JPS6259604A - Production of methacrylate polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer of a narrow MW distribution in good efficiency, by polymerizing a silyl group-containing methacrylate by using ketene silyl acetal as a polymerization initiator and using a source of (bi)fluoride ions as a cocatalyst. CONSTITUTION:A methacrylate monomer of formula I (wherein R<1> is 1-20 C monovalent hydrocarbon group having at least on silyl group in the carbon chain), e.g., formula II or III, is polymerized in the presence of a ketene silyl acetal of formula IV (wherein R<2>, R<3>, R<4> and R<5> are each H or a 1-10 C monovalent hydrocarbon group), e.g., formula V or VI, as a polymerization initiator and a source of fluoride bifluoride ions (e.g., tetrabutylammonium fluoride or potassium fluoride acidified with hydrofluoric acid) as a cocatalyst to obtain the purpose methacrylate polymer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a methacrylic ester polymer, in particular, a method for producing a methacrylic ester polymer, in particular a method for producing a methacrylic ester polymer having various functional groups in its ester moiety using ketene silyl acetal as a polymerization initiator. The present invention relates to a method for producing a methacrylic acid ester polymer by polymerization.

(Prior art) Various vinyl monomers containing methacrylic acid esters were mixed with trimethylsilylnitrile, [(1-methoxy-2-
It was known prior to this application that living polymers can be produced by polymerizing using methyl-1-propenyl)oxy]trimethylsilane as a polymerization initiator and a fluoride ion source or heavy fluoride ion source as a cocatalyst. However, this method has disadvantages in that the reaction is slow at low temperatures and it is difficult to obtain a polymer with a small molecular weight distribution.

(Structure of the Invention) The present invention relates to a method for producing a methacrylic acid ester polymer that solves these disadvantages.

This is expressed by the general formula % formula % (1) (where R1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group containing at least one silyl group in its carbon chain).
A methacrylic acid ester monomer represented by the general formula (where R1 is the same as above, R2, R3, R4, and R'' are each a hydrogen atom or a monovalent group having 1 to 10 carbon atoms) It is characterized by using a ketene silyl acetal represented by a hydrocarbon group as a polymerization initiator, and polymerizing in the presence of a fluoride ion source or heavy fluoride ion source as a cocatalyst.

That is, the present inventors used methacrylic acid ester.

In particular, as a result of various studies on effective polymerization methods for methacrylic acid esters containing various functional groups such as silyl groups in the ester moiety, we found that ketene silyl acetal represented by the above general formula (2) was used as the polymerization initiator. When used, various functional groups are added to the ester moiety, especially groups that are unstable to radical polymerization and are conventionally thought to be impossible to polymerize.
For example: It is possible to easily polymerize methacrylic monomers having SiH groups, etc., and thus copolymers of methacrylic acid esters having various functional groups can also be easily obtained at a set molecular weight; In addition, we discovered that this method yields a methacrylic acid ester polymer as a new crosslinking agent having, for example, Mi5i-H groups, and we also used known fluoride ion sources and heavy fluoride ion sources for this polymerization. It is useful as a catalyst, and furthermore, since the ketene silyl acetal represented by the formula (2) described above can be easily synthesized, this polymerization method can be carried out at low cost. After confirming this, the present invention was completed.

The methacrylic acid monomer used as an initiator in the method of the present invention is represented by the general formula %, where R is an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, a vinyl group, an allyl group, etc. Aryl groups such as alkenyl groups, phenyl groups, tolyl groups, 2
- Aralkyl groups such as phenylethyl, cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, or some or all of the hydrogen atoms bonded to carbon atoms of these groups can be replaced with halogen atoms, tertiary amino groups, acetoxy groups, epoxy groups, etc. 1 to 20 carbon atoms selected from groups substituted with
selected from monovalent carbon groups such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, turvyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-acetoxyethyl methacrylate, p-tolyl methacrylate, 2,2,
3,3,4゜4.4-Heptafluorobutyl methacrylate, glycidyl methacrylate, 2-methoxypropyl methacrylate, allyl methacrylate, etc., in which R contains at least one silyl group in its carbon chain. The above-mentioned monovalent hydrocarbon groups may be used, and examples thereof include the following.

CI(.

CH,=C-C-0(CH,), -3i-(CH=CH
,)3CH.

CH-=C-G O(CH-)3 Si(OCR
-)-CH,CH35i CH,CM.

i CHa CH=CHz CH, CH.

CH, CH□ Next, the ketene silyl acetal as a polymerization initiator used in the method of the present invention is represented by the general formula %, where R1 is the same as above. R2, R3, R4, Rs
has 1 to 1 carbon atoms selected from the same group as R1.
0 homologous or different unsubstituted or substituted monovalent hydrocarbons, including [(1-medoxy-2-methyl-1-propenyl)oxyfudimethylhydrosilane, [(2-ethyl-1- Examples include propoxy-1-butenyl)oxyfudimethylhydrosilane and those represented by the linear formula, but are not limited thereto.

C=C (CH3)z C=C CH.

C=C CH, CH.

Note that if the amount of the polymerization initiator used is less than 1 mole of O, OS per 100 moles of the methacrylic acid ester monomer mentioned above, the polymerization will not proceed quickly, and if the amount is more than 100 moles, the initiator and methacrylic acid ester monomer will be mixed. Since polymerization will not occur if only a 1:1 adduct of 0.05 to 100
The preferred range is 0.05 to 1 mole per 100 moles of methacrylic acid ester monomer.
It is considered a mole.

Furthermore, in the method of the present invention, a substance serving as a fluoride ion source or a heavy fluoride ion source is added as a cocatalyst in order to promote polymerization by the above-mentioned polymerization initiator. Examples of the ion source include tetrabutylammonium fluoride, tetramethylammonium fluoride, tris(dimethylamino)sulfonium difluorotrimethylsilicate, tris(diethylamino)sulfonium difluorotrimethylsilicate, hydrofluoric acid, acidic potassium fluoride, and the like. The amount of this added is such that the molar ratio of catalyst/polymerization initiator is 0.0 with respect to the above amount of polymerization initiator.
It may be in the range of 0.01 to 1, preferably in the range of 0.01 to 0.1.

The polymerization of the methacrylic acid ester monomer represented by the above general formula (1) by the method of the present invention can be carried out by the above general formula (
The polymerization is carried out using the ketene silyl acetal shown in 2) as a polymerization initiator in the presence of the above-mentioned fluorion source and heavy fluoride ion source.

This reaction may be carried out at a temperature range of -80°C to 70°C, preferably -40°C to 50°C.

This may be carried out in the presence of a solvent such as tetrahydrofuran, diethyl ether, acetonitrile, dimethoxyethane, jetoxyethane, toluene,
xylene, methylene chloride.

Examples include 1,2-dichloroethane, N,N-dimethylformamide, etc., but it is better to dry them before use.Also, the methacrylic acid ester monomer added to this reaction system may also be used, such as potassium hydride. It is preferable to use the product after drying it using a nitrogen gas, and it is further preferable to carry out this reaction in an inert gas atmosphere such as nitrogen or argon.

Next, examples of the present invention will be given. The methacrylic acid ester monomers used in the examples were dehydrated with potassium hydride and purified by distillation, and tetrahydrofuran (TH
F) was dried with sodium under an argon gas atmosphere, and the molecular weight of the (co)polymer obtained in this example was measured by gel permeation chromatography (GPC). When a substance is polydisperse, polydispersity (D) is defined by D=polymerization average molecular weight (My)/number average molecular weight (vLn).

Example 1 THFl 00+m in the reactor under argon gas atmosphere
Q1 [(1-methoxy-2-methyl-1-propenyl)oxy]dimethylhydrosilane, 1.8 g (1
1,3 mmol) and formula % formula % lotrimethylsilicate in 0.01 M THF solution 2 m
12 was charged, 48.2 g (482 mmol) of methyl methacrylate was added dropwise to the mixture at O''C while stirring, and 8
After stirring for an additional hour at room temperature, the poly(methyl methacrylate) was diluted with methanol.
g is obtained, and the polydispersity of this is Mw=5,890,
M n =4,940, D = 1.19.

Example 2 00ml of THFl in the reactor under argon gas atmosphere
0.8 g (3.0 mmol) of dimethylhydrosilane ((1-(3-dimethylvinylsilylpropoxy)-2-methyl-1-propenyl)oxy) and tris(diethylamino)sulfonium difluorotrimethyl A 0.OIM THF solution of silicate was charged with 2 Ω, and while stirring, 17.2 g (172 mmol) of methyl methacrylate was added dropwise at -12°C. After adding one drop, the mixture was further stirred at room temperature for 1 hour, and then diluted with methanol. As a result, poly(
17.4 g of methyl methacrylate) were obtained, the polydispersity of which was Mw = 8,700, M n = 7,860,
D=1.11 (theoretical molecular weight=6,020).

Example 3 In a reactor under an argon gas atmosphere, THF 100■a,
2.6 g (9.1 mmol) of ((1-(3-dimethylvinylsilylpropoxy)-2-methyl-1-propenyl)oxy]dimethylhydrosilane used in Example 2
and 0.0% of tris(diethylamino)sulfonium difluorotrimethylsilicate. OIM THF solution 21
1Q was charged, and 25.2 g (221 mmol) of ethyl methacrylate was added dropwise at -15°C while stirring in a rower.
After the completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, and then diluted with methanol. 27.2 g of poly(methyl methacrylate) having a vinylsilyl group at the end of one molecular chain was obtained, and the polydispersity of this was 3. ,570, M n =
3.360, D=1.06 (theoretical molecular weight=3,020)
Met.

Example 4 THFloomQ in a reactor under an argon gas atmosphere,
2.8 g (9,8 mmol) of [(1-(3-dimethylviny)Lt silylpropoxy)-2-methyl-1-propenyl)oxy]dimethylhydrosilane and 0.0 g of tris(diethylamino)sulfonium difluorotrimethylsilicate. Add 22.7 g (160 mmol) of n-butyl methacrylate dropwise to the OIM THFHF solution at -15°C while stirring and stir for another hour at room temperature, then dilute with methanol. As a result, 24.9 g of poly(n-butyl methacrylate) having a vinylsilyl group at one end of the molecular chain was obtained, and the polydispersity of this was Mw = 2,940, Mn
=2,730. D=1.08 (theoretical molecular weight=2,60
0).

Example 5 THFloomA,
((1-(3-dimethylvinylsilylpropoxy)-2
-methyl-1-propenyl)oxy]dimethylhydrosilane, 2.9 g (10,1 mmol) and 0.0 g of tris(diethylamino)sulfonium difluorotrimethylsilicate. Charge 2 mQ of OIMTHF solution and mix with formula CH at -20°C while stirring twice.

When 21.6 g (171 mmol) of allyl methacrylate represented by I was added dropwise and stirred for another hour at room temperature after the dropwise addition was completed, dilution with methanol revealed that poly(methacrylic acid) having a vinylsilyl group at the end of a molecular chain was obtained. allyl)
23.7 g were obtained, the polydispersity of which was Mw = 3
,660. Mn=3,200. D==1,14 (theoretical molecular weight=2,420).

Example 6 THF100+mR in the reactor under argon gas atmosphere
, [(1-(3-dimethylvinylsilylpropoxy)-
3 g (10.5 mmol) of 2-methyl-1-propenyl)oxy]dimethylhydrosilane and 0.0 g of tris(diethylamino)sulfonium difluorotrimethylsilicate. 10.0 g of methyl methacrylate at -15°C with stirring in 2N containing 20.0 g of OIM THFHF solution.
(10 mmol) was added dropwise, and after stirring for 30 minutes at -15°C after the dropwise addition, 10 mg of THF solution was taken out from one reactor and diluted with methanol, resulting in 1.0 g of poly(methyl methacrylate). obtained, the polydispersity of which is M w = 1,950. M n =
1,710°D=1.14 (theoretical molecular weight=1,240)
Met.

Next, 20.1 g (140 mmol) of n-butyl methacrylate was added to the THF solution remaining in one reactor at -15°C.
was added dropwise, and after the addition was completed, the mixture was further stirred at room temperature for 1 hour, and then diluted with methanol.

A block copolymer of methyl methacrylate and n-butyl methacrylate was obtained, and its polydispersity was M w
=4,180. M n =3,730, D=1.1
1 (theoretical molecular weight = 3,340).

Example 7 THFlooma in a reactor under argon gas atmosphere,
((1-(3-dimethylvinylsilylpropoxy)-2
-Methyl-1-propenyl)oxy]dimethylhydrosilane (2.6 g (9 mol) of 9,4S) and 0.0 IMTHF solution of tris(diethylamino)sulfonium difluorotrimethylsilicate were charged and heated to -15°C while stirring twice. Methyl methacrylate 11.1g
(111 mmol) was purified, and even after the dropwise addition was completed, the temperature remained at -15℃.
After stirring for 30 minutes, 10 mg of THF was removed from the reactor.
The solution was taken out and diluted with methanol.

1.1 g of poly(methyl methacrylate) was obtained, the polydispersity of which was M w = 2,390, M n = 2,
130, D=1.12 (theoretical molecular weight=1,470).

Next, 8.3 g (39 mmol) of the formula luprovir was added dropwise to the THF solution remaining in the reactor at -15°C, and after the completion of the dropwise addition, the mixture was stirred for an additional hour at room temperature and then diluted with methanol. Methyl and methacrylic acid 3-
A block copolymer with dimethylvinylsilylprobyl was obtained, which had a polydispersity of M w =3,910.
M n =3,450, D=1.13 (theoretical molecular weight =
2,440).

Example 8 THFloomff in the reactor under argon gas atmosphere
, 2.9 g (10,1 mmol) of dimethylhydrosilane ((1-(3-divinylmethylsilylpropoxy)-2-methyl-1-propenyl)oxy) and 0 of tris(diethylamino)sulfonium difluorotrimethylsilicate of the formula .OIM
2 ITHF solutions 2 solutions - 22.3 g of methyl methacrylate at 12°C (2 2
3 mmol) was added dropwise, and after the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour, and then diluted with methanol. As a result, 24.5 g of poly(methyl methacrylate) having a divinylsilyl group at the end of the molecular chain was obtained. The polydispersity of something is M
w=4,000. M n =3,660, D=1.
09 (theoretical molecular weight=2,530).

Example 9 THFl 00ra in the reactor under argon gas atmosphere
Q, 2.9 g (5.6 mmol) of ketene syriacetal having a trivinylcyclotetrasiloxy group of the formula % and 0.9 g (5.6 mmol) of tris(diethylamino)sulfonium difluorotrimethylsilicate. A 2mM OIM THF solution was charged, and 21.6 g (216 mmol) of methyl methacrylate was added dropwise at -15°C while stirring. After the dropwise addition, the mixture was further stirred at room temperature for 1 hour, and then diluted with methanol. Poly(methyl methacrylate) having a trivinylcyclotetrasiloxy group at one end of the molecular chain 22.
6 g is obtained, the polydispersity of which is Mw = 5,210
, M n =4,790, D=1.09 (theoretical molecular weight =
4,380).

Example 10 THFloomQ in a reactor under argon gas atmosphere,
4.8 g (9.2 mmol) of ketene syriacetal with trivinylcyclotetrasiloxy group used in Example 9 and 0.0 g of tris(diethylamino)sulfonium difluorotrimethylsilicate. OIM THFHF
10.5 g (105 mmol) of methyl methacrylate was added dropwise to the solution at -14°C while stirring, and after the dropwise addition was finished stirring at -15°C for 30 minutes, 10 mQ was added from the reactor. When a THF solution of was taken out and diluted with methanol, poly (methyl methacrylate) 1.1 having a trivinylcyclotetrasiloxy group at the end of the molecular chain was obtained.
g is obtained, and the polydispersity of this is M w ” 2,2
20. M n = 1,950 and D = 1.14 (theoretical molecular weight = i, 5so).

Next, add CH to the THF solution remaining in this reactor.

CH:l CH.

10.6 g (23.9 mmol) of methyl methacrylate having a trivinylcyclotetrasiloxy group represented by was added dropwise at -15'C, and after the completion of the addition, an additional 1 g (23.9 mmol) of methyl methacrylate was added at room temperature.
After stirring for an hour and diluting with methanol, 22.6 g of a copolymer of methyl methacrylate and methacrylic ester having trivinylcyclotetrasiloxy groups was obtained, and the polydispersity of this was Mw = 3, 370. ,
Mn = 3,100, D = 1.09 (theoretical molecular weight =
2°920).

Example 11 THF100Q,
2.8 g (17.8 mmol) of [(1-methoxy-2-methyl-1-propenyl)oxy]dimethylhydrosilane and tris(diethylamino)sulfonium difluorotrimethylsilica.

- Prepare O, OIM THF solution 2IIQ of
10.0 g (1
00 mmol) and 17.1 g (65.8 mmol) of a methacrylic acid ester having a hydrosilyl group represented by the formula were simultaneously added dropwise. After the addition, the mixture was stirred at room temperature for 1 hour and diluted with methanol. 2.120 in external absorption spectrum
27.0 g of a copolymer of methyl methacrylate with absorption derived from 5i-H of am-' and methacrylic ester having a hydroxyloxy group was obtained.

The polydispersity of this product is M W :2,610, M n
= 2.280, and D = 1.10 (theoretical molecular weight = 1,6
80).

Note that methyl methacrylate and methacrylic ester having a hydrosilyl group could not be detected in this reaction solution even by gas chromatography, and it was confirmed that these were completely copolymerized.

Example 12 00ml of THFl in the reactor under argon gas atmosphere
2, C (1-methoxy-2-methy#-1-propenyl)
1.0 g (6.3 mmol) of oxy]dimethylhydrosilane and 0.0 g (6.3 mmol) of tris(diethylamino)sulfonium difluorotrimethylsilicate. OIM THFH
Add 2 ml of F solution and add 5 ml of methyl methacrylate at 5°C.
．． 6 g (56 mmol) and 4.4 g (13.8 mmol) of a methacrylic acid ester having two hydrosilyl groups in one molecule with the formula %.
and were added dropwise at the same time with stirring, and after the completion of the two drops, the mixture was stirred at room temperature for 1 hour, and then diluted with methanol. -SL-
Copolymer of methyl methacrylate with absorption derived from H and methacrylic ester with two hydrosilyl groups 9
．． 6 g is obtained, the polydispersity of which is Mw = 3,00
0, Mn=2,720 and D=1.10 (theoretical molecular weight=1
, 770).

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (Here, R^1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms or at least one silyl group in its carbon chain. A methacrylic acid ester monomer represented by a monovalent hydrocarbon group containing R^4
, R^5 each has a hydrogen atom or a carbon number of 1 to 1
A methacrylic acid ester polymer characterized in that it is polymerized using a ketene silyl acetal represented by (0 monovalent hydrocarbon group) as a polymerization initiator and in the presence of a fluoride ion source or heavy fluoride ion source as a cocatalyst. manufacturing method. 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 is the same as above) R^1 of the methacrylic acid ester polymer is the formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, X, Y, and Z are each a hydrogen atom or 1 carbon number
~4 alkyl group, vinyl group, phenyl group, -CH_2
CH_2CF_3, -CH_2CH_2C_4F_9,
-OSiX'Y'Z'(X'Y'Z' each is a hydrogen atom or a group selected from an alkyl group having 1 to 4 carbon atoms, a vinyl group, and a phenyl group), -OX'(X' is the same as above)
The method for producing a methacrylic acid ester polymer according to claim 1, wherein m is selected from 0 to 5, and n is 0 to 5.