JPH0618808B2 - Manufacturing method of vinyl polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a vinyl polymer, and more particularly to a method for producing a vinyl polymer using a novel initiator.

2. Description of the Related Art Conventionally, various initiators have been used for the polymerization of vinyl monomers. Particularly in the case of anionic polymerization, an alkali metal such as lithium, potassium or sodium as an initiator,
Alkyl alkali metals, Grignard reagents, alkali metal alcoholates and the like are generally used.

Problems to be Solved by the Present Invention However, the above-mentioned initiators have very high activity, but have the following problems.

First, since it has strong nucleophilicity and strong basicity with respect to vinyl-based monomers, unnecessary side reactions that are not desirable in the polymerization of a monomer having a polar group, such as monomer Decomposition, termination of polymer chain growth due to recombination of monomer decomposition products, and gelation due to grafting of polymer chains are likely to occur, and therefore these initiators are applied to polymerization of monomers having polar groups. However, obtaining a polymer having a high molecular weight and imparting a living property to the polymer chain have been greatly limited.

Secondly, it is generally chemically unstable, is not easy to store and handle, is easily deactivated by a very small amount of water, and has a risk of ignition or explosion due to contact with air.

Thirdly, in severe reaction conditions for polymerization, for example, in anionic polymerization using an alkali metal as a catalyst, the initiator generally reacts with a polar solvent as a polymerization medium and is easily deactivated at a high temperature. In order to obtain the polymer (1), it is often necessary to cool to tens of degrees below zero.

In order to solve the problems of these conventional initiators for anionic polymerization, the development of a novel initiator that is chemically stable, has low basicity, and has selective nucleophilicity has been required. .

On the other hand, in recent years, the silylation reaction of an electrophilic organic compound utilizing the high affinity of a fluoride ion for a silicon atom is an excellent method for generating a nucleophilic species having low basicity and high selectivity. Has been reported.

In order to overcome the drawbacks of conventional initiators in anionic polymerization of vinyl-based monomers, the present inventors have diligently studied a novel polymerization initiator based on the reaction derived from the affinity between a silicon atom and a fluoride ion. As a result, the silyl anion-like species generated by the reaction between the polysilane compound and the fluoride ion is an excellent initiator that gives a polymer having a high molecular weight and living property to the monomer having a polar group. Found.

Based on this finding, we have completed a method for producing a vinyl polymer that solves the problems of conventional initiators.

That is, an object of the present invention is to provide a method for producing a vinyl-based polymer, which is capable of obtaining a vinyl-based polymer having a high molecular weight living property under mild conditions by using a compound that is chemically extremely stable at room temperature and atmospheric pressure. To do.

Means for Solving the Problems That is, the present invention provides a vinyl-based monomer with (A) general formula (I) [In the formula, R can be selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 10 carbon atoms, and may be the same or different, and n is 0 to 4
A compound represented by the general formula (II) [Wherein, R is the same as in the general formula (I), and may be the same or different, and m is an integer of 4 to 6], and at least one selected from the group consisting of An initiator, and (B) an onium compound serving as a source of fluorine ions,
Provided is a method for producing a vinyl polymer, which comprises contacting with at least one cocatalyst selected from the group of alkali metal fluorides and alkali metal bifluorides.

The alkyl group having 1 to 8 carbon atoms used in the definitions of the general formulas (I) and (II) includes linear, branched, and cyclic alkyl groups such as methyl group and ethyl group. Group, n-propyl group, iso-propyl group,
n-butyl group, sec-butyl group, tert-butyl group, amyl group, n-pentyl group, n-hexyl group, n-
Examples thereof include an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a benzyl group. Among these, a methyl group, an ethyl group, and the like which are not sterically bulky can be preferably mentioned. .

Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a naphthyl group, a xylyl group, a mesityl group, and preferably a phenyl group.

Specific examples of the compound represented by formula (I), which is the component (A) used in the present invention, include 1,2-dimethyldisilane, 1,2-diethyldisilane, and 1,2-bis (n-). Propyl) disilane 1,2-bis (iso-propyl) disilane, 1,2-bis (n-butyl) disilane, 1,2-bis (sec-butyl) disilane, 1,2-bis (tert-butyl) disilane 1,2-diamyldisilane, 1,2-bis (n-hexyl) disilane, 1,2-bis (n-octyl) disilane, 1,2-bis (cyclopropyl) disilane, 1,2-bis (cyclobutyl) Disilane, 1,2-bis (cyclopentyl) disilane, 1,2-bis (dichlorohexyl) disilane, 1,2-dibenzyldisilane, 1,1,2,2-tetramethyldisilane, 1,1,2,2-tetraethyldisilane, 1,1,2,2-tetrakis (n-propyl) disilane, 1,1,2,2-tetrakis (iso-propyl) disilane, 1,1,2,2 -Tetrakis (n-butyl) disilane, 1,1,2,2-Tetrakis (sec-butyl) disilane, 1,1,2,2-Tetrakis (n-hexyl) disilane, 1,1,2,2-Tetrakis (N-octyl) disilane, 1,1,2,2-tetrakis (cyclopropyl) disilane, 1,1,2,2-tetrakis (cyclobutyl) disilane, 1,1,2,2-tetrabenzyldisilane, 1, 2-diphenyldisilane, 1,2-ditolyldisilane, 1,2-dinaphthyldisilane, 1,2-dixylyldisilane, 1,2-dimentyldisilane, 1,1,2,2-ther Traphenyldisilane, 1,1,2,2-tetratolyldisilane, 1,1,2,2-tetraxyldisilane, hexamethyldisilane, hexaethyldisilane, hexakis (n-propyl) disilane, hexakis (iso-propyl) ) Disilane, hexakis (n-butyl) disilane, hexakis (sec-butyl) disilane, hexakis (n-hexyl) disilane, hexakis (n-octyl) disilane, hexakis (dichloropropyl) disilane, hexaphenyldisilane, hexatolyldisilane, Hexaxylyldisilane, 1,2-diethyl-1,1,2,2-tetramethyldisilane, 1,2-bis (n-propyl) -1,1,2,2-tetramethyldisilane, 1,2- Bis (iso-propyl) -1,1,2,2-
Tetramethyldisilane, 1,2-bis (n-butyl) -1,1,2,2-tetramethyldisilane, 1,2-bis (sec-butyl) -1,1,2,2-tetramethyldisilane, 1,2-bis (tert-butyl) -1,1,2,2-
Tetramethyldisilane, 1,2-diamyl-1,1,2,2-tetramethyldisilane, 1,2-bis (n-hexyl) -1,1,2,2-tetramethyldisilane, 1,2-bis (N-octyl) -1,1,2,2-tetramethyldisilane, 1,2-bis (cyclopropyl) -1,1,2,2-tetramethyldisilane, 1,2-bis (cyclobutyl) -1 , 1,2,2-Tetramethyldisilane, 1,2-bis (cyclopentyl) -1,1,2,2-tetramethyldisilane, 1,2-bis (cyclohexyl) -1,1,2,2-tetra Methyldisilane, 1,2-dibenzyl-1,1,2,2-tetramethyldisilane, 1,2-diphenyl-1,1,2,2-tetramethyldisilane, 1,2-ditolyl-1,1,2 , 2-Tetramethyldisila 1,2-dixylyl-1,1,2,2-tetramethyldisilane, 1,2-dimesityl-1,1,2,2-tetramethyldisilane, 1,2-dinaphthyl-1,1,2, 2-tetramethyldisilane, 1,2-dimethyl-1,1,2,2-tetraethyldisilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Propyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (is
o-propyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Butyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Pentyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Hexyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Octyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Cyclopropyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Cyclobutyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Cyclopentyl) disilane, 1,2-dimethyl-1,1,2,2-tetrakis (n-
Cyclohexyl) disilane, 1,2-dimethyl-1,1,2,2-tetraphenyldisilane, 1,2-dimethyl-1,1,2,2-tetratolyldisilane, 1,2-dimethyl-1,1, 2,2-tetraxylyldisilane, 1,2-dimethyl-1,1,2,2-tetramenthyldisilane, 1,1,1-trimethyl-2,2,2-triethyldisilane, 1,1,1- Trimethyl-2,2,2-tris (n-propyl) disilane, 1,1,1-trimethyl-2,2,2-tris (iso
-Propyl) disilane, 1,1,1-trimethyl-2,2,2-tris (n-butyl) disilane, 1,1,1-trimethyl-2,2,2-tris (sec
-Butyl) disilane, 1,1,1-trimethyl-2,2,2-tris (ter
t-butyl) disilane, 1,1,1-trimethyl-2,2,2-triamyldisilane, 1,1,1-trimethyl-2,2,2-tris (n-pentyl) disilane, 1,1, 1-trimethyl-2,2,2-tris (n-hexyl) disilane, 1,1,1-trimethyl-2,2,2-tris (n-octyl) disilane, 1,1,1-trimethyl-2, 2,2-tris (cyclopropyl) disilane, 1,1,1-trimethyl-2,2,2-tris (cyclobutyl) disilane, 1,1,1-trimethyl-2,2,2-tris (cyclopentyl) disilane 1,1,1-trimethyl-2,2,2-tris (cyclohexyl) disilane, 1,1,1-trimethyl-2,2,2-triphenyldisilane, 1,1,1-trimethyl-2,2 , 2-Torito Ryldisilane, 1,1,1-trimethyl-2,2,2-trixylyldisilane, 1,1,1-trimethyl-2,2,2-trimethyldisilane, 1,1,1-trimethyl-2,2,2 -Trinaphthyldisilane, 1,1,1-trimethyl-2,2,2-tribenzyldisilane, 1,1,1-triethyl-2,2,2-tris (n-propyl) disilane, 1,1,1 -Triethyl-2,2,2-tris (n-butyl) disilane, 1,1,1-triethyl-2,2,2-tris (n-pentyl) disilane, 1,1,1-triethyl-2,2 , 2-Tris (n-hexyl) disilane, 1,1,1-triethyl-2,2,2-tris (n-octyl) disilane, 1,1,1-triethyl-2,2,2-tris (cyclo) Propyl) disilane, 1,1 1-triethyl-2,2,2-tris (cyclohexyl) disilane, 1,1,1-triethyl-2,2,2-triphenyldisilane, 1,1,1-triethyl-2,2,2-tritolyl Disilane, 1,1,1-triethyl-2,2,2-trixylyldisilane, 1,1,1-triethyl-2,2,2-trimenthyldisilane, 1,1,1-triethyl-2,2 2-trinaphthyldisilane, 1,1,1-triethyl-2,2,2-tribenzyldisilane, pentamethyldisilane, pentaethyldisilane, pentakis (n-propyl) disilane, pentakis (iso-propyl) disilane, pentakis ( n-butyl) disilane, pentakis (sec-butyl) disilane, pentakis (n-pentyl) disilane, pentakis (n-hex) Di), pentakis (n-octyl) disilane, pentakis (cyclopropyl) disilane, pentaphenyldisilane, pentatolyldisilane, pentaxylyldisilane, methyl-pentaethyldisilane, methyl-pentakis (n-propyl) disilane, methyl- Pentakis (n-butyl) disilane, methyl-pentakis (n-pentyl) disilane, methyl-pentakis (n-hexyl) disilane, methyl-pentakis (n-octyl) disilane, methyl-pentakis (cyclopropyl) disilane, methyl-penta Benzyldisilane, Methyl-pentaphenyldisilane, Methyl-pentatolyldisilane Methyl-pentaxylyldisilane Methyl-pentamesityldisilane, Octamethyltrisilane, Decamethyltetrasilane Dodecamethylpentasilane, tetradecamethylhexasilane, and the like, preferably 1,2-dimethyldisilane, 1,2-diphenyldisilane, 1,2-bis (cyclopropyl) disilane, 1,1,2,2- Tetramethyldisilane, 1,1,2,2-tetraphenyldisilane, 1,1,2,2-tetrakis (cyclopropyl) disilane, hexamethyldisilane, hexaethyldisilane, hexakis (n-butyl) disilane, hexaphenyldisilane 1,2-diethyl-1,1,2,2-tetramethyldisilane, 1,2-diphenyl-1,1,2,2-tetramethyldisilane, 1,2-bis (cyclopropyl) -1,1 , 2,2-Tetramethyldisilane, 1,1,1-trimethyl-2,2,2-triethyldisilane, 1,1, -Trimethyl-2,2,2-triphenyldisilane, 1,1,1-trimethyl-2,2,2-tris (cyclopropyl) disilane, pentamethyldisilane, pentaethyldisilane, pentaphenyldisilane, methyl-pentaethyl Disilane, methyl-pentaphenyldisilane, octamethyltrisilane, decamethyltetrasilane, dodecamethylpentasilane, tetradecamethylhexasilane, etc. are particularly preferred, tetramethyldisilane, hexamethyldisilane, pentamethyldisilane, octamethyl Examples thereof include trisilane, decamethyltetrasilane, dodecamethylpentasilane, and tetradecamethylhexasilane.

Further, the general formula (II) which is the component (A) used in the present invention
Specific examples of the compound represented by: octamethylcyclotetrasilane, octaethylcyclotetrasilane, octaphenylcyclotetrasilane, decamethylcyclopentasilane, decaethylcyclopentasilane, dodecamethylcyclohexasilane, dodecaethylcyclohexane Silane, etc. can be mentioned.

Among the compounds represented by the general formula (II), preferred specific examples include octamethylcyclotetrasilane, decamethylcyclopentasilane, and dodecamethylcyclohexasilane.

Examples of the source of the fluorine ion as the component (B) used in the production method of the present invention include, for example, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tris (dimethylamino) sulfonium difluorotrimeryl silicate, Onium compounds such as lithium fluoride, sodium fluoride, potassium fluoride,
Mention may be made of alkali metal fluorides such as cesium fluoride and alkali metal bifluorides such as potassium bifluoride.

Particularly when an alkali metal fluoride is used, 12-crown-4, 15-crown-5, 18-crown-6,
Dibenzo-18-crown-6, dicyclohexyl-1
By using crown ethers such as 8-crown in combination, the action as a cocatalyst can be enhanced.

Among the above, preferred as the cocatalyst is an ion source of fluoride ions.

Examples of the vinyl-based monomer polymerized by the production method of the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, lauryl methacrylate and triethylene glycol. Methacrylic acid esters such as dimethacrylate, methyl acrylate, ethyl acrylate, propyl metalylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, and other acrylic acid esters, methacrylonitrile, acrylonitrile Unsaturated nitriles such as, N, N-dimethylmethacrylamide, N, N-diethylmeta N, N-dialkyl unsaturated amides such as crylamide, styrene, p-methoxystyrene, p-chlorostyrene, α-methylstyrene, p-dimethylaminostyrene, and other vinyl aromatic compounds, preferably acrylic ester. And methacrylic acid esters, vinyl aromatic compounds, and the like.

These monomers can be used alone or in combination.

In the production method of the present invention, the initiator of the component (A) usually has a molar ratio to the monomer of 1 or less, preferably 1/1000.
The cocatalyst as the component (B) is used in such an amount that the molar ratio to the initiator is in the range of 1/1000 to 100, preferably 1/10 to 1.

The polymerization reaction in the production method of the present invention can be carried out in a wide temperature range from low temperature to high temperature, but preferably -3.
It is carried out at 0 ° C to 100 ° C.

The production method of the present invention can be carried out in a wide pressure range from reduced pressure to high pressure, but is preferably carried out under 1 to 50 atmospheric pressure.

It is generally desirable to carry out the production method of the present invention in an organic solvent, but when the monomers to be subjected to the polymerization reaction are liquid under the polymerization conditions, it is not necessary to use a solvent.

If the monomers are solid under the polymerization conditions, it is necessary to use a sufficient amount of solvent for the initiator and cocatalyst to work effectively. When a solvent is used, the concentration of the monomer is 0.
The amount of the solvent used is 01% by weight or more, preferably 10% by weight or more, and the amount of the reaction system required to maintain a liquid state under the polymerization conditions.

Examples of the solvent used in the present production method include ether solvents such as dimethyl ether, diethyl ether, dibutyl ether, dimethoxyethane, diethylene glycol, dimethyl ether, dioxane, and tetrahydrofuran,
Nitrile solvents such as acetonitrile and propionitrile, halogenated hydrocarbon solvents such as dichloromethane and dichloroethane, saturated or unsaturated hydrocarbon solvents such as petroleum ether, n-hexane, n-octane, benzene, toluene and xylene. Other hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N
-Methylpyrrolidone, dimethylformamide, aprotic polar solvents such as tetramethylsulfone, preferably with ether solvents, nitrile solvents, aprotic polar solvents or halogenated hydrocarbon solvents or saturated or unsaturated hydrocarbons. A mixed solvent with an ether solvent, a nitrile solvent, or an aprotic polar solvent, and particularly preferably an ether solvent can be mentioned.

Although the initiator and the cocatalyst in the present invention are stable to water as individual compounds, the production method of the present invention is preferably carried out under substantially anhydrous conditions, and the water present in the reaction system is It is necessary to keep the concentration of the cocatalyst, which is the component (B), at most.

When the water content exceeds the concentration of the cocatalyst, it is difficult for the polymerization reaction to proceed, and even when the water content is below the cocatalyst concentration, it is difficult to obtain a high molecular weight polymer when a considerable amount of water exists.

Therefore, in order to produce a high molecular weight polymer by the production method of the present invention, it is preferable to sufficiently dehydrate the solvent, the monomer, the initiator, the cocatalyst and the like used in advance.

Further, in the production method of the present invention, in order to prevent the invasion of water, it is important to carry out the polymerization in a sufficiently dry atmosphere, and as such an atmosphere, for example, dry air, dry nitrogen, or an inert gas such as argon. The atmosphere can be mentioned, and a dry inert gas atmosphere is preferably used.

In the production method of the present invention, the addition order of the initiator, the cocatalyst and the monomer to the reaction system is not particularly limited, and the polymerization reaction proceeds in any addition order. However, the method of adding the monomer or the solution thereof to the solvent solution of the initiator and the cocatalyst is preferable because the reaction can be easily controlled under the polymerization conditions where the concentration of the monomer is high. When the concentration of the monomer is low and the heat of polymerization can be easily removed, a method of adding the cocatalyst or the initiator to the solution of the monomer and the initiator or the solution of the monomer and the cocatalyst is preferable.

When an initiator or cocatalyst is added to the reaction,
Usually, the initiator or the cocatalyst is added as a solution dissolved in an aprotic polar solvent capable of dissolving, for example, tetrahydrofuran or the same solvent used for the polymerization reaction,
When the cocatalyst to be added is an inorganic compound or the like which is poorly soluble in the solvent, it is added as it is without using the solvent.

When a block copolymer is produced by using two or more kinds of monomers by the production method of the present invention, first, the monomers are polymerized using an initiator and a cocatalyst, and then obtained. The second monomer may be added to the obtained polymer solution as it is or as a solution prepared by dissolving the second monomer in an appropriate solvent, usually the same solvent as the reaction solvent. At this time, if the cocatalyst added first is already deactivated, the required amount of cocatalyst is added.

In order to stop the polymerization reaction in the production method of the present invention,
A compound having acidic hydrogen such as water, alcohol, phenol and carboxylic acid may be added to the reaction system, and alcohol such as methanol and ethanol is usually used.

The compound having acidic hydrogen is added in an amount of at least the number of moles of the cocatalyst in the reaction system, preferably the number of moles of the polymerization initiator and the cocatalyst, whichever is greater.

Action The present invention provides the above-mentioned general formula (I) having a silicon-silicon bond.
Alternatively, the co-catalyst is caused to act on the initiator represented by (II) to generate a silyl anion-like chemical species, and this is caused to act on the vinyl monomer that is an acceptor, thereby giving a silyl-substituted carbanion. By generating seeds, the vinyl monomer is polymerized to obtain a high molecular weight polymer.

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

Example 1 (Production of Polymethyl Methacrylate with Hexamethyldisilane and Fluoride Ion) At 25 ° C. under a dry nitrogen stream, 1.5 g (10.18 mmol) of hexamethyldisilane was added to 46 ml of anhydrous tetrahydrofuran (THF). THF solution of tetrabutylammonium fluoride (TBAF) 0.2
Addition of ml (anhydrous TBAF; 0.1 mmol) gave a slightly exothermic, pale yellow solution.

Next, 5.3 g (52.94 mmol) of methyl methacrylate was added dropwise over 10 minutes while stirring this solution. During this time, the temperature of the reaction solution rose to a maximum of 35 ° C. After the completion of dropping, the mixture was stirred for 70 minutes, and 10 ml of methanol was added to stop the polymerization. After removing the solvent of the obtained reaction mixture under reduced pressure, it was dissolved in 40 ml of toluene,
When the polymer was added to 600 ml of methanol and the polymer was precipitated and coagulated to recover, 4.65 g (yield 87.7%) of white powder of polymethylmethacrylate was obtained.

The polystyrene reduced number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained polymethylmethacrylate are T
It was measured by gel permeation chromatography (GPC) using HF as a mobile phase. The infrared absorption spectrum (IR) was measured using a sample prepared by coating a toluene solution of the polymer on a sodium chloride single crystal plate and drying.

The results obtained are as follows.

Mn; 30,300 Mw; 61,500 Mw / Mn; 2.03 IR (cm ^-1 ); 1740, 1750 (> C = O) 1065, 752 Example 2 (polymethyl with hexamethyldisilane and fluoride ion) Production of Methacrylate) Anhydrous THF3 at 25 ° C. under a dry nitrogen stream.
0 ml, THF solution of hexamethyldisilane 0.5 ml
In a mixed solution of (hexamethyldisilane; 0.25 mmol) and 2.00 g (19.98 mmol) of methyl methacrylate, 0.25 ml of anhydrous TBAF in THF (anhydrous TBA
F; 0.13 mmol) was added and stirred.

An exothermic reaction occurs after about 3 minutes, and the temperature of the reaction solution is up to 3
It rose to 5 ° C.

After the addition of TBAF, the reaction solution was stirred directly for 1 hour and the reaction solution was added directly to 50
The polymer was recovered by pouring it into 0 ml of methanol to stop the polymerization reaction and precipitating and coagulating the polymer. As a result, 1.8 g of white powdery polymethylmethacrylate was obtained.
(Yield 94.5%) was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 47,000 Mw; 119000 Mw / Mn; 2.52 Example 3 (Production of polymethylmethacrylate from hexamethyldisilane and fluoride ion) Anhydrous hexamethylphosphoric acid at 25 ° C under a dry nitrogen stream. Hexamethyldisilane 1.49 g (10.16 mmol) and anhydrous T in 46 ml of rutriamide (HMPA)
0.2 ml of THF solution of BAF (anhydrous TBAF; 0.1
mmol), and 5.57 g (55.63 mmol) of methyl methacrylate over 10 minutes while stirring the solution.
Was dripped.

During this time, the temperature of the reaction solution rose up to 40 ° C. After completion of dropping, the mixture was further stirred for 30 minutes and then 5 ml of methanol and 30 ml of toluene were added to terminate the polymerization.

The obtained reaction mixture was poured into 2 of methanol to recover the polymer by precipitating and coagulating the polymer, and 4.5 g (yield; 81.3%) of polymethylmethacrylate having a pale yellow-green fluorescence was obtained. It was

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 4,500 Mw; 361,500 Mw / Mn; 80.14 Example 4 (Production of polymethylmethacrylate from hexamethyldisilane and fluoride ion) To 25 ml of anhydrous toluene in 46 ml of anhydrous toluene under a stream of dry nitrogen. Hexamethyldisilane (10.14 mmol),
0.4 ml of anhydrous TBAF in THF (anhydrous TBAF;
0.2 mmol) and 5.37 g of methyl methacrylate
(53.64 g) was added and the reaction solution was heated to 60 ° C. and stirred for 2 hours.

Then, the reaction solution was added to 600 ml of methanol, and the polymer was recovered by precipitation and coagulation. As a result, 4.12 g (yield; 76.7%) of white powdery polymethyl methacrylate was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 3,200 Mw; 57,600 Mw / Mn; 17.88 Example 5 (Production of polymethylmethacrylate from hexamethyldisilane and fluoride ion) 46 ml of anhydrous cyclohexane under a dry nitrogen stream,
Hexamethyldisilane 1.506 g (10.22 mmo
l), 0.4 ml of anhydrous TBAF in THF (anhydrous TBAF
AF; 0.2 mmol) and methyl methacrylate 6.7
When a solution consisting of 5 g (67.42 mmol) was heated and stirred at 60 ° C. for 1 hour, precipitation of a white lump polymer was observed.

After the contents were poured into a large amount of methanol and collected, 40 ml of a toluene solution was prepared and precipitated in 600 ml of methanol.
When it was recovered again by coagulation, 5.54 g of white powdery polymethylmethacrylate (yield: 8
2.1%) was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 16,300 Mw; 126,200 Mw / Mn; 7.75 Example 6 (Production of polymethylmethacrylate from hexamethyldisilane and fluoride ion) 10 ml of anhydrous THF was added at 25 ° C under a stream of dry nitrogen. Hexamethyldisilane in anhydrous THF 1.0
ml (hexamethyldisilane; 0.5 mmol), methyl acrylate 1.93 g (22.42 mmol) and anhydrous T
0.5 ml of BAF in THF (anhydrous TBAF0.25
(mmol) and stirred for 30 minutes, 10 ml of methanol was added to terminate the polymerization.

Next, the solvent and unreacted monomers were removed under reduced pressure, diluted with toluene, and washed 3 times with ion-exchanged water.

After drying with a molecular sieve 4Å and then drying under high vacuum, 1.682 g of resinous polymethyl acrylate (yield: 8
7.2%) was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethyl acrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 2,030 Mw; 8,100 Mw / Mn; 3.99 Example 7 (Poly-by hexamethyldisilane and fluoride ion)
Production of tert-butyl methacrylate) In a dry nitrogen stream, at 25 ° C., 10 ml of anhydrous THF was added to an anhydrous THF solution of hexamethyldisilane 1.0.
ml (hexamethyldisilane; 0.5 mmol), tert
-Butyl methacrylate 2.94 g (20.68 mmol)
And 0.5 ml of anhydrous TBAF in THF (anhydrous TBAF
AF 0.25 mmol) and stirred for 30 minutes, then 1
The polymerization was stopped by adding 0 ml of methanol.

Then, the solvent and the unreacted monomer were removed under reduced pressure, and the residue was dissolved in toluene and coagulated in 800 ml of methanol to give poly-tert-butyl methacrylate 2.
54 g (yield; 86.4%) was obtained.

M of the obtained poly-tert-butyl methacrylate
The results of measuring n, Mw, and Mw / Mn in the same manner as in Example 1 are as follows.

Mn; 81,600 Mw; 118,500 Mw / Mn; 1.45 Example 8 (Production of polyacrylonitrile from hexamethyldisilane and fluoride ion) Anhydrous THF1 at 25 ° C. under a dry nitrogen stream.
Anhydrous THF solution of hexamethyldisilane 1.0 ml in 0 ml
ml (hexamethyldisilane; 0.5 mmol), acrylonitrile 1.80 g (33.92 mmol) and anhydrous TB
0.5 ml of AF solution in THF (anhydrous TBAF 0.25 mm
ol) was added and stirring was continued for 2 hours, and a yellowish white precipitate was formed. Then, 10 ml of methanol was added to stop the polymerization, and the solvent and unreacted monomers were removed under reduced pressure to give a yellowish white polyacrylonitrile 1.1.
0 g (yield; 61%) was obtained.

Example 9 (Production of polystyrene from hexamethyldisilane and fluoride ion) Hexamethyldisilane 3 was added to 30 ml of anhydrous hexamethylphosphoramide at 25 ° C. under a dry nitrogen stream.
After adding 19 mg (2.16 mmol) and 0.4 ml of a solution of anhydrous TBAF in THF (anhydrous TBAF; 0.2 mmol),
9.75 g of styrene (93.6 g) while stirring this solution.
1 mmol) was added dropwise over 10 minutes.

The reaction solution was initially pale yellow, but the color of the living anion became red by the addition of styrene, and the temperature of the solution rose to a maximum of 35 ° C. After the dropping was completed, the mixture was stirred at room temperature for 30 minutes, and then 5 ml of methanol and 3 ml of toluene were added.
Polymerization was stopped by adding 0 ml. At this time, when methanol was added to the red polymerization solution, the red color of the solution disappeared and changed to pale yellow.

The obtained polymerization solution was added to 650 ml of methanol,
By solidifying and collecting, 8.70 g (yield; 89.3%) of white powder polystyrene was obtained.

Mn, Mw, and Mw / Mn of the obtained polystyrene
The results of measurement in the same manner as in Example 1 are as follows.

Mn; 19,200 Mw; 205,000 Mw / Mn; 10.66 Example 10 (Production of block copolymer of styrene-methylmethacrylate with hexamethyldisilane and fluoride ion) At 25 ° C under a dry nitrogen stream. Hexamethyldisilane 5 in 30 ml of anhydrous hexamethylphosphoramide
00 mg (3.39 mmol) and 0.4 ml of anhydrous TBAF in THF solution (anhydrous TBAF; 0.2 mmol) were added, and 2.30 g of styrene (22.08 mm) while stirring this solution.
ol) was added dropwise over 10 minutes.

The reaction solution changed from pale yellow to red color of living anion, and an increase in solution viscosity was observed.

After the addition of styrene was completed, stirring was continued for 1 hour, and then 2.57 g (25.67 mmol) of methyl methacrylate was added to 10
Dropped in minutes.

Upon the addition of methylmethacrylate, the color of the solution changed from red to yellow and an exotherm was observed. After the completion of the addition of methyl methacrylate, stir for another 30 minutes, then 10 ml
Polymerization was stopped by adding methanol.

Then after adding 60 ml of toluene to the polymerization solution,
The polymer was coagulated and recovered in 1.5 methanol to obtain 4.46 g (yield: 91.6%) of a styrene-methyl methacrylate block copolymer. The polystyrene obtained by polymerizing styrene and then sampling had Mn of 15,100 and Mw of 154,0.
00, Mw / Mn is 10.20, Mn of the polymer after copolymerization of methyl methacrylate is 19,500,
Mw was 255,100 and Mw / Mn was 13.10, showing that the obtained polymer was a block copolymer.

Example 11 (Production of Polymethyl Methacrylate Using Dodecamethylcyclohexasilane and Fluoride Ion) 175 mg (0.50) of dodecamethylcyclohexasilane in 10 ml of anhydrous THF at 25 ° C. in a dry nitrogen stream.
2 mmol), 1.85 g of methyl methacrylate (18.4)
8 mmol) and 0.5 ml of anhydrous TBAF in THF
(Anhydrous TBAF 0.25 mmol) was added and stirred for 35 minutes, and then 5 ml of methanol was added to terminate the polymerization.
Then, the solvent and unreacted monomers were removed from the obtained solution under reduced pressure, and the polymer was diluted with 20 ml of toluene to obtain 4
By coagulating and collecting in 00 ml of methanol,
1.00 g (yield; 54.1%) of polymethylmethacrylate was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 25,200 Mw; 48,450 Mw / Mn; 1.92 Example 12 (Production of polymethylmethacrylate with hexamethyldisilane and fluoride ion) Anhydrous 1,3-dimethyl at 25 ° C in a dry nitrogen stream. Two
-Hexamethyldisilane 1 in 18 ml of imidazolidinone
54 mg (1.04 mmol) and anhydrous cesium fluoride 2.
0 g (13.2 mmol), 18-crown-6 0.50
g (1.89 mmol) and methyl methacrylate 95 g
(94.4 mmol) was added, and heating and stirring were continued at 60 ° C.
After 4 hours, 10 ml of methanol was added to terminate the polymerization, cesium fluoride was filtered off, and then the polymer was coagulated and recovered in methanol of 2 to obtain 2.9 g of polymethyl methacrylate (yield: 30 .5%) was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are as follows.

Mn; 12,410 Mw; 580,600 Mw / Mn; 4.68 Examples 13-14, Comparative Examples 1-2 Initiators used in the present invention (Examples 13-14) and existing initiators (Comparative Examples). Chemical stability with respect to acid and alkali with 1 and 2) was compared, and the polymerization initiation ability of the chemically treated initiator with respect to a vinyl monomer was compared using methyl methacrylate as an example.

Acid treatment 0.01 ml of 100 ml of a 5% solution of the initiator in ethyl ether was added.
After shaking for 1 minute in a separating funnel with an aqueous solution of N-sulfuric acid, the aqueous layer was separated, the organic layer was pre-dried with 10 g of anhydrous magnesium sulfate, and then dried and purified through an anhydrous activated alumina column under a nitrogen stream. .

Alkali treatment The same treatment as the acid treatment was carried out except that a 0.01 N NaOH aqueous solution was used as the alkali.

Evaluation of Polymerization Initiation Ability of Vinyl Monomer Acid Treated, Alkali Treated or Untreated Initiator Solution
20 ml of anhydrous THF, 5 ml of anhydrous HMPA, 10.0 g of methyl methacrylate and, if necessary, 0.5 ml of a THF solution of anhydrous TBAF as a co-catalyst (anhydrous TBA
F0.25 mmol) and stirred at room temperature or low temperature (-70 ° C.) for 30 minutes, the solution was poured into methanol 1 and the dry weight of the coagulated polymer was evaluated.

The results are shown in Table 1. From Table 1, it can be seen that the initiators of the present invention, hexamethyldisilane and dodecamethylcyclohexasilane, have extremely high chemical stability as compared with conventional initiators.

Example 15 (Production of polymethylmethacrylate from octamethyltrisilane and fluoride ion) Synthetic literature of octamethyltrisilane; Kumada, et al. J. Orga
nomet. Chem. , 1963, 1 , p157, octamethyltrisilane was synthesized.

Production of polymethylmethacrylate 10 ml of anhydrous THF at 25 ° C in a dry nitrogen stream.
Octamethyltrisilane 102mg (0.500mm
ol), 1.85 g of methyl methacrylate (18.48)
mmol) and anhydrous TBAF in 0.5 ml of THF
(Anhydrous TBAF 0.25 mmol) was added and stirred for 30 minutes, and then 5 ml of methanol was added to terminate the polymerization.

Then, the solvent and unreacted monomers were removed from the obtained solution under reduced pressure, and then diluted with 20 ml of toluene, and the polymer was coagulated and collected in 400 ml of methanol to obtain 1.50 g (yield). 81.1%) of polymethylmethacrylate was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results were as follows.

HexamethyldiMn 30.100 in 46 ml of anhydrous toluene at 25 ° C. under a dry nitrogen stream.
0 Mw; 52,500 Mw / Mn; 1.92 Example 16 (Production of polymethylmethacrylate from octaphenylcyclotetrasilane and fluoride ion) Petrarch Systems Inc. , Manufactured, octaphenylcyclotetrasilane 100 mg (0.13
7 mmol), and methyl methacrylate 15.0 g
To a solution of (0.150 mmol) and 20 ml of anhydrous THF was added 0.5 ml of a THF solution of anhydrous TBAF (0.25 mmol of anhydrous TBAF) at room temperature under a dry nitrogen stream. After stirring for a few minutes, the solution changed from colorless to pale yellow and an exotherm was observed. After stirring for 30 minutes, 10m
The reaction was stopped by adding 1 liter of methanol,
7.8 g by dissolving in 1 l of toluene, pouring into about 1 of methanol to coagulate the polymer, filtering and drying.
Polymethylmethacrylate (yield 52.0%) was obtained.

The Mn, Mw, and Mw / Mn of the obtained polymethylmethacrylate were measured in the same manner as in Example 1, and the results are:
It was as follows.

Mn; 19,800 Mw; 40,500 Mw / Mn; 2.05 The effect of the invention The compound that serves as the initiator of the component (A) used in the production method of the present invention is under normal conditions of normal temperature and atmospheric pressure. Since it is chemically extremely stable, is unlikely to be altered by moisture, and is stable even in a diluted mineral acid or alkaline aqueous solution, it has the advantage of being extremely easy to store and handle without requiring special care. Moreover, such an initiator is (B)
When combined with a cocatalyst as a component, it exhibits high catalytic activity and has an advantage that a polymer having an extremely high molecular weight can be produced even under mild conditions such as normal temperature and atmospheric pressure.
Furthermore, the production method of the present invention is different from living anion polymerization of vinyl-based monomers using conventionally known alkali metals and organic metals, and is an alkali metal that corrodes other metals or crosslinks the polymer itself to gel. It is possible to provide a living polymer containing no harmful inorganic metal.

Therefore, it can be used as a material for which it is required to prevent harmful inorganic metals from mixing as much as possible, for example, as a supporting material and coating material for semiconductors, electronic devices, and optical parts, and as various structural materials and paints.

Claims (1)

[Claims] 1. A vinyl-based monomer containing (A) general formula (I) [In the formula, R can be selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 10 carbon atoms, and may be the same or different, and n is 0 to 4
A compound represented by the general formula (II) [Wherein, R is the same as in the general formula (I), and may be the same or different, and m is an integer of 4 to 6], and at least one selected from the group consisting of An initiator, and (B) an onium compound serving as a source of fluorine ions,
A process for producing a vinyl polymer, which comprises contacting with at least one cocatalyst selected from the group of alkali metal fluorides and alkali metal bifluorides.