JPS624706A - Alkoxysilyl group-containing condensible macromonomer - Google Patents

Abstract

PURPOSE:To obtain the titled macromonomer useful as an intermediate for a comb-like polymer excellent in surface migration, water repellency and adhesion, by polymerizing a specified mercaptosilane compound with a vinyl monomer. CONSTITUTION:The titled macromonomer of formula III (wherein n is 1-10,000) is obtained by polymerizing, by application of heat or light, 0.01-5pts.wt. mercaptosilane compound (A) of formula I (wherein R<1-2> are each a 1-4C alkyl, R<3> is any one of R<1-2>, -OR<1-2>, a 1-4C alkyl and R<4> is a 1-4C alkylene), e.g., 3-mercaptopropylmethyldimethoxysilane, with a vinyl monomer (B) of formula II [wherein R<5> is H or CH3, X<1> is (substituted) alkyloxycarbonyl, cycloalkyloxycarbonyl or phenyl], e.g., methyl methacrylate, in the presence of, optionally, a radical initiator.

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 provides 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 them, certain block polymers, graft polymers, and comb-shaped polymers are already known as those having surface migration properties. However, the synthesis of these polymers may result in poor yields of the desired product, complex reactions involving multiple steps, or
Furthermore, there were drawbacks such as high cost.

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 properties:
0R2 or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkylene group having 1 to 4 carbon atoms.] A mercaptosilane compound represented by the formula, [in the formula, R
5 is hydrogen or a methyl group, and Xl is an alkyloxycarbonyl group, a substituted alkyloxycarbonyl group, or a cycloalkyloxycarbo vinyl monomer is polymerized in the presence of a radical initiator if necessary to form the formula, [ wherein R1, R2, R3, R4, R5 and Xl have the same meanings as above, and n is an integer from 10,000 to 10,000. The present invention provides a method for producing an alkoxysilyl group-containing condensable macromonomer, and (2) a condensable macromonomer of the formula CI+ obtained by the production method.

A specific example of the mercaptosilane compound of the above formula [■] used in the present invention is mercaptomethylmethyl dime)
Toxysilane (referring to dimethoxysilane and di△ethoxysilane, hereinafter the same) Toxysilane, 2-mercaptoethylmethyl (dimer) Toxysilane, 2-mercaptoethyl ethyl (dimer) Toxysilane, 3-mercaptoprobil Examples include methyldimethoxysilane, 3-mercaptoprobyl ethyldimethoxysilane, 4-mercaptobutylmethyldimethyldimethoxysilane, 4-mercaptobutylethyldimethyldimethoxysilane, etc., and one or more of these can be used. put it into use. The amount used is usually 0 parts per 100 parts (parts by weight, hereinafter the same) of the vinyl monomer.
．． It may be selected within the range of 01 to 5 parts.

The vinyl monomer CIII used in the present invention refers to a monomer containing a vinyl group, a vinylene group, or a vinylidene group, and specifically, for example, ethyl acrylate,
Propyl acrylate, n-butyl acrylate, imbutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, methyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy Propyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate , 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-methocinoethyl methacrylate, 2-ethoxyethyl methacrylate, 2,2,3.3-tetrafluoropropyl acrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, styrene, etc. is,
In addition to this, it can be used in place of or in combination with, for example, maleic anhydride, tetravinyl acetate, 4-META (4-methacryloxyethyl trimellitic anhydride), HEMAP (acid phosphooxyethyl methacrylate), methacrylic acid, acrylic acid. , vinyl propionate, vinyl persate (trade name Beoba, manufactured by Shell Chemical), vinyl chloride, acrylonitrile, acrylamide, N-methylolacrylamide, vinylpyridine, vinylpyrrolidone, butadiene, etc. species or two
Use seeds or more.

The alkoxysilyl group-containing condensable macromonomer of the above formula [I] according to the present invention can be produced according to the following procedure.

A predetermined proportion of the mercaptone compound [■] is blended with the above-mentioned vinyl monomer [■], and these are polymerized by heat or light according to usual conditions, if necessary in the presence of a radical initiator. 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 so preferred because the alkoxysilyl group of the mercaptosilane compound [■] may be hydrolyzed. The above radical initiator is usually o,
It may be used in the range of o s to 0.1 part, and specific examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobisisovaleronitrile, 2 , 2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), C-butyroperoxide, methyl ethyl ketone peroxide, etc., and redox catalysts used in redox polymerization (transition metal salts, amines, etc.). A combination of peroxide-based radical initiators may be employed.

In addition, in the case of photopolymerization, the radical initiator may or may not be used.

By polymerizing the vinyl monomer CIII] and the mercaptosilane compound [11], the condensable macromonomer [I] of the present invention having an alkoxysilyl group at the terminal can be obtained. In addition, when B or PO is used as a radical initiator, the benzoic acid decomposed and produced along with radical polymerization becomes a catalyst, and if water is present in the system, the condensation polymerization described below occurs simultaneously, resulting in comb formation in one step. type polymer can be obtained.

The condensable macromonomer CII of the present invention is useful as an intermediate for a comb-shaped polymer, which is the final objective.

That is, the condensable macro-7mer [I] can be used alone or with the formula [
In the formula, k6 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R7 and R8 are the same or different and each is an alkyl group having 1 to 4 carbon atoms, and x2 is hydrogen, an alkyl group, a phenyl group, chlorine, or an alkoxysilyl group. group or -N
is an alkyl group having a H2, -NH-, -H5 or -CN group], and if necessary, carry out condensation polymerization in the presence of a polycondensation catalyst,
Formula, + [wherein R1, 2. R3, R4, R5, R6, Xl,
x2 and n are as defined above, 1 is an integer of 1 to 2o, and m is 0 or an integer of 1 to 1o.] A silicon-containing comb-shaped polymer is produced.

The above-mentioned dialkoxysilane compound [Machi] can introduce its functional group into the main chain of the desired comb-shaped polymer to further improve various physical properties such as adhesion.
2-Amine Ethynoly 3-aminoprobylmethyldimethoxysilane, 3-aminoprobylmethyljethoxysilane, chloromethylmethyljethoxysilane Robylmethyldimethoxysilane, 2-cyanoethylmethyljethoxysilane, diethyljethoxysilane, dimethyl Jetoxysilane, diphenyljethoxysilane, diphenyldimethoxysilane, 3-mercaptoprobylmethyldimethoxysilane, methyljethoxysilane, methyldimethoxychlorosilane, methyldimethoxysilane, methyldodecyljethoxysilane, methyloctadecyljethoxysilane, methylphenyldimethoxysilane Ethoxysilane, methylphenyldimethoxysilane 3,3.3-t! J Fluoroprobil) dialkoxysilane compounds such as methyljethoxysilane, vinylmethyldiacetoxysilane, vinylmethyljethoxysilane, and 1,1,
4.4-tetramethyl-1.

Examples include 4-jethoxysilylethylene, 1,1,3.3-tetramethyl-1,3-jethoxydisiloxane, and one or more of these may be used.

The amount to be used is usually 100 parts or less, preferably 5 parts or less, based on 1100 parts of condensable macro-hetamine [I]. By using this dialkoxysilane compound,
For example, a dialkyldialkoxysilane is selected to improve water repellency, and a dialkoxysilane having an adhesive group (NH2, -SH group, etc.) is selected to improve adhesion.

The above condensation polymerization may be carried out normally at room temperature to 80°C for 48 to 5 hours, and examples of catalysts used include titanate esters such as tetrabutyl titanate and tetrapropyl titanate, dibutyltin dilaurate, and dibutyltin dilaurate. Tin maleate, dibutyltin diacetate, tin octylate, tin naphthenate. Organotin compounds such as n-butyltin oxide; lead octylate, nibbutylamine, octylamine, dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine , diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2.

4,6-tris(dimethylaminomethylraphenol,
Examples include amine compounds such as morpholine, N-methylmorpholine, and 1,3-diazabicyclo(5.4.6) undecene-7 (DBU), or salts of these carboxylic acids, and one or two of these. The above shall be made available for use. The amount used is usually condensable macroseptumer [:I]
The amount may be selected within the range of 0.01 to 1 part per 100 parts.

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

The comb-shaped polymer obtained as described above is a relatively simple 2
It can be efficiently produced by a step reaction (in some cases, a one-step reaction), and because of its surface migration property, it can exhibit a surface or interface modification effect (for example, anti-fouling effect) even when added in a small amount. Furthermore, those in which a dialkoxysilane compound (Oka functional group) is 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, as well as uses due to its surface active action.

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

Example 1 Methyl methacrylate (MMA, 15(1,3-mercaptoprobyl methyldimethoxysila 4.9y, AIB
No. 08y and 25p of toluene are placed in a glass polymerization tube, cooled and desilvered, and then melt-sealed. This is polymerized while being shaken in a 60° C. bath, and after about 8 hours, a highly viscous toluene solution of the condensable macromonomer is obtained. Weight change method (10
The yield determined at 5° C. for 4 hours was 96%. This macromonomer was confirmed to be Nyolipo IJMMA by IR spectroscopy (manufactured by JASCO Corporation). Furthermore, gel permeation chromatography (GPC) revealed that the number average molecular weight was 9.8×10 3 .

Reference Example 1 Add 0.5 parts of dibutyltin dilaurate to 100 parts of the polyMMA toluene solution of Example 1, spread it as thinly as possible in a Petri dish, and leave it at room temperature for 7 days. The toluene solvent evaporates and a solid polymer film is obtained. It will be done. A part of this was dissolved in tetrahydrofuran, and G
When PC was measured, the number average molecular weight was 4.5X10
Met.

From this, it is recognized that it is a comb-shaped polymer represented by the following formula.

Furthermore, when 2 parts of dimethyljethoxysilane, 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 stirred at 1,60'C for 8 hours, the viscosity became higher. . When this was measured by GPC, it was found that it was a polymer with a molecular weight of 7.8 x 10'. From this, it is found that the main chain is organopolysiloxane, and the average molecular length is 9.8 x 10. JMM
It is recognized that A is a comb-shaped polymer having about 8 side chains.

Example 2 10 g of butyl acrylate and 0.59 g of 3-mercaptoprobylmethyldimethoxysilane are placed in a glass polymerization tube, cooled and desilvered, and then sealed. This was placed in a water tank at 15° C., and photopolymerization was performed while irradiating it with UV (Toshiba 5HL-100) from a distance of 10 CIR. The contents were taken out at 10 o'clock, and the yield was determined by the weight change method, and was found to be 95%. Furthermore, the number average molecular weight is 4.5X10 as determined by GPC measurement.
It was 3.

Reference Example 2 To 100 parts of the product of Example 2, 5 parts of methyldimethoxysilane, 0.5 parts of n-butyl silver oxide, and a small amount of ion-exchanged water were added, and after thoroughly dispersing the water, 1
Leave it for a day. The number average molecular weight of this polymer was measured by GPC and was found to be 3.8 x 104. From this, it can be recognized that it is a comb-shaped polymer represented by the following formula H. This comb-shaped polymer has strong adhesion to the aromatic surface.

Example 3 MMA 8g, octafluoropentyl methacrylate 2
g, 3-mercaptoprobylmethyldimethoxysilane 0.01f, I-toluene 2g and AxBNo, 01g
was polymerized at 60°C for 8 hours to obtain a condensable macro-septumer of copolymer resin. Then n-butyltin oxide 0.
When the comb-shaped polymer obtained had excellent water repellency and oil repellency, it was found that the resulting comb-shaped polymer had excellent water repellency and oil repellency.

Claims (1)

[Claims] 1. Formulas, ▲ Numerical formulas, chemical formulas, tables, etc. -OR^1
, -OR^2 or an alkyl group having 1 to 4 carbon atoms, R^4
is an alkylene group having 1 to 4 carbon atoms, R^5 is hydrogen or a methyl group, X^1 is an alkyloxycarbonyl group, substituted alkyloxycarbonyl group, cycloalkyloxycarbonyl group, or phenyl group, and n is 10,000 to 10,000 An alkoxysilyl group-containing condensable macromonomer, which is an integer of . 2. Formulas, ▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 are the same or different and each is an alkyl group 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] There are mercaptosilane compounds represented by formulas, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [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.] Then, it is polymerized in the presence of a radical initiator to form a formula, ▲mathematical formula, chemical formula, table, etc.▼ [In the formula, R^1, R^2, R^3, R^4, R^5 and X ^1 has the same meaning as above, and n is an integer from 10,000 to 10,000.] A method for producing an alkoxysilyl group-containing condensable macromonomer, which is characterized by obtaining an alkoxysilyl group-containing condensable macromonomer.