JPH0641496B2 - Method for producing graft polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a graft polymer, and more particularly to a method for producing a living graft polymer.

[Conventional technology]

Conventionally, as a method for producing a graft polymer using a vinyl-based monomer, a graft polymerization method in which a radical species is generated on the polymer has been generally used. The radical species are generated by partially decomposing the polymer by irradiation with radiation having high energy such as ultraviolet rays, X-rays, γ rays, electron beams and α rays, or generating radical species by activating the polymer. Method, a method of generating a radical species by extracting a hydrogen radical from the polymer by contacting a special catalyst, a compound that decomposes by heating or irradiation to generate a radical species is previously copolymerized with the polymer, or A method is known in which a radical species is generated by introducing it into a polymer as a pendant by means such as esterification and then heating or irradiating with radiation.

On the other hand, as a method for producing a graft polymer without using a radical reaction, a method for producing a graft polymer by ionic polymerization using an active anion or the like as a grafting point is also known,
For example, as anionic polymerization initiators for grafting vinyl monomers, conventionally, K, Na, Li and other alkali metals, K
Alkyl alkali metals such as R, NaR, LiR (R is an alkyl group), Grignard reagents, and alkali metal alcoholates have been used.

[Problems to be solved by the invention]

The radical reaction-initiating species for graft polymerization generated in the polymerization system by the conventional method is a chain transfer reaction with a solvent molecule or a group other than the vinyl group of the monomer at the same time as the polymerization of the vinyl monomer. Therefore, there is a drawback that it is easily deactivated and that it does not have a direct chemical bond with the polymer, that is, a non-grafted polymer is by-produced. Therefore, in the production of a graft polymer using a radical reaction initiation species, the graft ratio to the polymer is generally low even if the consumption rate of the monomer is increased, and the material properties of the graft polymer, such as stability of quality, are A special process such as fractional coagulation was required in order to sufficiently remove the ungrafted polymer, which is the cause of the decrease. On the other hand, a drawback of the method for producing a graft polymer by ionic polymerization is that an extremely highly reactive metal-based catalyst such as alkyllithium is required to generate anions on the polymer, and the polymer to which the metal-based catalyst is added is required. Has a living property only at an extremely low temperature, and it is very difficult to sufficiently suppress chain transfer and by-products of a homopolymer due to an unreacted metal-based catalyst.

In order to solve the problems of these conventional graft polymerization methods, while having high polymerizability for various vinyl monomers at room temperature, the chain transfer is extremely low, and disproportionation due to recombination is caused. There has been a demand for the development of a novel method of generating a so-called living-initiated polymerization initiation species that does not occur in the polymer to be grafted.

[Means for solving problems]

The present inventors have keenly studied a novel graft polymerization method based on a reaction derived from a strong affinity between a silicon atom and a fluoride ion in order to overcome the problems in the conventional graft polymerization of vinyl monomers. As a result of the research, the silyl group is eliminated by contacting a polymer with a compound that generates a fluoride ion or a bifluoride ion (hereinafter also referred to as a cocatalyst), which will be described in detail later. It was found that a polymer containing an extremely stable anion-like chemical species generated can be obtained, and this polymer easily reacts with a monomer having a polar group to give a graft polymer having a high living property, The present invention has been completed based on this finding.

Therefore, the present invention provides (a) the general formula (I) (In the formula, R is an alkyl group having 1 to 16 carbon atoms or 6 carbon atoms.
To 10 aryl groups, and R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and are the same. Or may be different), and a polymer of α-silyl acrylate represented by the formula (b), and (b) at least one monomer selected from the group of α-silyl acrylate represented by the general formula (I). A polymer selected from a copolymer consisting of a monomer and at least one monomer selected from the compounds copolymerizable therewith (hereinafter referred to as “trunk polymer”) is added with a fluoride ion or a heavy fluoride. At least one compound that can serve as an ion source of a compound ion is contacted to generate an anion-like polymerization initiation species, and at least one vinyl monomer is graft-polymerized to the polymer having the anion-like polymerization initiation species. Characterized by A method for producing graft polymers.

In the general formula (I), R is an alkyl group having 1 to 16 carbon atoms or an aryl group having 6 to 10 carbon atoms. 1 to 16 carbon atoms
Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and specific examples include a methyl group, an ethyl 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-heptyl group, n-octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, benzyl group, decyl group , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, bentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like.

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

R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or carbon water 6 to 10
Of aryl groups, which may be the same or different.
Specific examples of the alkyl group and the aryl group include the above-mentioned examples excluding the alkyl group having 9 to 16 carbon atoms, and the alkoxy group includes such an alkyl group.

Specific examples of the compound represented by the general formula (I) include methyl α-trimethylsilyl acrylate ethyl α-trimethylsilyl acrylate α-trimethylsilyl acrylate n-propyl α-trimethylsilyl acrylate iso-propyl α-trimethylsilyl acrylate n -Butyl α-trimethylsilyl acrylate sec-butyl α-trimethylsilyl acrylate tert-butyl α-trimethylsilyl acrylate amyl α-trimethylsilyl acrylate n-pentyl α-trimethylsilyl acrylate n-hexyl α-trimethylsilyl acrylate n-heptyl α- Trimethylsilyl acrylate n-octyl α-trimethylsilyl acrylate cyclohexyl α-trimethylsilyl acrylate α-trimethylsilyl acrylate n-decyl α-trimethylsilyl N-dodecyl acrylate n-tetradecyl acrylate n-tetradecyl acrylate n-hexadecyl acrylate n-hexadecyl α-trimethylsilyl acrylate n-octadecyl α-trimethylsilyl phenyl acrylate α-trimethylsilyl acrylate tolyl α-trimethylsilyl acrylate naphthyl α-trimethylsilyl acrylate Xylyl acrylate α-Trimethylsilyl Methyl acrylate α-Triethylsilyl methyl acrylate α-Triethylsilyl ethyl acrylate α-Triethylsilyl acrylate iso-Propyl α-Triethylsilyl n-butyl α-Triethylsilyl acrylate sec-Butyl α-triethylsilyl tert-butyl acrylate α-triethylsilyl amyl α-triethylsilyl n-octyl acrylate α- Cyclohexyl triethylsilyl acrylate α-Triethylsilyl benzyl benzyl α-Triethylsilyl hexadecyl acrylate α-Triethylsilyl octadecyl acrylate α-Triethylsilyl phenyl phenyl α-Triethylsilyl naphthyl acrylate α-Triethylsilyl mesyl acrylate α-Tris Methyl (n-butyl) silyl acrylate α-Tris (n-butyl) silyl ethyl acrylate α-Tris (n-butyl) silyl n-butyl acrylate α-Tris (n-butyl) silyl n-octyl acrylate α -Tris (n-butyl) silyl cyclohexyl α-tris (n-butyl) silyl octadecyl acrylate α-tris (n-butyl) silyl phenyl α-tris (n-butyl) silyl acrylate Methyl α-tris (n-octyl) silyl acrylate α-Tris (n-octyl) silyl acrylate α-Tris (n-octyl) silyl acrylate n-butyl α-Tris (n-octyl) silyl acrylate Cyclopropyl α-tris (n-octyl) silyl cyclohexyl α-tris (n-octyl) silyl octadecyl α-tris (n-octyl) silyl phenyl α-tris (n-octyl) silyl naphthyl acrylate α- (Dimethylphenyl) silyl methyl acrylate α- (Dimethylphenyl) silyl ethyl acrylate α- (Dimethylphenyl) silyl n-butyl acrylate α- (Dimethylphenyl) silyl n-octyl acrylate α- (Dimethylphenyl) Cyclohexyl acrylate α- (Dimethylphenyl) silyl octadecyl acrylate α- (Dimethylphenyl) silyl phenyl α- (Dimethylphenyl) silyl naphthyl acrylate α- (Diphenylmethyl) silyl methyl acrylate α- (Diphenylmethyl) silyl acrylate ethyl α- (Diphenylmethyl) silyl acrylic acid n-butyl α- (diphenylmethyl) silyl acrylic acid n-octyl α- (diphenylmethyl) silyl acrylic acid cyclohexyl α- (diphenylmethyl) silyl acrylic acid octadecyl α- (diphenylmethyl) Phenyl silyl acrylate α- (diphenylmethyl) silyl naphthyl acrylate α-Triphenyl silyl methyl acrylate α-Triphenyl silyl acrylate α-Triphenyl silyl acrylate n-butyl α- Triphenylsilyl acrylic acid n-octyl α-triphenylsilyl acrylic acid cyclohexyl α-triphenylsilyl acrylic acid octadecyl α-triphenylsilyl acrylic acid phenyl α-triphenylsilyl acrylic acid naphthyl α- (tert-butyldimethyl) silyl acrylic Methyl acid α- (tert-butyldimethyl) silyl ethyl acrylate α- (tert-butyldimethyl) silyl n-butyl acrylate α- (tert-butyldimethyl) silyl n-octyl acrylate α- (tert-butyldimethyl) Cyclohexyl acrylate α- (tert-Butyldimethyl) silyl octadecyl acrylate α- (tert-Butyldimethyl) silyl phenyl α- (tert-Butyldimethyl) silyl naphthyl acrylate α-Trimethoxysilylmethyl acrylate Benzyl trimethoxysilyl acrylate α-triethoxysilyl methyl acrylate α-triethoxysilyl benzyl α-trisbutoxysilyl methyl acrylate α-trisbutoxysilyl benzyl benzyl α-trisoctyloxysilyl methyl acrylate α- Benzyl trisoctyloxysilyl acrylate and the like, preferably α-trimethylsilyl methyl acrylate α-trimethylsilyl acrylate ethyl α-trimethylsilyl acrylate n-propyl α-trimethylsilyl acrylate iso-propyl α-trimethylsilyl acrylate n-butyl α- Trimethylsilyl acrylate sec-Butyl α-Trimethylsilyl tert-butyl α-Trimethylsilyl Cyclohexyl α-Trimethylsilyl benzene Α-Trimethylsilyl phenyl acrylate α-Trimethylsilyl naphthyl acrylate α-Triethylsilyl methyl acrylate α-Triethylsilyl ethyl acrylate α-Triethylsilyl acrylic acid n-propyl α-Triethylsilyl acrylate iso-propyl α-Triethylsilyl acrylic Acid n-butyl α-triethylsilyl acrylate sec-butyl α-triethylsilyl tert-butyl α-triethylsilyl acrylate cyclohexyl α-triethylsilyl benzyl α-triethylsilyl phenyl α-triethylsilyl naphthyl acrylate And so on.

The trunk polymer (a) is a homopolymer of α-silylacrylic acid ester represented by the above general formula (I), or these α-silylacrylic acid esters.
It is a copolymer of two or more monomers selected from the silyl acrylate group, and the trunk polymer (b) is at least one monomer selected from the α-silyl acrylate group and this monomer. At least 1 selected from compounds copolymerizable with
It is a copolymer composed of one kind of monomer.

Examples of the compound copolymerizable with the α-silyl acrylate include styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, α-vinylnaphthalene, β-vinylnaphthalene, vinylpyridine, N
-Aromatic vinyl compounds such as vinylcarbazole and divinylbenzene, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, phenyl acrylate and allyl acrylate, methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, sec-butyl methacrylate, tret-butyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate,
Methacrylic acid esters such as lauryl methacrylate, triethylene glycol dimethacrylic acid ester, and 1,3-butadiene, isoprene, chloroprene, 2-
Diene compounds such as trimethylsilyl-1,3-butadiene may be mentioned.

These trunk polymers (a) and (b) can be produced by a radical polymerization method. Examples of the radical polymerization method include a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method. The bulk polymerization method and the solution polymerization method are preferably used. As the polymerization initiator in these radical polymerization methods, benzoyl peroxide, cumene videloperoxide, t
An organic peroxide such as butyl hydroperoxide or an azo compound such as azobisisobutyronitrile is used, and it is usually polymerized at 40 to 90 ° C. under an atmosphere of an inert gas such as nitrogen.

In addition, α- contained as a (co) polymerization component in the trunk polymer
The (co) polymerization amount of the silyl acrylate is not particularly limited as long as the total number of moles exceeds the number of moles of acidic hydrogen-containing substance contained in the graft polymerization system described later, for example, water. 0.01 mol% or more in the (co) polymer, preferably 0.01 to 50 mol%, particularly preferably 0.01 to
30 mol%.

The cocatalyst used in the present invention, that is, a compound that can be an ion source of fluoride ion or bifluoride ion is an onium compound, an alkali metal fluoride, or an alkali metal bifluoride. Specific examples of the onium compound include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tris (dimethylamino) sulfonium difluorotrimethylsilicate and the like. Specific examples of alkali metal fluorides include:
Lithium fluoride, sodium fluoride, potassium fluoride,
There are cesium fluoride and the like, and specific examples of the alkali metal bifluoride include potassium bifluoride and the like. Among these compounds, onium compounds are preferably used. When an alkali metal fluoride is used, crown ethers such as 12-crown-4,15-crown-5,18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and the like. When used together, the action as a cocatalyst can be enhanced.

The amount of the above-mentioned cocatalyst used is determined according to the number of anion-like polymerization initiation species generated in the trunk polymer, that is, the number of grafting points, but it is (co) polymerized as a (co) polymerization component in the trunk polymer. molar ratio in which α- silyl acrylate is usually 1/10 ³ to 10 ^2/1, preferably 1 / 10-1 /
It is used so as to be in the range of 1.

Vinyl-based monomers used for grafting onto the trunk polymer in the present invention include methyl acrylate, ethyl acrylate, n-butyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, acrylic acid 2 -Acrylic acid esters such as trimethylsiloxyethyl, methyl methacrylate, ethyl methacrylate,
N-butyl methacrylate, sec-butyl methacrylate,
Methacrylic acid esters such as tert-butyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, lauryl methacrylate, triethylene glycol dimethacrylate, and α-silyl acrylic acid represented by the above general formula (I). Esters,
N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide,
Unsaturated amides such as N, N-diethylmethacrylamide, unsaturated nitriles such as methacrylonitrile and acrylonitrile, styrene, o-, m- or p-methylstyrene, o-, m- or p-methoxystyrene , Α
-Aromatic vinyl compounds such as methylstyrene, o-, m- or p-dimethylaminostyrene, o-, m- or p-chlorostyrene, and the like, preferably the above-mentioned methacrylic acid esters and acrylic acid esters. , Unsaturated amides and the like. These monomers can be used alone or in combination.

The graft polymerization reaction in the present invention can be carried out in a wide temperature range from a low temperature to a high temperature, and in a wide pressure range from a reduced pressure to a high pressure, but is usually -50 to 100 ° C.
It is carried out under 1 to 50 atmospheric pressure, but most commonly at room temperature and atmospheric pressure.

Generally, the graft polymerization reaction is preferably carried out in an organic solvent, but when the trunk polymer and vinyl monomer used in the polymerization reaction are liquid under the polymerization conditions, the solvent may not be used. . However, when the trunk polymer and the vinyl-based monomer are solid under the graft polymerization conditions,
It is necessary to use a sufficient amount of solvent for the cocatalyst to work effectively.

Examples of the solvent that can be used in the present invention include ether solvents such as dimethyl ether, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, dioxane and tetrahydrofuran,
Nitrile solvents such as acetonitrile and propionitrile, halogenated hydrocarbon solvents such as dichloromethane and dichloroethane, hydrocarbon solvents such as petroleum ether, n-hexane, n-octane, benzene, toluene and xylene, and hexamethylphosphor Examples thereof include aprotic polar solvents such as luamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfolane and dimethylsulfoxide. These solvents can be used alone or as a mixture.

In the present invention, since the active species for graft polymerization generated in the trunk polymer are anion-like chemical species, they are easily deactivated by a compound having acidic hydrogen such as water and alcohol, and the polymerization initiation ability is lost. Therefore, the solvent used in the production of the graft polymer of the present invention should be free from compounds having water or acidic hydrogen in excess of the number of moles of active silyl groups and the number of moles of cocatalyst in the trunk polymer used. It is necessary to dehydrate or purify and use for polymerization. Particularly, as will be described later, it is used when the graft side chain having a blocking property is introduced into the trunk polymer by carrying out the second and subsequent polymerizations while maintaining the living property of the polymerization growth terminal during the graft polymerization. It is preferable that not only the solvent but also the monomer, the cocatalyst, and the polymerization vessel are thoroughly dehydrated in advance.

Although the method of the present invention can be carried out in dry air, it is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

In the method of the present invention, the order of addition of the trunk polymer, the cocatalyst and the monomer to the reaction system is not particularly limited and may be any order of addition. However, under polymerization conditions where the concentration of the monomer is high, the method of adding the monomer to the solution consisting of the trunk polymer, the cocatalyst and the solvent is preferable because the reaction can be easily controlled. When the concentration of the monomer is low and the heat of polymerization is relatively small, the solution of the monomer and the co-catalyst, or the solution of the monomer and the co-catalyst, respectively, the solution of the co-catalyst or the trunk polymer Can also be added. When a solid trunk polymer or vinyl monomer is added to the reaction system under graft polymerization conditions, these are dissolved and an aprotic polar solvent, for example, a solvent similar to the solvent used for the polymerization reaction is used. Although the cocatalyst to be added is a solid that is hardly soluble in the solvent, the cocatalyst can be added as it is.

In the method of the present invention, it is possible to produce a graft polymer having a blocking side chain by using two or more vinyl monomers. In this case, first, a co-catalyst is added to the trunk polymer to generate a polymerization initiation species, and then a first vinyl monomer is added to perform graft polymerization, and after the monomer is consumed, The second monomer is added to carry out the polymerization, or the co-catalyst is added to the solution of the trunk polymer and the first monomer to carry out the graft polymerization to carry out the second polymerization after the monomer is consumed. A monomer may be added.

Further, in the graft polymerization method of the present invention, when the graft polymer is produced by using a small number of moles of the cocatalyst with respect to the number of moles of the α-silylacrylic ester in the trunk polymer, Since a silyl group that can be activated by a cocatalyst remains on the trunk polymer, contact the graft polymer with a monomer that is the same as or different from the vinyl monomer previously used with the cocatalyst. It is also possible to produce a desired graft polymer by further performing graft polymerization by.

In order to terminate the graft polymerization reaction, a compound having acidic hydrogen such as water, alcohol, phenol or carboxylic acid may be added to the reaction system. Usually, methanol,
Ethanol or water is used. The compound having this acidic hydrogen is at least the number of moles of the cocatalyst in the reaction system,
Preferably, the amount of the α-silyl acrylic acid ester copolymerization component in the trunk polymer and the cocatalyst, which is the larger of the number of moles, is added.

The graft polymer produced by the method of the present invention is a thermoplastic resin having excellent mechanical properties, optical properties, or moldability, or as a thermoplastic elastic body, a structural material such as optical equipment, a semiconductor, an electric device. Can be used as a coating material. Further, by adding a photosensitive crosslinking agent or a thermal crosslinking agent to a graft polymer of a monomer having an appropriate unsaturated group, it can be used as a photosensitive material or a thermosetting material having excellent mechanical properties.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The analytical instruments used in the following examples are as follows. ¹ H-NMR spectrum ... Hitachi R-600 type Fourier transform high resolution nuclear magnetic resonance apparatus (60 MHz)
Infrared absorption spectrum: IRA-1 Grating Infrared Spectrometer, manufactured by JASCO Corporation. Gel Permeation Chromotograph 150-C, manufactured by Waters, Inc. Differential scanning calorimetry: 990 Thermal Analyzer and 910-Differential Scanning Calorimeter, manufactured by DuPont Instruments. Further, the number average molecular weight ( _n ) and the weight average molecular weight ( _w ) in the following examples are polystyrene equivalent values.

Example 1 (A) Synthesis of trunk polymer α-Trimethylsilyl n-butyl acrylate (5.00 g, 25.00 mmol), styrene (25.00 g, 240.00 mmol) and benzoyl peroxide (450.4 mg, 1.86 mmol) under a nitrogen stream. ,
The polymerization solution obtained by heating and stirring at 80 ° C. for 18 hours was diluted with toluene (30 g) and then coagulated with methanol (900 ml). Next, the coagulation solvent was removed by decantation, vacuum drying was performed, and the residue was redissolved in toluene (60 g) and n-hexane (1.5) was added.
The resulting resinous polymer was vacuum dried at 60 ° C. for 12 hours to obtain 19.73 g of a copolymer of n-butyl α-trimethylsilylacrylate and styrene.

The obtained polymer is α-trimethylsilylacrylic acid n-
The fact that it was a copolymer of butyl and styrene was tested by the method described below.

1) The ¹ H-NMR spectrum of the polymer measured in d ₆ -acetone showed peaks corresponding to trimethylsilyl group and phenyl group at δ / ppm −0.40 to +0.20 and 6.20 to 7.40, respectively. The copolymerization ratio calculated from the integral ratio is the molar ratio α
-N-butyl trimethyl acrylate / styrene =
The ratio was 0.13 / 1, which almost coincided with the charged molar ratio.

2) The infrared absorption (IR) spectrum of the polymer is 1730 cm
Stretching vibration absorption of the carbonyl group of the ester at ^-1
It showed absorptions at out-of-plane deformation vibration of the phenyl group to 0 cm ^-1 and 750 cm ^-1.

3) In a differential thermal analysis (DSC) spectrum measured in a nitrogen stream at a temperature rising rate of 20 ° C / min, a temperature different from that of polystyrene Tg (100 ° C), that is, a change indicating the presence of Tg at 87 ° C. Presented a turning point.

4) _n determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase is 1.77 × 10 ⁴ , _w is 3.43 × 10 ⁴ , _w /
_n was 1.94. The GPC spectrum is shown in FIG.

(B) Graft polymerization (1) The trunk polymer synthesized in (A) above (0.85 g) and a cocatalyst tetrabutylammonium fluoride (TBAF) (5.9 × 10 ^-2 mm
ol) in THF (30 ml) with methyl methacrylate (1.58 g, 1
5.78 mmol) was added over 5 minutes, and the mixture was stirred at 25 ° C under a nitrogen stream for 30 minutes. The occurrence of graft polymerization of methyl methacrylate with respect to the trunk polymer was confirmed by the following analysis results using a sample obtained by coagulating and drying a part of the polymerization solution with methanol.

1) In the ¹ H-NMR spectrum of the graft polymer, the peak of the trimethylsilyl group was not detected, and an absorption peak indicating the presence of the desilylated trunk polymer and the polymer of methyl methacrylate was recognized. Also, with a phenyl group in the trunk polymer,
The copolymerization ratio in the graft polymer, calculated from the integral ratio of the methoxy groups present in the ester part of the graft chain, is consistent with the ratio of the prepared backbone polymer and methyl methacrylate, and the graft polymerization of methyl methacrylate is quantitative. Showed what was going on.

2) In the DSC spectrum, a new inflection point corresponding to Tg of the polymer of methyl methacrylate appeared at 119 ° C. The Tg (87 ° C) of the trunk polymer disappeared, and a new
It showed Tg.

3) GPC spectrum is _n = 3.45 × 10 ⁴ , _w = 9.63 ×
A single peak at 10 ⁴ , _w / _n = 2.79 was shown, indicating that no unreacted trunk polymer and methyl methacrylate homopolymer were contained, and that the molecular weight was increased by graft polymerization. The GPC spectrum is shown in FIG.

4) The copolymerization ratio of each polymer fractionally precipitated by dropping methanol as a precipitant into the acetone solution of the graft polymer was almost the same as that before fractionation.

(B) Graft polymerization (2) Methacrylic acid n was added to the graft polymer solution in the living state before coagulation with methanol obtained in (B) graft polymerization (1) above.
-Butyl (1.84 g, 12.94 mmol) was added at 25 ° C and stirred, and as a result, an increase in the viscosity of the solution was observed. After 2 hours, a white polymer (3.82 g) was obtained by coagulating and collecting the polymer with methanol (750 ml). It was confirmed from the following facts that the graft chain obtained by the graft polymerization has a living property.

1) The ¹ H-NMR spectrum of the obtained polymer was obtained by adding n-butyl methacrylate to the end of the graft chain in addition to the grafted product of methyl methacrylate obtained in (B) Graft polymerization (1) above. It was shown that the above polymer was bound.

2) The GPC spectrum of the obtained polymer is _n = 5.95 ×
10 ⁴ , _w = 1.81 × 10 ⁵ , _w / _n = 3.04 showed a single peak, unreacted trunk polymer and first stage graft polymer were not mixed, and in comparison with both, clear A significant increase in molecular weight was observed. The GPC spectrum is shown in FIG.

3) Even if TBAF and methyl methacrylate were added to the anhydrous THF solution of the graft polymer coagulated and recovered in the above (B) graft polymerization (1), the graft polymerization of methyl methacrylate did not occur. This indicates that in (B) graft polymerization (2), the polymerization initiation species of n-butyl methacrylate are at the ends of the graft chains generated in the first stage grafting and are in a living state.

Example 2 Synthesis of (A) Trunk Polymer n-Butyl α-trimethylsilylacrylate (10.00 g, 4
9.91 mmol), styrene (10.00 g, 96.02 mmol) and benzoyl peroxide (250.3 mg, 1.03 mmol) under nitrogen flow at 80 ° C for 18
After heating and stirring for an hour, dilute with toluene (20 g) and add methanol.
Copolymerization (11.22 g) was obtained by coagulating with (600 ml). The obtained polymer has _n = 4.
It was found that 07 × 10 ³ , _w = 2.99 × 10 ⁴ , and _w / _n = 7.34, and the Tg determined from the DSC spectrum was 80 ° C.

(B-1) Graft polymerization of n-butyl acrylate The trunk polymer (0.51 g) synthesized in (A) above and TBAF (0.1 mmo)
n-Butyl acrylate (1.28 g, 9.99 mmol) was added to a THF solution (5.0 ml) of l) at 0 ° C under a nitrogen stream, stirred for 30 minutes, and then the polymer was coagulated and recovered with methanol (100 ml). Thus, a resinous graft polymer (1.70 g) was obtained. From the GPC spectrum of the obtained polymer, _n = 2.15 × 10 ⁴ ,
It was found that _{w 2} = 4.26 × 10 ⁴ and _w / _n = 1.99.

(B-2) Graft Polymerization of Benzyl Methacrylate The trunk polymer (0.50 g) synthesized in (A) above and TBAF (0.1 mmo
l) THF solution (5.0 ml) under a nitrogen stream at 25 ° C, benzyl methacrylate (1.18 g, 9.35 mmol) was added, and after stirring for 30 minutes, the polymer was coagulated and recovered with methanol (100 ml). A resinous graft polymer (1.40 g) was obtained. The polymer obtained had _n = 3.40 × 10 ⁴ ,
It was found that _w = 1.16 × 10 ⁵ and _w / _n = 3.40.

(B-3) Graft Polymerization of 2-Trimethylsiloxyethyl Methacrylate The trunk polymer (0.50 g) synthesized in (A) above and TBAF (0.1 mmo
2-trimethylsiloxyethyl methacrylate (1.78 g, 8.78 mmol) was added to a THF solution (5.0 ml) of (1) under a nitrogen stream at 25 ° C., and the mixture was stirred for 30 minutes. In addition to 100 ml), 1.4
8 g of polymer was obtained. The polymer was insoluble in chloroform, acetone and toluene but slightly dissolved in THF and methanol. The IR spectrum of the polymer showed characteristic absorption of hydroxy group in 3600 cm ^-1, it was desilylated since not exhibit characteristic absorption of siloxy groups appearing around 1100 cm ^-1 was confirmed. The graft ratio of the charged 2-hydroxyethyl methacrylate to the trunk polymer was 86%.

Example 3 Polymer of α-trimethylsilylmethyl acrylate synthesized by solution radical polymerization ( _n = 5.00 × 10 ³ ) (1.00 g)
And methyl methacrylate (2.00g, 19.98mmol) in THF
(20 ml) in a nitrogen stream at 25 ° C with TBAF 0.1M TH
F solution (1.0 ml) was added and stirred for 30 minutes, then methanol
Graft polymer (2.80g) by coagulation at (1.5)
Got The obtained polymer is _n
It was found that = 1.40 × 10 ⁴ , _w = 3.8 × 10 ⁴ , and _w / _n = 2.71.

Example 4 Synthesis of (A) Trunk Polymer Methyl α-trimethylsilylacrylate (5.00 g, 31.59 mm
ol), butadiene (20.00 g, 370.0 mmol) and benzoyl peroxide (50 mg, 0.21 mmol) in toluene (100 ml) at 60 ° C.
By stirring for 12 hours, a copolymer (21.00 g) was obtained.
From the GPC spectrum, the polymer obtained was _n = 1.24.
It was found that × 10 ⁵ , _w = 5.96 × 10 ⁵ , and _w / _n = 4.81.

(B) Graft Polymerization In a THF solution (30 ml) of the trunk polymer (0.90 g) synthesized in (A) above and methyl methacrylate (9.21 g, 91.98 mmol) under a nitrogen stream at 25 ° C., a 0.1 M THF solution of TBAF was added. (1.0 ml) added,
After stirring for 1 hour, the polymer was coagulated and recovered with methanol (1.5) to obtain a graft polymer (8.57 g).
The obtained polymer has _n = 2.01 × from GPC spectrum.
It was found that 10 ⁵ , _w = 1.23 x 10 ⁶ , and _w / _n = 6.11.

Example 5 (A) Synthesis of trunk polymer n-butyl α-trimethylsilyl acrylate (5.00 g, 25.
00 mmol), methyl methacrylate (15.00 g, 150.0 mmol) and benzoyl peroxide (600 mg, 2.48 mmol) under a nitrogen stream at 80
Copolymer (10.00g) by stirring and heating at ℃ for 12 hours
Got The obtained polymer is _n
It was found that = 1.20 × 10 ⁴ , _w = 2.40 × 10 ⁴ , and _w / _n = 2.00.

(B) Graft Polymerization In a THF solution (30 ml) of the trunk polymer (1.00 g) synthesized in (A) above and methyl methacrylate (3.00 g, 30.00 mmol), in a nitrogen stream at 25 ° C., a 0.1 M THF solution of TBAF was added. (1.0 ml) was added and the mixture was stirred for 1 hour, and then the polymer was coagulated and recovered with methanol (1) to obtain a graft polymer (3.82 g). The obtained polymer has _n = 4.
It was found that 00 × 10 ⁴ , _w = 8.51 × 10 ⁴ , and _w / _n = 2.13.

Example 6 Synthesis of (A) trunk polymer n-butyl α-trimethylsilyl acrylate (2.00 g, 9.9 g)
8 mmol), styrene (1.00 g, 9.60 mmol) and benzoyl peroxide (33.9 mg, 0.14 mmol) were stirred and heated at 80 ° C. for 18 hours under a nitrogen stream to obtain a copolymer (1.36 g). The polymer obtained had _n = 4.50 × 1 from the GPC spectrum.
It was found that 0 ⁴ , _w = 7.42 × 10 ⁴ , and _w / _n = 1.65.

(B) Graft Polymerization (1) To a solution of the trunk polymer (0.51 g) synthesized in (A) above and methyl methacrylate (1.15 g, 11.49 mmol) in THF (10 ml) under a nitrogen stream at 25 ° C. and TBAF of 0.1. M THF solution (0.25 ml) was added, the mixture was stirred for 1 hour, coagulated with methanol (300 ml), and collected to obtain a graft polymer (1.39 g). The obtained polymer has _n = 2.
It was found that 13 × 10 ⁴ , _w = 5.49 × 10 ⁴ , and _w / _n = 2.58.

(C) Graft polymerization (2) Methanol pre-coagulation graft polymer synthesized in (B) graft polymerization (1) (0.74 g) and tert-butyl methacrylate (1.
To a THF solution (10 ml) of 37 g, 9.63 mmol), at 25 ° C., under nitrogen flow, was added 0.1M THF solution of TBAF (0.2 ml), and
After stirring for 1 minute, coagulation and recovery with methanol (400 ml) gave a graft polymer (1.89 g). The obtained polymer was analyzed by GPC to find that _n = 6.40 × 10 ⁴ , _w =
It was found that 2.03 × 10 ⁵ , _w / _n = 3.18.

〔The invention's effect〕

(A) The trunk polymer used in the present invention is chemically extremely stable under normal conditions of room temperature and atmospheric pressure, and is stable in a catalyst such as water or alcohol unless a catalytic amount of acid or base is present. Is.

(B) When these core polymers are contacted with the cocatalyst of the present invention, extremely active initiation species for graft polymerization are generated.

(C) When a vinyl-based monomer is brought into contact with the trunk polymer that has generated this starting species, Michael type addition is carried out, and a graft polymer having stable active points at the polymerization growth terminals is obtained. In this graft polymerization reaction, since it is possible to selectively generate polymerization active points on the trunk polymer, a homopolymer which was a problem of the conventional graft polymerization method is not generated,
It is possible to obtain a graft polymer that does not substantially contain these homopolymers. Therefore, the target graft polymer can be obtained in high purity without requiring any particular purification means. Furthermore, it is possible to produce a graft polymer having a blocking property in the side chain, which is difficult by the conventional method.

(D) Regulation of the number of grafting points is controlled by α contained in the trunk polymer.
Possible by adjusting the amount of silyl acrylate and the amount of co-catalyst fluoride ion or bifluoride ion source, and for the polymerization reaction at temperature compared to the conventional radical polymerization graft polymerization method Since the influence is small, the graft point can be regulated with extremely high reproducibility.

(E) According to the method of the present invention, since the active species for graft polymerization have a high living property, the degree of polymerization of the graft polymer is as long as the added monomer is ideally purified. Depends on the amount of the monomer, and a very high molecular weight graft polymer can be produced.

(F) The graft polymerization method of the present invention is an excellent polymerization method in terms of controlling the number of graft points and controlling the degree of polymerization.

(G) In the living anionic polymerization method using a conventional alkali metal or organic metal, when the obtained polymer comes into contact with another metal, the metal is corroded or the polymer itself is deteriorated. Although there is a problem, such a problem does not occur in the method of the present invention because such metals are not used.

[Brief description of drawings]

FIG. 1 shows the trunk polymer and graft polymerization obtained in Example 1.
The weight concentration (vertical axis) of the polymer obtained in (1) and (2) is GP
It is the graph plotted with respect to C elution count (horizontal axis).

Claims (2)

[Claims] 1. (a) General formula (I) (In the formula, R is an alkyl group having 1 to 16 carbon atoms or 6 carbon atoms.
Is an aryl group having ₁ to 10 and R ₁ , R ₂ and R ₃ are respectively an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and are the same. Or may be different), and a polymer of α-silyl acrylate represented by the formula (b), and (b) at least one monomer selected from the group of α-silyl acrylate represented by the general formula (I). A polymer selected from a copolymer consisting of a monomer and at least one monomer selected from a compound copolymerizable therewith, and at least 1 which can serve as an ion source of a fluoride ion or a bifluoride ion. A graft polymer characterized in that at least one vinyl-based monomer is graft-polymerized to a polymer having the anion-like polymerization initiation species by contacting two kinds of compounds with each other. Manufacturing method. 2. The compound capable of serving as an ion source of fluoride ion or bifluoride ion is at least one compound selected from an onium compound, an alkali metal fluoride, and an alkali metal bifluoride. 1
A method for producing a graft polymer according to the item.