JPH0533247B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is useful as an alkoxysilyl group-containing condensable macromonomer, more specifically, as an intermediate for a comb-shaped polymer having an organopolysiloxane as a main chain and a vinyl polymer as a side chain. This invention relates to a novel macromonomer and its production method. The above-mentioned comb-shaped polymer is a novel polymer that has surface migration properties and can impart water repellency (for paint) and adhesion.

Prior Art and Problems to be Solved In recent years, various functional polymers have been synthesized in the field of polymer synthesis. Among these, certain types of block polymers, graft polymers, and comb-shaped polymers are already known as having surface migration properties. However, the synthesis of these polymers has disadvantages such as poor yields of the desired product, complex reactions involving multiple steps, and high costs.

Therefore, the present inventors conducted intensive research to create a new polymer with surface migration properties easily and at low cost. As a result, the present inventors used a mercaptosilane compound having a dialkoxysilyl group as a chain transfer agent and a vinyl monomer. The polymer obtained by polymerization and having an alkoxysilyl group at the end functions as a condensable macromonomer, and the desired comb-shaped polymer can be obtained by condensation polymerization of this polymer alone or in combination with a dialkoxysilane compound. I found it.

The present invention was completed based on this knowledge, and its purpose is to provide an intermediate for the above-mentioned comb-shaped polymer.

Structure and Effects of the Invention In other words, the present invention has the following features: [In the formula, R ¹ and R ² are the same or different alkyl groups each having 1 to 4 carbon atoms, and R ³ is -
OR ¹ , -OR ² or an alkyl group having 1 to 4 carbon atoms,
and R ⁴ is an alkylene group having 1 to 4 carbon atoms]; and at least one mercaptosilane compound represented by the formula, [In the formula, R ⁵ is hydrogen or a methyl group, and X ¹
is an alkyloxycarbonyl group, a substituted alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, or a phenyl group. , [In the formula, R ⁵ and X ¹ have the same meanings as above] Consisting of 10,000 to 10,000 repeating units of at least one of the following, and CH ₂ at one end has the formula, To obtain an alkoxysilyl group-containing condensable macromonomer having a dialkoxysilyl group [wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as above] and having H at the other end. The present invention provides a method for producing an alkoxysilyl group-containing condensable macromonomer characterized by the following, and (2) the above-mentioned alkoxysilyl group-containing condensable macromonomer obtained by the production method.

Specific examples of the zircaptosilane compound of the above formula [] used in the present invention include mercaptomethylmethyldime(et)toxysilane (dimethoxysilane and diethoxysilane are referred to hereinafter), mercaptomethylethyldime(et)toxysilane, 2 -mercaptoethylmethyldime(eth)toxysilane, 2-mercaptoethylethyldime(eth)toxysilane, 3-
Mercaptopropylmethyldime(et)toxysilane, 3-mercaptopropylethyldime(et)toxysilane, 4-mercaptobutylmethyldime(et)toxysilane, 4-mercaptobutylethyldime(et)toxysilane
Examples include toxisilane, and one or more of these may be used. The amount used is usually per 100 parts (parts by weight, same below) of vinyl monomer.
It may be selected within the range of 0.01 to 5 parts.

Vinyl monomer used in the present invention []
refers to monomers having a vinyl group, vinylene group, or vinylidene group, and specifically, for example, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-
Ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, methyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate ,
Tridecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2
-Methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, styrene, etc., and in place of or in combination with these. For example, maleic anhydride, vinyl acetate, 4-META (4-methacryloxyethyl trimellitic anhydride),
HEMAP (acid phosphooxyethyl methacrylate), methacrylic acid, acrylic acid, vinyl propionate, vinyl versatate (trade name Beova, manufactured by Ciel Chemical), vinyl chloride, acrylonitrile, acryl amide, N-methylol acrylic amide, vinyl Examples include pyridine, vinylpyrrolidone, butadiene, and the like. One or more of these may be used.

The alkoxysilyl group-containing condensable macromonomer according to the present invention can be produced according to the following procedure.

A predetermined proportion of the mercaptosilane compound [ ] is blended with the above vinyl monomer [ ], and these are polymerized by heat or light under conventional conditions in the presence of a radical initiator if necessary. This polymerization may be carried out without a solvent or in a solution, but emulsion polymerization or suspension polymerization in which water coexists is not very preferable because the alkoxysilyl group of the mercaptosilane compound [] may be hydrolyzed. The above radical initiator is usually used per 100 parts of vinyl monomer.
It may be used in the range of 0.005 to 0.1 part, and specific examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobisisovaleronitrile, 2,2'-azobisisobutyronitrile (2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), t-
Butyloperoxide, methyl ethyl ketone peroxide, etc., or a combination of a redox catalyst (transition metal salt, amine, etc.) used in redox polymerization and a peroxide radical initiator may be employed.
In addition, in the case of photopolymerization, the radical initiator may or may not be used.

By polymerizing the vinyl monomer [] and the mercaptosilane compound [], the condensable macromonomer of the present invention having an alkoxysilyl group at the terminal can be obtained. The structure when one type of monomer [] and one type of mercaptosilane compound [] are used can be shown by the following formula [I].

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X ¹ have the same meanings as above, and n is an integer from 10,000 to 10,000] In addition, when BPO is used as a radical initiator teeth,
Benzoic acid decomposed and generated during radical polymerization acts as a catalyst, and if water is present in the system, condensation polymerization described below occurs simultaneously, making it possible to obtain a comb-shaped polymer in a one-step reaction.

The condensable macromonomer of the present invention is useful as an intermediate for a comb-shaped polymer, which is the final objective. That is, the condensable macromonomer may be used alone or with the formula, [In the formula, R ⁶ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁷ and R ⁸ are the same or different alkyl groups having 1 to 4 carbon atoms, and
X ² is hydrogen, alkyl group, phenyl group, chlorine, alkoxysilyl group or -NH ₂ , -NH-, -SH
or an alkyl group having a -CN group] At least one dialkoxysilane compound represented by the formula is used in combination, and if necessary, the condensation polymerization is carried out in the presence of a polycondensation catalyst, for example, the above-mentioned condensable macromonomer [I] and, if necessary, one type of dialkoxysilane compound [], the formula, [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X ¹ , X ²
and n is as defined above, is an integer of 1 to 20, and m is 0 or an integer of 1 to 10.] A silicon-containing comb-shaped polymer is produced.

The above dialkoxysilane compound [] can further improve various physical properties such as adhesion by introducing its functional group into the main chain of the desired comb-shaped polymer. Specific examples thereof include N-(2-amino ethyl)-3-
Aminopropylmethyldimethoxysilane, 3-
Aminopropylmethyldiethoxysilane, chloromethylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 2-cyanoethylmethyldiethoxysilane, diethyldiethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, diphenyl Dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyldiethoxysilane, methyldimethoxychlorosilane, methyldimethoxysilane, methyldodecyldiethoxysilane, methyloctadecyldiethoxysilane, methylphenyldiethoxysilane, methylphenyldimethoxysilane,
Dialkoxysilane compounds such as (3,3,3-trifluoropropyl)methyldiethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, and 1,1,4,4-tetramethyl-1,4 -diethoxysilylethylene,
Examples include 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, and one or more of these may be used. The amount used is usually
The amount may be selected at 100 parts or less, preferably 5 parts or less, based on 100 parts of the condensable macromonomer. By using this dialkoxysilane compound, for example, dialkyldialkoxysilane is selected to improve water repellency, and dialkoxysilane having an adhesive group (-NH ₂ , -SH group, etc.) is selected to improve adhesion. It will be done.

The above condensation polymerization may be carried out under the conditions of usually room temperature to 80°C for 48 to 5 hours, and the catalysts used include, for example, titanate esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyl Organotin compounds such as tin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, n-butyltin oxide;
Lead octylate; butylamine, octylamine,
Dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,
4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 1,
3-diazabicyclo(5,4,6)undecene-
7 (DBU) or salts of these carboxylic acids, etc.
The species or species are provided for use. The amount used is usually 0.01 to 1 per 100 parts of condensable macromonomer.
The selection can be made within the scope of the department.

Through such condensation polymerization, for example, in the case of solution polymerization, a viscous solution system is obtained, but when this solution is removed by a normal method, the desired comb-shaped polymer is obtained in the form of a solid at room temperature or a highly viscous oil. Manufactured. The comb-shaped polymer is highly viscous with a low glass transition point when butyl acrylate is used as the vinyl monomer, but in other cases it is mostly a glassy white powder solid.

The comb-shaped polymer obtained as described above can be efficiently produced by a relatively simple two-step reaction (in some cases, a one-step reaction), and because of its surface migration property, it can be easily produced on the surface or interface by adding a small amount. It is possible to exhibit a modification effect (for example, an anti-fouling effect). Furthermore, those having a functional group of a dialkoxysilane compound [] introduced into the main chain have improved physical properties such as water repellency and adhesion. As described above, the comb-shaped polymer may be used as a water repellent agent for paints, an adhesion agent (particularly for glass surfaces), and a release agent, and may also be used as a surface-active agent.

Next, the present invention will be described in more detail with reference to Examples.

Example 1 Methyl methacrylate (MMA) 50g, 3-mercaptopropylmethyldimethoxysilane 0.9
g, AIBN0.08g and toluene 25g are placed in a glass polymerization tube, cooled and degassed, and then melt-sealed. This is 60
Polymerization is carried out with shaking in a ℃ bath, and a highly viscous toluene solution of the condensable macromonomer is obtained after about 8 hours. The yield determined by the weight change method (105°C, 4 hours) was 96%. This macromonomer is IR
It was confirmed by a spectrometer (manufactured by JASCO Corporation) that it was polyMMA. Furthermore, gel permeation chromatography (GPC) revealed that the number average molecular weight was 9.8×10 ³ .

Reference Example 1 0.5 part of dibutyltin dilaurate is added to 100 parts of the polyMMA toluene solution of Example 1, spread on a shear plate as thinly as possible, and left at room temperature for 7 days. The toluene as a solvent evaporates and a solid polymer film is obtained. When a part of this was dissolved in tetrahydrofuran and GPC was measured in the same manner as in Example 1, the number average molecular weight was 4.5×10 ⁴ . From this, it is recognized that it is a comb-shaped polymer represented by the following formula.

Additionally, 2 parts of dimethyldiethoxysilane, 5 parts of ion-exchanged water, and 0.5 parts of n-butyltin oxide were added to 100 parts of the same polyMMA toluene solution, and 8 parts of the solution was heated at 60°C.
The viscosity became higher after stirring for a longer time. of this
GPC measurements revealed that it was a polymer with a molecular weight of 7.8×10 ⁴ . From this, it is assumed that organopolysiloxane is the main chain and the average molecular weight is 9.8×10 ³
It is recognized that it is a comb-shaped polymer with about 8 polyMMA side chains.

Example 2 10 g of butyl acrylate and 0.5 g of 3-mercaptopropylmethyldimethoxysilane are placed in a glass polymerization tube, cooled and degassed, and then melt-sealed. This is approx.
Place it in a water tank at 15℃ and apply UV (Toshiba SHL-100) for 10 minutes.
Photopolymerization is performed while irradiating from a distance of cm. After 10 hours, the contents were taken out and the yield was determined by the weight change method and was found to be 95%. Furthermore, the number average molecular weight was 4.5×10 ³ as determined by GPC.

Reference Example 2 To 100 parts of the product of Example 2, 5 parts of methyldimethoxysilane, 0.5 parts of n-butyltin oxide, and a small amount of ion-exchanged water were added, the water was well dispersed, and the mixture was left at 80°C for one day. do. The number average molecular weight of this polymer was measured by GPC and was found to be 3.8×10 ⁴ . From this, it is recognized that it is a comb-shaped polymer represented by the following formula.

This comb-shaped polymer has strong adhesion to glass surfaces.

Example 3 8 g of MMA, 2 g of octafluoropentyl methacrylate, 0.01 g of 3-mercaptopropylmethyldimethoxysilane, 2 g of toluene and
0.01 g of AIBN is polymerized at 60°C for 8 hours to obtain a condensable macromonomer for the copolymer resin. Then n-
When 0.05 g of butyltin oxide was blended and this was applied onto a glass surface and left for 7 days, the resulting comb-shaped polymer had excellent water repellency and oil repellency.

Claims (1)

[Claims] 1 formula, [In the formula, R ⁵ is hydrogen or a methyl group, and X ¹
is an alkyloxycarbonyl group, a substituted alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, or a phenyl group] and consists of 10,000 to 10,000 repeating units of at least one type _of [In the formula, R ¹ and R ² are the same or different alkyl groups each having 1 to 4 carbon atoms, and R ³ is -
OR ¹ , -OR ² or an alkyl group having 1 to 4 carbon atoms,
and R ⁴ is an alkylene group having 1 to 4 carbon atoms]
An alkoxysilyl group-containing condensable macromonomer having a dialkoxysilyl group and H at the other end. 2 formulas, [In the formula, R ¹ and R ² are the same or different alkyl groups each having 1 to 4 carbon atoms, and R ³ is -
OR ¹ , -OR ² or an alkyl group having 1 to 4 carbon atoms,
and R ⁴ is an alkylene group having 1 to 4 carbon atoms]
At least one mercaptosilane compound represented by the formula, [In the formula, R ⁵ hydrogen or a methyl group, and X ¹ are an alkyloxycarbonyl group, a substituted alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, or a phenyl group] Then, by polymerization in the presence of a radical initiator, the formula: [In the formula, R ⁵ and X ¹ have the same meanings as above] Consisting of 10,000 to 10,000 repeating units of at least one of the following, and CH ₂ at one end has the formula, To obtain an alkoxysilyl group-containing condensable macromonomer having a dialkoxysilyl group [wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as above] and having H at the other end. A method for producing an alkoxysilyl group-containing condensable macromonomer, characterized by: