-(2-(meth)acryloyloxyethoxy)globiltrichlorosilane, 3-(2-( meth)acryloyloxyethoxy)propyldimethoxysilane, 3-(2-(meth)acryloyloxyethoxy)propyldimethylchlorosilane,
5-((meth)acryloyloxy)pentyltrimethoxysilane, 5-((meth)acryloyloxy)pentyltrichlorosilane, 5-((meth)acryloyloxy)pentyldimethylmethoxysilane, 5-((meth)acryloyloxy) Examples include pentyldimethylchlorosilane. Among these, γ-methacryloxyglobyltrimethoxysilane is most preferred in terms of availability and low cost.

The reaction between the silicone represented by the general formula (A) and the acrylic compound represented by the general formula (B) proceeds very smoothly according to ordinary organic chemical reaction operations.

For example, when X in the acrylic compound represented by the general formula (B) is a chlorine atom, the silicone represented by the general formula (A) and the acid acceptor are dissolved in an appropriate solvent shown below at a concentration of 10 to 50% by weight. Aku IJ represented by general formula (B) is added to the solution.
) compound or this in the appropriate solvent shown below for 10~
If a solution dissolved at a concentration of 50% by weight is added dropwise at room temperature,
The reaction proceeds immediately and smoothly. After the reaction, the produced acid acceptor hydrochloride is filtered out, and then the desired acrylic-modified silicone can be obtained by washing with water in some cases and evaporating the solvent. The solvent that can be used is preferably a solvent that dissolves both reaction components and is inert to both reaction components under the reaction conditions. Suitable solvents include diethyl ether, tetrahydrofuran, acetone, benzene, toluene, xylene, mineral spirit, etc. Known amines can be used as the acid acceptor, and preferably pyridine, triethylamine, aniline, etc. are used.The amount of acid acceptor used is 1. About twice the molar amount is desirable.

X of the acrylic compound represented by general formula (B) has 1 carbon number
In the case of ~10 alkoxy groups, it is a dealcoholization reaction between the 7 silicone represented by the general formula (A) and the acrylic compound represented by the general formula (B). Although this reaction can be carried out without a catalyst, catalysts conventionally used in transesterification reactions are used to accelerate the reaction, such as sulfuric acid, P-)luenesulfonic acid, sodium hydroxide, potassium hydroxide, potassium acetate, and dibutyltin. Dilaurate etc. can be used. The amount of catalyst is desirably about 0.1 to 5% by weight based on the total amount of silicone and acrylic compound.

The reaction temperature is preferably 50°C or higher (generally, a temperature of 100°C or higher is adopted. Also, this reaction can be carried out without a solvent or with a solvent. Usable solvents include benzene, toluene, and xylene. , mineral spirits, etc.

In addition, when X of the acrylic compound represented by the general formula (B) is an acetoxy group, the reaction is an acetic acid decondensation reaction between the silicone represented by the general formula (A) and the acrylic compound represented by the general formula (B). . In this case, the same reaction operation as in the case where X is an alkoxy group can be used.

As mentioned above, acrylic modified silicone has the general formula (A
) (hereinafter simply referred to as silicone) and an acrylic compound represented by general formula (B) (hereinafter simply referred to as acrylic), but the reaction equivalent ratio of the two can be determined freely depending on the purpose. can be selected.

For example, if you want to obtain an oily silicone-based graft copolymer that can be used as a sealant, it depends on the type of radically polymerizable monomer used when radically copolymerizing the acrylic-modified silicone and the radically monomerizable monomer. , as mentioned above, mainly silicone is n=20
It can be easily obtained by using an acrylic-modified silicone with a large molecular weight of 0 to 500, so it has little to do with the reaction equivalent ratio of silicone and acrylic during the production of acrylic-modified silicone, but in general, the 5i-OH of silicone
Preferably 0.1 to 5i-X of acrylic per equivalent
1 equivalent, more preferably silicone 5i-OI(1
5i-X of acrylic per equivalent is 0.2 to 0.8 equivalent.

Acrylic S per equivalent of silicone Si -OH
If i-X is less than 0.1 equivalent, there will be a large amount of unreacted silicone, and if it exceeds 1 equivalent, the resulting silicone-based graft copolymer tends to have poor fluidity.

In addition, conventional silicone-based sealants have low stain resistance, low strength, and high moisture permeability, resulting in significant corrosion of the base material, whereas in the present invention, acrylic-modified silicone is preferably %, a silicone-based graft copolymer with excellent stain resistance, strength, and moisture permeability can be obtained.

If the proportion of acrylic-modified silicone is less than 5% by weight, it is difficult to obtain weather resistance and water repellency, while if it exceeds 60% by weight, strength tends to decrease.

On the other hand, if you want to obtain a silicone-based raft copolymer that can be dissolved in solvents used in organic solvent-based paints, such as toluene, xylene, acetone, methyl ketone, and thinner, The reaction equivalent ratio is preferably 01-08 equivalents of 5i-X of acrylic per equivalent of 5i-OH of silicone, more preferably 02-07 equivalents of 5i-X of acrylic per equivalent of 5i-OH of silicone. do. Silicone Si-OH Acrylic Si-
When X is less than 01 equivalent, unreacted silicone increases,
When the amount exceeds 0.8 equivalent, gelation is likely to occur when the resulting acrylic-modified silicone is radically copolymerized with a radically polymerizable monomer, making it difficult to obtain a silicone-based graft copolymer that can be dissolved in a solvent.

In addition, a silicone-based graft copolymer obtained by copolymerizing preferably 5 to 60% by weight of acrylic-modified silicone with a radically polymerizable monomer can itself be used as a paint vehicle and can be dried at room temperature, resulting in a coating film. It is flexible and has excellent weather resistance.

If the proportion of acrylic modified silicone is less than 5% by weight, weather resistance and water repellency will not be sufficient, and if it exceeds 60% by weight, the strength will tend to decrease.

In this way, the reaction equivalent ratio of silicone and acrylic can be appropriately selected depending on the intended use.

In addition, to obtain a silicone-based graft copolymer used as a surface modifier, monomers are copolymerized with acrylic-modified silicone obtained by using a silicone with n = 100 or more, and the number average molecular weight is 10,000 to 20,000. A silicone-based graft copolymer.

The unreacted silicone contained in the acrylic-modified silicone is directly subjected to radical copolymerization with a radically polymerizable monomer in the next step, and after obtaining a silicone-based graft copolymer, it can be recovered as necessary. can.

The thus obtained acrylic-modified silicone, which is suitable for the intended use, has extremely high M attachment properties and can be copolymerized very smoothly with most ordinary radically polymerizable monomers, making it suitable for silicone-based graft copolymerization. The combination can be easily obtained and its molecular weight can be controlled by known polymerization techniques.

Examples of radically polymerizable monomers (hereinafter simply referred to as monomers) suitable for use in the present invention include olefinic compounds such as low molecular weight linear unsaturated hydrocarbons such as ethylene, propylene, and butylene, vinyl chloride, and fluorinated Vinyl halides such as vinyl, vinyl esters of organic acids such as vinyl acetate, styrene, styrene substitutes, and other vinyl aromatic compounds such as vinylpyridine and vinylnaphthalene, acrylic acid, methacrylic acid, and esters thereof. , amide-containing acrylic acid, methacrylic acid, acrolein, acrylonitrile, N-vinylpyrrolidone, and N-bi4capsicutam.
Examples include -vinyl compounds, vinyl silicon compounds such as vinyltriethoxysilane, and acrylic silicon compounds such as γ-methacryloxyglobyltrimethoxysilane. Disubstituted ethylene can also be used, examples of which include vinylidene fluoride, vinylidene chloride, etc.
Mention may also be made of esters of maleic anhydride, maleic acid and fumaric acid.

The monomers can be used alone or in combination of two or more types.

The radical copolymerization ratio of the acrylic modified silicone and the monomer is 1
Preferably, 2 to 90 M parts of the acrylic modified silicone and 98 to 10 parts by weight of the monomer are used per 00 parts by weight, and the copolymerization ratio can be selected over a wide range depending on the intended use.

Conventionally known methods can be used for the radical copolymerization of the acrylic-modified silicone and the monomer, such as radiation irradiation, radical M (using an intermediate initiator), etc. (The method is preferable for the ease of superposition operation, the molecular weight adjustment of the resulting silicone graft copolymer σ), the ease of valley σ], a, specifically, the solution polymerization method in which the solvent is transferred to the moon, Bulk polymerization methods, emulsion polymerization methods, etc. can also be used.

As the radical polymerization initiator that can be used in the present invention, any of the general radical polymerization initiators (for combination (X, °C, σ) can be used, and an appropriate one can be selected depending on the superposition method. Examples Examples of inorganic radical polymerization initiators include ammonium persulfate; examples of organic radical polymerization initiators include no-oxyketal, no-hydrocarbon oxide, dialkyl leno<-makeside, diacyl peroxide, and no-( -Oxy-cabonates, peroxyesters and azobisisophs.

In order to obtain a silicone-based graft copolymer with a relatively clear structure σ, such as azo compounds such as tyronitrile (any one can be used, organic peroxides and azo compounds with low decomposition temperatures) are used. Preferred are azo compounds, particularly preferred. As the azo compound, both nitrogen atoms of the azo bond are bonded to the sixth carbon atom 1-1, and the remaining valence of the sixth carbon atom is preferably a nitrile having 1 to 18 carbon atoms;
It is an azo compound satisfied by a carboxyalkyl, cycloalkylene or alkyl group, and azobisisobutyronitrile (hereinafter abbreviated as AIBN) is the most preferred.

When copolymerizing by ultraviolet irradiation method, radical ](
A known sensitizer is used as an intermediate initiator, whereas when copolymerization is carried out by electron beam irradiation, it is not necessary to use a radical polymerization initiator.

The amount of radical polymerization initiator is generally from 0.01 to 5% by weight, preferably from 0.1 to 2% by weight, based on the total weight of the reaction components.
It is.

The reaction temperature for radical copolymerization is preferably higher than the decomposition temperature of the radical polymerization initiator, but if the reaction temperature is too high, undesirable reactions such as crosslinking will occur, making it difficult to obtain a silicone-based graft polymer with a clear structure. Therefore, the reaction temperature is preferably as low as possible. Generally the reaction temperature is 5
The temperature is 0 to 100°C, preferably 60 to 90°C.

The reaction time is generally 3 to 100 hours, preferably 10 to 100 hours.
It is 25 hours.

When the acrylic modified silicone and the monomer are radically copolymerized using AIBN, which is the most suitable initiator in the method of the present invention, in addition to being able to easily obtain a silicone-based graft copolymer, the initiator AIBN
Since the hydrogen abstraction ability of silicone is low (and the reaction temperature is low, unreacted silicone can remain as it is in the silicone-based graft copolymer produced, and such unreacted silicone is transferred to n- It can be recovered by extraction using a solvent such as xane, mineral spirit, acetone, etc.

That is, one embodiment of the present invention is to react an acrylic-modified silicone produced from silicone and acrylic with a monomer by radical copolymerization to produce a silicone-based graft copolymer, and then remove unreacted silicone in the graft copolymer. This is a method for producing a silicone-based graft copolymer, which comprises a step of recovering a silicone-based graft copolymer. The unreacted silicone can be recovered by extracting the solvent-insoluble silicone graft copolymer and the solvent-soluble silicone using a conventional method.

The resulting silicone-based graft copolymer is a graft copolymer in which the polymer obtained from monomers (hereinafter referred to as organic polymer) forms the outer trunk, and the components containing silicone units form the branch parts. Since the component containing the silicone unit is not bonded to the organic polymer through bonds such as 5i-0-C, it is extremely stable against hydrolysis.

The number of branch points in the produced graft copolymer can be determined by the molecule i of the acrylic modified silicone used, the molecular weight of the monomer, the molecular weight of the silicone-based graft copolymer, and the silicone content in the silicone-based graft copolymer. be able to.

The molecular weight of the silicone unit, which is the branch part of the silicone-based graft copolymer obtained according to the method of the present invention, depends on the type of acrylic-modified silicone used, and the molecular weight of the silicone that is the raw material for producing the acrylic-modified silicone [the general formula ( The value of n in A) can be easily controlled by appropriately selecting the value of n, and polymerization can be performed at low temperatures using a particularly preferred polymerization initiator such as AI BN. No graft polymerization or crosslinking reactions occur, and
By using a commonly used chain transfer agent, the molecular weight of the silicone-based graft copolymer produced can also be easily controlled.

As described above, the method of the present invention can produce various silicone-based graft copolymers through extremely simple operations, and has extremely high industrial value.

In addition, the silicone-based graft copolymer obtained by the method of the present invention has a silicone unit-containing component in the comonomer,
Since it contains a silanol unit at its terminal, the silanol unit can be crosslinked by using a commonly used terminal silanol type silicone crosslinking agent and crosslinking accelerator.

Furthermore, the silicone ground copolymer obtained by the method of the present invention can be used as a raw material or surface modifier for sealing agents, various plastic films, molded products, fibers, rubber, paints, adhesives, etc. It can provide the properties of silicone, such as water resistance, heat resistance, and weather resistance.

Next, Examples, Reference Examples, and Comparative Examples are listed in order to explain the present invention more specifically.

Note that parts on each side represent parts by weight.

Example 1 α,ω-Dihydroxypolydimethylsiloxane CH.

(0.01%) and viridiy 1.5B, F (0.02 mol) were dissolved in 400 m of diethyl ether,
γ-methacryloxyglobildimethylchlorosilane 3
．． 31 g (0,015 mol) of a 10% diethyl ether solution was gradually added dropwise at room temperature over 20 minutes. The reaction proceeded immediately and white crystals of pyridine hydrochloride were precipitated. After the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour, and the crystals of pyridine hydrochloride were removed by filtration. Next, put this filtrate into a separating funnel and add 500 ml of water (shaking and washing with water were performed).

After washing with water, the separatory funnel was left standing to separate the upper ether layer and the lower aqueous layer, and anhydrous sodium sulfate was added to the obtained ether layer, which was then left at room temperature overnight to dehydrate. Thereafter, anhydrous sodium sulfate was removed by filtration, and the resulting filtrate was distilled under reduced pressure to remove ether, yielding colorless and transparent acrylic-modified silicone 2059.

Next, per 40 parts of the obtained acrylic modified silicone, 30 parts of styrene, 60 parts of butyl acrylate, AIBNI
The mixture was placed in a flask equipped with a condenser, a stirrer, and a nitrogen (hereinafter abbreviated as N2) inlet tube, and polymerized under N2 at a temperature of 70°C for 10 hours. Heat a small amount of unreacted upper material to 80°C.
It was removed under reduced pressure of 1 mmHg. The obtained silicone-based graft copolymer was a white uniform oil, and remained an extremely uniform white oil even after being stored at room temperature for 2 months. It was also suitable as a sealant.

Examples 2.6 and 4 α,ω-Dihydroxypolenemethylsiloxane CH.

CH.

To a solution of 9.48.9 (0.12 mol) of pyridine and 9.48.9 (0.12 mol) of γ-methacryloxypropyltrichlorosilane dissolved in diethyl ether 400
, 0333 mol) in diethyl ether was gradually added dropwise at room temperature over 20 minutes. Thereafter, acrylic modified silicone 22111 was obtained in the same manner as in Example 1.

This acrylic modified silicone and butyl methacrylate were copolymerized at each ratio shown in Table 1. For copolymerization, acrylic modified silicone, butyl methacrylate, and a mixture thereof were added with 0.5% AIBN in a test tube, and N
The mixture was heated at a temperature of 80° C. for 7 hours.

Table 1 shows the properties of the obtained silicone graft copolymer.
It was shown to.

Table-1 Example 5 and Comparative Example 1 4 with a stirrer, thermometer, condenser, and N2 inlet pipe
α,ω-dihydroxypolycarbonate dimethylsiloxane [HO℃5iO−)=11 n is the average CH.

30) 336 g (0.15 mol), 124 g (0.0
5 mol), potassium acetate filter, 5. Prepare fJ N211
The reaction was carried out at a temperature of 50° C. for 20 hours. The cooled hindlimb reaction product was poured into 1360 g of toluene to precipitate potassium acetate,
Potassium acetate was removed by filtration.

Methyl methacrylate (per 791.000 parts of 20% toluene solution of acrylic modified silicone obtained)
Add 400 parts of MMA (hereinafter abbreviated as MMA), 400 parts of ethyl acrylate (hereinafter abbreviated as EA), 10 parts of A, IBN, and 1530 parts of toluene to form a homogeneous solution under N2.
The reaction was carried out at a temperature of 5° C. for 7 hours. The obtained silicone-based graft copolymer (30%) was formed into a film using a bar coater on an aluminum plate, and after air-drying at room temperature for one day, the physical properties of the coating film (silicone-based graft polymer) were measured. did.

The results are shown in Table 2 as Example 5. The obtained silicone-based graft copolymer was suitable as a paint vehicle.

In addition, the physical properties of a Koa polymer coating film obtained by polymerizing MMA and EA at a weight ratio of MMA/EA=1/1 without using the above-mentioned acrylic modified silicone are shown in Table 2 as Comparative Example 1. The MMA/EA=1/1 copolymer coating film is MMA/E.
A, 600 parts of l/1 mixture, 700 parts of toluene, AI
3 parts of BN was polymerized and formed into a film in the same manner as in Example 5.

*Contact angle of water on the surface of the paint film that is in contact with the air (measured in 2 parts with a goniometer and a contact angle measuring device at ℃) **Round test: Make cuts in 2 mm square shapes with a knife, The holes were wiped off with cellophane tape, and the residual rate was expressed in % and evaluated.

Examples 6 and 7 3-(2-Methacryloxyethoxy) propyl Dimethylchlorosilane 1
05. A 10% diethyl ether solution of '8 Il (0.4 mol) was gradually added dropwise at room temperature over 20 minutes. Thereafter, acrylic modified silicone 61 was prepared in the same manner as in Example 1.
2g was obtained. Table 6 shows the obtained acrylic modified silicone.
It was copolymerized with the monomer shown in For copolymerization, per 5 parts of acrylic modified silicone, 5 parts of copolymerization monomer, A113
Put 0.05 parts of N into a test tube and heat at 80℃ under N2 for 7 hours.
heated for an hour. The properties of the obtained silicone-based graft copolymer are shown in Table 3.

Table-3 Example 8 α,ω-dihydroxypolydimethylsiloxane C), 1
3 H3 mol) and pyridine (19.0 g (0.24 mol)) dissolved in diethyl ether (400 mol), 5-(methacryloxy)pentyldimethylchlorosilane (24.86 mol)
g (0.1 mol) of a 10% diethyl ether solution was gradually added dropwise at room temperature over 20 minutes. Thereafter, in the same manner as in Example 1, Aku II/silicone-modified silicone 2-Og was obtained. MMA per 20 parts of this acrylic modified silicone
40 parts of Bi, 12 parts of Bi, parts of AIBNi, and 233 parts of toluene were placed in a flask equipped with a stirrer, a thermometer, a condenser, N, and an inlet tube, and copolymerization was carried out at a temperature of 75° C. under N2 for 7 hours. Obtained silicone-based graft copolymer 3α
% toluene solution was formed into a film on an aluminum plate using a Nokuichi coater, and after air-drying at room temperature for one day, the physical properties of the coating film (silicone graft polymer) were measured.

The coating film has pinholes, etc. (uniformly transparent, 20μ thick, the contact angle on the coating surface is 102°', and the adhesion is 100%.
Met. The contact angle and adhesion were measured in the same manner as in Example 5. The obtained silicone-based kraft copolymer was suitable as a paint vehicle.

Example 9 In a flask equipped with a stirrer, an H-tube equipped with a condenser, a thermometer, and a lower funnel, 67.219 (0.03 mol) of α,ω-dihydro CI (3 H3 on average 30), P-)luene were added. Sulfone pa, 14 parts,) solution of 60 parts of toluene (
Hereinafter, this will be abbreviated as liquid A), and 2.gamma-methacryloxyfurobyltrimethoxysilane is charged into the dropping funnel.
A solution of 48 g (0.01 mol) and 10 parts of toluene (hereinafter referred to as Solution B) was charged. While boiling Solution A, 3 portions of Solution B were added dropwise, and after the addition was completed, the reaction solution was further boiled for 60 minutes. After cooling, the reaction solution was neutralized by adding an excess of anhydrous soda carbonate, and the excess anhydrous soda carbonate was removed by filtration. The obtained filtrate was distilled under reduced pressure to obtain colorless and transparent acrylic modified silicone 659. Next, 70 parts of MMA, 1 part of AIBN, and 190 parts of toluene were charged per 60 parts of this acrylic modified silicone into a flask equipped with a stirrer, a condenser, a thermometer, and an N2 inlet tube.
After heating at a temperature of 75°C under N2 for 4 hours, an additional portion of AIBNI was added and heated at the same temperature for an additional 4 hours. The resulting solution was distilled under reduced pressure to obtain a white crystalline silicone-based kraft copolymer. The amount of silicone contained in this silicone-based graft copolymer is 60.9%, and the amount of acrylic modified silicone extracted with n-hexane is 75%.
Met. To analyze the amount of silicone, accurately weigh approximately 0.25' of the silicone-based graft copolymer into a platinum crucible, add approximately 3 ml of concentrated sulfuric acid, and heat it in an electric furnace at 700°C for 2 hours to determine the silicone as Sin. I met. In addition, to analyze the amount of n-hexane extracted, accurately weigh approximately 5 g of silicone graft copolymer into an Erlenmeyer flask, add approximately 20 g of n-hexane,
After adding 0d and leaving it at room temperature for 1 day, filter, dry, and accurately weigh (different), extract with n-hexane and measure the amount of acrylic modified silicone (W).
, -W2) X 100 /W, (%).

Comparative Example 2 40 parts of α,ω-dihydroxypolydimethylsiloxane used in Example 1, 60 parts of styrene, 30 parts of butyl acrylate, and part AIBNI were copolymerized in the same manner as in Example 1. The obtained copolymer was non-uniform, with the upper layer being a cloudy oil and the lower layer being a white solid.

Comparative Examples 6 and 4 Copolymerization was carried out in the same manner as in Examples 6 and 7 using the α,ω-dihydroxypolydimethylsiloxane used in Examples 6 and 7 and the same copolymerization monomer as in Examples 6 and 7. . The results are shown in Table-4.

Note that Comparative Examples 6 and 4 correspond to Examples 6 and 7, respectively.

Table 4 Reference Example 1 The γ-methacryloxyglobyltrimethoxysilane used in Example 9 was 5.95S! (0,024 mol) was used, but the same procedure as in Example 9 was conducted to obtain 67 parts of a colorless and transparent acrylic-modified silicone. Example 9 below
Copolymerization of acrylic-modified silicone and MMA was carried out in the same manner as above, but a silicone-based graft copolymer that gelled within 30 minutes from the start of polymerization and was well soluble in toluene could not be obtained.

Comparative Example 5 100 parts of αα,ω-dihydroxyboridimethylsiloxane H3 I H3, 83 parts of styrene, 67 parts of butyl acrylate, and 0.75 parts of di-t-butyl peroxide were placed in a flask equipped with a condenser and a stirrer. N2 lower 1
The reaction was carried out at a temperature of 22°C for 7 hours.

Add a small amount of unreacted monomer to 1 mml'-11! at 80°C.
was removed under reduced pressure.

The reaction product was a white highly viscous oil, which
When stored in a container, the oil was non-uniform, with a hard oil in the lower layer and a soft oil in the upper layer. Further, even when an attempt was made to dissolve the reaction product in toluene, there were undissolved substances, resulting in a cloudy toluene solution.

Patent applicant Toa Kaisei Chemical Industry Co., Ltd. Procedure? ili official book April 1982! Kazuto Wakasugi, Commissioner of the Japan Patent Office1, Indication of the case, Patent Application No. 231226 of 1982, Name of the invention, Process for producing a silicone graft copolymer, 3, Person making the amendment, Relationship to the case, Address of the patent applicant. 4 Nishi-Shinbashi 1-14-1, Minato-ku, Tokyo, Detailed explanation of the invention column 5 of the specification subject to amendment, Contents of the amendment (1) 1 methyl ketone in the 8th line from the top of page 14 of the specification.''
Correct the statement to "methyl ethyl ketone."

(2) r n = 10 on the 5th line from the bottom of No. 15 of the specification
The phrase ``0 or more'' is corrected to ``r n = 100 or less.''

Claims (1)

[Scope of Claims] 1 Silicone represented by the following general formula (A) and the general formula (
A method for producing a silicone-based graft copolymer, which comprises radically copolymerizing an acrylic-modified silicone, which is a condensation reaction product with an acrylic compound represented by B), and a radically polymerizable polymer. R' (A) HO+5iOiH 2 However, R1 and R2 are a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group, or a -valent halogenated hydrocarbon group. n is a positive number of 2 or more. (B) CHrC-C-0-(-C114-e-0%
-Q]2CH2CM2S i (R')2X1 and/or 3 CH2=C-C-0+CH! -i←Momochi H,, CH2C
l1. SiX. 1 However, R3 is a hydrogen atom or a methyl group. W is a methyl group, an ethyl group, or a phenyl group. m is 0 or 1゜l is an integer of 0 to 2 when m = 0; when m = 1, 2゜X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom.