JPH09132647A - Production of graft polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silane compound which permits the synthesis of a graft polymer controlled in the length of a graft chain, the number and span of graft points, etc., in good operability and reproducibility by selecting a specified silane compound. SOLUTION: A silane compound represented by formula I (wherein Ar<1> is aryl; Ar<2> is arylene; R<1> and R<2> are each an alkyl or an aryl; R<3> is an alkylene or an arylene; and X<1> is a halogen) is selected. This compound is reacted with a carbanion-terminated polymer to obtain a polymer having a group of formula II at least one terminal. This polymer is reacted with a carbanion-terminated polymer and then reacted with a dihalohydrocarbon compound represented by formula V (wherein R<4> is an alkylene or an arylene; X<3> and X<4> are halogens) to obtain a polymer having at least one group represented by formula III (wherein X<2> is a halogen). Further, this polymer is reacted with a carbanion- terminated polymer to obtain a graft polymer having at least one branched structure represented by formula IV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a specific silane compound, a polymer such as a graft polymer which can be derived from the silane compound, and a method for producing the polymer.

[0002]

2. Description of the Related Art In recent years, studies have been conducted on the synthesis of graft polymers for the purpose of enhancing the functionality and performance of polymeric materials. As a general synthesis method of the graft polymer,
(1) A method in which a polymer serving as a backbone is combined with a polymer serving as a graft chain by a polymer-polymer reaction, and (2) a monomer serving as a graft chain is reacted with the polymer serving as a trunk to polymerize the graft chain. Polymer-to-monomer reaction method (3)
A so-called macromonomer method is known, which is a copolymerization of a monomer serving as a backbone and a polymer serving as a graft chain. The synthesis method of the graft polymer of the above (1) and (2) is
It is widely used industrially because it can be carried out with excellent economic efficiency by a method called so-called reactive processing, which uses an extruder as a reaction field. That is, the synthesis method of the above (1) includes a polymer having two kinds of functional groups capable of reacting with each other, for example, a carboxyl group and a hydroxyl group, an acid anhydride group and an amino group, etc. in the middle of the molecular chain and a terminal of the molecular chain. It can be carried out by kneading with the polymer in 1. in an extruder. Also,
The synthesis method of (2) above is a radical-generating group, for example, a polymer having a functional group such as a peroxide group, an azo group, a thiol group, a perester ester group, and an unsaturated group in the middle of a molecular chain and a radical. It can be carried out by kneading an initiator, for example, benzoyl peroxide, to generate a radical, then adding a monomer to this, and reacting under a kneading condition. In addition, in the synthesis method (3) above, a graft polymer having a controlled chemical structure of a graft chain is obtained by using a macromonomer synthesized by a living polymerization method and having a controlled average molecular weight and molecular weight distribution. It is attracting attention because it can

[0003]

It is more important for polymer materials to have optimum performance according to their applications. With the progress of polymer alloy technology, the average molecular weight, molecular weight distribution, graft chain A graft polymer in which the chain length, the number of graft chains and the like are precisely controlled is required on an industrial level.

However, in the conventional synthesis method, it is difficult to synthesize a graft polymer by precisely controlling its molecular structure, and it is difficult to obtain desired physical properties. For example, in the case of the above-mentioned synthesis method (1), since the trunk polymer is generally synthesized by radical polymerization, the functional group serving as a graft point is stochastically introduced into the polymer. Is. As a result, it cannot be said that the spacing between grafting points and the number of graft chains are precisely controlled in the finally obtained graft polymer. Also,
In the synthesis method of (1) above, it is also possible to use a polymer serving as a backbone, which is produced by using an anionic polymerization method. That is, a monomer having an anionic initiator is polymerized to obtain a polymer having an active anion terminal, and this is reacted with a trihalogenated silane compound (eg, methyltrichlorosilane, ethyltribromosilane, propyltrichlorosilane, etc.). To obtain a polymer having a dihalogenated silyl group at the terminal of the molecule, and then to one molecule of the polymer having a dihalogenated silyl group at the terminal of the molecule (two molecules of the polymer having an anion terminal The two molecules of may have different molecular structures), thereby synthesizing a graft polymer having one graft chain in which the chain length of the graft chain and the position of the graft point are controlled. In theory it is possible. However, in the case of this method, in practice, there are restrictions on the reaction conditions such as the order of addition of the polymers, and side reactions such as coupling reactions between the polymers are highly likely to occur, so that the desired structure It is very difficult to selectively synthesize the graft polymer of 1) with good reproducibility. In the case of the above-mentioned synthesis method (2), the trunk polymer is generally synthesized by the radical polymerization method. Therefore, as in the case of the above-mentioned synthesis method (1), the distance between the graft points and the graft point It is difficult to obtain a graft polymer whose number, graft chain length, molecular weight distribution, etc. are precisely controlled. Further, in the case of the above synthesis method (3), even if a macromonomer having a controlled average molecular weight and molecular weight distribution is used, if it is copolymerized with a monomer by a radical polymerization method, the resulting graft polymer is The number of chains can only be controlled stochastically. Further, when the macromonomer and the monomer are copolymerized by an ionic polymerization method, the versatility is low due to restrictions such as the fact that the structures of the two need to be similar.

By the way, 1,1-diarylethylene such as 1,1-diphenylethylene has the advantages that it is not self-polymerizable and that it reacts with the anion end of the living polymer to quantitatively generate carbanions. Therefore, its application has been attempted for the purpose of synthesizing the polymer by precisely controlling the average molecular weight, the molecular weight distribution and the like. 1,1
-If a polymer having a structure corresponding to diarylethylene at the molecular end can be synthesized with good operability and reproducibility, the graft length of the graft chain, the number of graft points, the spacing between the graft points, etc. can be controlled. It is expected that the polymer can be manufactured industrially, and the application of the graft polymer to elastomers, plastic materials, resin modifiers, etc. will be expanded significantly.

Therefore, the first object of the present invention is to
-Providing a novel low molecular weight compound which enables a polymer having a structure corresponding to diarylethylene at least one molecular chain end to be synthesized with good operability and reproducibility, and is easy to synthesize itself To do. A second object of the present invention is to handle the low-molecular compound with good operability,
And to provide a polymer having a structure corresponding to 1,1-diarylethylene which can be derived with good reproducibility at at least one of the molecular chain ends. A third object of the present invention is that it can be derived from the polymer with good operability and reproducibility, and is useful as a precursor of a graft polymer.
It is to provide a polymer in which a functional group-containing structure is introduced into a molecular chain. A fourth object of the present invention is that the functional group-containing structure can be derived from the polymer introduced into the molecular chain with good operability and reproducibility, and the molecular weight of the graft chain, the number of graft points, and the graft point. It is an object of the present invention to provide a graft polymer whose structure such as chain length can be controlled. A fifth object of the present invention is to provide a method for producing a polymer having a structure corresponding to the above 1,1-diarylethylene at a molecular chain terminal with good operability and reproducibility. A sixth object of the present invention is to provide a method for producing a polymer having the functional group-containing structure introduced into its molecular chain with good operability and reproducibility. A seventh object of the present invention is to provide a method for producing the above graft polymer with good operability and good reproducibility.

[0007]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that a specific silane compound having a group corresponding to 1,1-diarylethylene and a halogenated hydrocarbon group. But 1,1 at the end of the polymer chain
From a polymer having a structure corresponding to 1,1-diarylethylene at at least one molecular chain end, which enables introduction of a group corresponding to diarylethylene quantitatively and with good operability. The inventors have found that a graft polymer having an extremely controlled molecular structure can be produced, and completed the present invention.

According to the invention, the first object mentioned above is of the general formula

[0009]

[Chemical 6]

(In the formula, Ar ¹ represents an aryl group, and Ar ²
Represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, R ³ represents an alkylene group or an arylene group, and X ¹ represents a halogen atom. )

This is accomplished by providing a silane compound represented by (hereinafter referred to as "silane compound (I)").

According to the present invention, the above second object is the general formula

[0013]

Embedded image

(In the formula, Ar ¹ represents an aryl group, and Ar ²
Represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, and R ³ represents an alkylene group or an arylene group. )

It is achieved by providing a polymer having a group represented by the formula (1) at least at one end of its molecular chain (hereinafter referred to as "diarylethylene-terminated polymer (II)").

According to the present invention, the above third object is to provide a compound of the general formula

[0017]

Embedded image

(In the formula, Ar ¹ represents an aryl group, and Ar ²
Represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, R ³ and R ⁴ each represent an alkylene group or an arylene group, and X ² represents a halogen atom. )

A polymer having at least one group represented by (hereinafter referred to as "halogenated hydrocarbon group-containing polymer (II
I) ”) is provided.

According to the present invention, the above fourth object is to provide a compound of the general formula

[0021]

Embedded image

(In the formula, Ar ¹ represents an aryl group, and Ar ²
Represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, and R ³ and R ⁴ each represent an alkylene group or an arylene group. )

It is achieved by providing a graft polymer having at least one branched structure represented by (hereinafter referred to as "graft polymer (IV)").

According to the present invention, the fifth object is to provide the silane compound (I) and a polymer having a carbanion terminal, and the carbanion in the polymer having the carbanion terminal. It is achieved by providing a method for producing the above-mentioned diarylethylene-terminated polymer (II), which is characterized by using 1 mol or more per 1 mol of the above and reacting.

According to the present invention, the sixth object is to react the above-mentioned diarylethylene-terminated polymer (II) with a polymer having a carbanion terminal, and then to obtain a product of the general formula

[0026]

Embedded image

(In the formula, R ⁴ represents an alkylene group or an arylene group, and X ³ and X ⁴ represent different halogen atoms.)

A method for producing the above halogenated hydrocarbon group-containing polymer (III), which comprises reacting a dihalogenated hydrocarbon compound represented by (hereinafter referred to as "dihalogenated hydrocarbon compound (V)") It is achieved by providing.

According to the present invention, the seventh object is the above graft polymer characterized in that the halogenated hydrocarbon group-containing polymer (III) is reacted with a polymer having a carbanion terminal. This is achieved by providing a manufacturing method of (IV).

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the above general formulas (I), (II), (III) and (IV), the aryl group represented by Ar ¹ is
Examples thereof include a phenyl group, an o-, m- or p-tolyl group, and a naphthyl group. Of these, a phenyl group is preferable. Examples of the arylene group represented by Ar ² include an o-, m- or p-phenylene group, a tolylene group and a naphthylene group, and among these, an o-, m- or p-phenylene group, and particularly an m-phenylene group. preferable. R ¹
R ² and R ² each represent an alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group, an o-, m- or p-tolyl group, or a naphthyl group, and among these, a methyl group is preferable. R ³ is an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, or an o-, m- or p-phenylene group,
It represents an arylene group such as a tolylene group and a naphthylene group, and of these, a trimethylene group is preferable. In the general formula (I), the halogen atom represented by X ¹ is preferably a chlorine atom, a bromine atom, an iodine atom or the like, and among these, a chlorine atom is preferable. The above general formula (II
In I), (IV) and (V), R ⁴ is an alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group or o-, m- or p-phenylene group, tolylene group, naphthylene group, etc. Of these, a trimethylene group is preferable among them.
The halogen atom represented by X ² in the general formula (III) is preferably a chlorine atom, a bromine atom, an iodine atom or the like,
Among these, a chlorine atom is preferred. The above general formula (V)
In the above, the mutually different halogen atoms represented by X ³ and X ⁴ are preferably selected from the group consisting of chlorine atom, bromine atom and iodine atom, and among these, a combination of chlorine atom and bromine atom is preferable.

Examples of the silane compound (I) of the present invention include 1- [3-[(chloromethyl) dimethylsilyl].
Phenyl] -1-phenylethylene, 1- [3-[(2
-Chloroethyl) dimethylsilyl] phenyl] -1-phenylethylene, 1- [3-[(3-chloropropyl)
Dimethylsilyl] phenyl] -1-phenylethylene,
1- [3-[(chloromethyl) methylethylsilyl] phenyl] -1-phenylethylene, 1- [4-[(chloromethyl) dimethylsilyl] phenyl] -1-phenylethylene, 1- [2-[( Chloromethyl) dimethylsilyl] phenyl] -1-phenylethylene, 1- [3-
[(Iodomethyl) dimethylsilyl] phenyl] -1-
Examples include phenylethylene. Among them, from the viewpoint of easiness of synthesis operation and purification operation, 1- [3-[(3
-Chloropropyl) dimethylsilyl] phenyl] -1-
Phenylethylene is preferred. The silane compound (I) of the present invention has high stability such as being less susceptible to hydrolysis because the halogen atom is not directly connected to the silicon atom,
It does not easily deteriorate even in the air. Therefore, it is easy to handle when using it.

The silane compound (I) is, for example, 1- (3
-Bromophenyl) -1-phenylethylene, 1- (4
-Bromophenyl) -1-phenylethylene, 1- (3
-Chlorophenyl) -1-phenylethylene and other general formulas

[0034]

Embedded image

(In the formula, Ar ¹ and Ar ² are as defined above, and X ⁵ represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.)

The Grignard reagent synthesized from the halide represented by and general (chloromethyl) (chloro) dimethylsilane, (2-chloroethyl) (chloro) dimethylsilane, (3-chloropropyl) (chloro) dimethylsilane, etc. formula

[0037]

Embedded image

(In the formula, R ¹ , R ² , R ³ and X ¹ are as defined above, and X ⁶ is a halogen atom such as chlorine atom, bromine atom or iodine atom.)

A dihalogenosilane compound represented by
It is possible to easily synthesize the compounds by reacting them in an equimolar ratio. The reaction is usually an aromatic hydrocarbon solvent such as benzene, toluene or xylene; an aliphatic hydrocarbon solvent such as n-hexane, n-octane or isooctane; an alicyclic system such as methylcyclopentane, cyclohexane or cyclooctane. Hydrocarbon-based solvent; in an organic solvent such as an ether-based solvent such as THF (tetrahydrofuran), dioxane, and diethyl ether, with stirring, -100 ° C to
It can be performed at a temperature within the range of about + 100 ° C. After the reaction, the silane compound (I) can be isolated and purified from the obtained reaction mixture, for example, by the following method. That is, the reaction mixture is dissolved in an organic solvent such as THF, toluene, hexane, and methylcyclohexane after evaporating and removing the solvent as needed, and the solution is -4
The mixture was cooled to a temperature of 0 ° C. or lower, and a diphenylmethyl-type anion such as diphenylethylene dimer dilithium salt or diphenylhexyllithium was added to the solution until a red color indicating a carbanion derived from a diaryl group was generated in the solution.
F, toluene, hexane, methylcyclohexane, and the like were added dropwise in the form of a solution, and the mixture was stirred at that temperature for several hours and then heated to room temperature to deactivate the anions (the carbanion color disappears), The target silane compound (I) can be separated and obtained by evaporating the organic solvent and then distilling the residue.

The diarylethylene-terminated polymer (II) of the present invention is a polymer having a group represented by the above-mentioned general formula (II) at at least one of the molecular chain terminals, and its molecular chain is linear. The polymer is roughly classified into a polymer in which the group is present at one end of the molecular chain and a polymer in which the group is present at both ends of the molecular chain. In any case, it is preferable that the main chain of the molecular chain is a polymer composed of an anion-polymerizable monomer. Preferable examples of the polymer composed of an anion-polymerizable monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylates such as pentenyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, Poly (meth) acrylic acid ester-based polymers containing acrylates such as isopropyl acrylate, butyl acrylate, isobutyl acrylate, pentenyl acrylate, etc. as main polymerization units; poly (meth) acrylonitrile-based polymers containing acrylonitrile, methacrylonitrile, etc. as main polymerization units Polymer; 1,3-butadiene, 1,3-pentadiene,
Polyconjugated diene-based polymer having a conjugated diene such as 2,3-dimethyl-1,3-butadiene, 2,4-hexadiene, 2-phenyl-1,3-butadiene and isoprene as a main polymerization unit; styrene, α- Methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, methoxystyrene, 1-vinylnaphthalene, 3-ethyl-1-vinylnaphthalene, p-N, N-dimethylaminostyrene, 2-vinylpyridine, Aromatic polymer having vinyl aromatic compound such as 4-vinylpyridine as a main polymerized unit; copolymer composed of a plurality of the above polymerized units (for example, styrene-methyl methacrylate copolymer,
Butadiene-styrene copolymer, etc.) and the like. The molecular weight of the diarylethylene-terminated polymer (II) is not particularly limited and may be appropriately set according to the purpose. However, for the purpose of using the diarylethylene-terminated polymer (II) as a precursor polymer of a graft polymer having a controlled molecular structure, the number average molecular weight is preferably in the range of 300 to 500,000, and 500 to 100,000. It is particularly preferable that it is within the range. Further, for that purpose, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the gel permeation chromatography (GPC) method is 1.0 to 1.3. It is preferably within the range, and more preferably within the range of 1.0 to 1.1.

The diarylethylene-terminated polymer (II) is
It can be produced by reacting the silane compound (I) with a polymer having a carbanion terminal.
In the reaction, the silane compound (I) is used in a proportion of 1 mol or more with respect to 1 mol of the carbanion in the polymer having a carbanion terminal. Silane compound (I)
When less than 1 mol is used for 1 mol of the carbanion in the polymer having carbanion ends, 2 molecules of the polymer having carbanion ends for 1 molecule of the silane compound (I) Is not preferable because a side reaction such as a reaction occurs. There is no particular limitation on the upper limit of the amount of the silane compound (I) used, but it is meaningless to use more than the necessary amount, and rather the amount of unreacted silane compound (I) to be removed after the reaction increases. It will be. From the above points, the amount of the silane compound (I) used is preferably in a range of 1 to 3 mol with respect to 1 mol of the carbanion in the polymer having a carbanion terminal.
It is more preferable that the ratio be within the range of 1.2 mol. The reaction between the silane compound (I) and the carbanion-terminated polymer is generally within the range of -100 ° C to + 150 ° C, preferably within the range of -90 ° C to + 100 ° C, more preferably within the range of -80 ° C to +80. By bringing them into contact with each other at a temperature within the range of ° C, it is possible to proceed easily and almost quantitatively. In this case, in order to suppress side reactions, it is preferable to remove impurities such as water and air from the reaction system as much as possible. Further, the reaction is carried out by using an aromatic hydrocarbon solvent such as benzene, toluene or xylene; an aliphatic hydrocarbon solvent such as n-hexane, n-octane or isooctane; an alicyclic ring such as methylcyclopentane, cyclohexane or cyclooctane. Formula hydrocarbon solvent; it is preferably carried out in an organic solvent such as an ether solvent such as tetrahydrofuran, dioxane or diethyl ether.

The above-mentioned polymer having a carbanion terminal is a polymer having a carbanion at the end of at least one molecular chain, and a linear polymer and a carbanion having a carbanion at only one terminal of the molecular chain are used. Examples are linear polymers having both ends of the molecular chain. By reacting a linear polymer having a carbanion on only one end of the molecular chain with a silane compound (I), a diarylethylene-terminated polymer (II) can be obtained by the reaction of the general formula (II)
It is possible to obtain a linear polymer having a group represented by the above at only one end of the molecular chain. Further, by reacting a linear polymer having carbanions at both ends of the molecular chain with a silane compound (I), a group represented by the general formula (II) is converted into a molecule as a diarylethylene terminal polymer (II). It is possible to obtain a linear polymer with both ends of the chain.

The polymer having a carbanion terminal can be produced by a conventional method such as an anionic polymerization method or a method of lithiating a polymer having a halogen atom at a molecular chain terminal. For the purpose of producing a graft polymer having a controlled molecular structure, it is preferable that the molecular structure of the polymer having a carbanion terminal be controlled as much as possible. From this viewpoint, it is preferable to use, as the polymer having a carbanion terminal, a polymer having a carbanion obtained by the anion living polymerization method at at least one molecular chain terminal, that is, a so-called living polymer. When the polymer having the above carbanion terminal is produced by the anion living polymerization method,
The anionic polymerizable monomer may be polymerized using an anionic polymerization initiator according to a conventional method. As the anionic polymerization initiator, when it is desired to produce a polymer having a carbanion at only one end of the molecular chain, a monofunctional anionic polymerization initiator such as a monolithio compound is used, and the carbanion of the molecular chain is When it is desired to produce a polymer having both terminals, a bifunctional anionic polymerization initiator such as a dilithio compound is used. Examples of monofunctional anionic polymerization initiators include sec-butyllithium and t-butyllithium, and examples of difunctional anionic polymerization initiators include 1,4-dilithiobutane, dilithiobutadiene and dilithio. Examples thereof include naphthalene. These anionic polymerization initiators may be combined with diphenylethylene, α-methylstyrene, etc. to form the initiator system. Examples of the anion-polymerizable monomer include methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate and pentenyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, Acrylate such as isobutyl acrylate and pentenyl acrylate; acrylonitrile; methacrylonitrile; 1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3
-Butadiene, 2,4-hexadiene, 2-phenyl-
Conjugated dienes such as 1,3-butadiene and isoprene; styrene, α-methylstyrene, p-methylstyrene, o-
Methylstyrene, p-butylstyrene, methoxystyrene, 1-vinylnaphthalene, 3-ethyl-1-vinylnaphthalene, p-N, N-dimethylaminostyrene, 2-
Examples thereof include vinyl aromatic compounds such as vinyl pyridine and 4-vinyl pyridine. These monomers may be used alone or in combination of two or more. A copolymer having an arbitrary monomer composition can be obtained by simultaneously using and polymerizing two or more kinds of anionically polymerizable monomers in combination. Further, after completion of the polymerization of one kind of monomer, by successively polymerizing with another kind of monomer, a block polymer having an arbitrary monomer composition and structure (diblock copolymer, A triblock copolymer or a multiblock copolymer) can be obtained. The anionic living polymerization can be carried out in the absence of a solvent, but it can also be carried out in the presence of a suitable organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; n
-Hexane, n-octane, isooctane, and other aliphatic hydrocarbon solvents; methylcyclopentane, cyclohexane, cyclooctane, and other alicyclic hydrocarbon solvents; tetrahydrofuran, dioxane, diethyl ether, and other ether solvents. . The reaction temperature of anionic living polymerization varies depending on the type of polymerization initiator, monomer and solvent used, etc., but is usually preferably in the range of −100 ° C. to + 150 ° C., and in the range of −80 ° C. to + 80 ° C. Is more preferred. As the polymerization conditions, it is possible to use the polymerization conditions adopted in ordinary anionic living polymerization, in order not to deactivate the living site of the polymerization initiator and the polymerization end, oxygen, carbon dioxide in the polymerization system,
It is preferable to adopt a condition in which water or the like is not mixed. For example, under high vacuum or in an atmosphere in which water is removed as much as possible (for example, in a dry nitrogen atmosphere), a polymerization initiator is added to a degassed / dehydrated solvent, and then a monomer is added to carry out anionic polymerization. The polymerization reaction can be carried out by either a batch system or a continuous system, and the polymerization initiator and the monomer may be gradually added, rather than added all at once. The average molecular weight of the diarylethylene-terminated polymer (II) can be arbitrarily controlled by the average molecular weight of the carbanion-terminated polymer used for its production. When a polymer having a carbanion terminal is produced by an anion living polymerization method, the average molecular weight of the obtained polymer having a carbanion terminal is almost uniquely determined by the molar ratio of the monomer and the polymerization initiator. The average molecular weight can be easily controlled to a desired value by appropriately changing the ratio of the amounts of the monomer and the polymerization initiator used.

A reaction system containing the carbanion living polymer obtained by the anion living polymerization method as described above may be added, if necessary, to diphenylstyrene and α.
-Methylstyrene or the like is added to modify the end of the molecular chain, and then a predetermined amount of silyl compound (I) is added as it is or in a state of being dissolved in a solvent and reacted to produce a diarylethylene-terminated polymer (II). It is particularly preferable because it is easy to do. After the reaction, isolation of the diarylethylene-terminated polymer (II) from the obtained reaction mixture
Purification can be performed, for example, by the following method. That is, the solvent is removed from the reaction mixture by evaporation, and the resulting crude product is subjected to a fractionation operation such as a fractionation method using a solvent (for example, Soxhlet extraction) or a GPC fractionation fractionation method to obtain a diarylethylene-terminated polymer ( The purified product of II) can be obtained. When the diarylethylene-terminated polymer (II) is used in the reaction with the below-described carbanion-terminated polymer, it is not always necessary to use a purified product as the diarylethylene-terminated polymer (II). Alternatively, the above crude product can be used.

Halogenated hydrocarbon group-containing polymer (III)
Is a polymer having at least one group represented by the above general formula (III) in the molecular chain. The part other than the group constituting the polymer (that is, the main component of the molecular chain) is anionic polymerized. It is preferably a fragment of a polymer composed of a polymerizable monomer. Preferable examples of the polymer composed of an anion-polymerizable monomer include the same as those described above for the diarylethylene-terminated polymer (II). The molecular weight of the halogenated hydrocarbon group-containing polymer (III) is not particularly limited and may be appropriately set according to the purpose. However, for the purpose of using the halogenated hydrocarbon group-containing polymer (III) as a precursor polymer of a graft polymer having a controlled molecular structure, the number average molecular weight is preferably in the range of 500 to 1500000, It is particularly preferable that it is in the range of 1,000 to 500,000. Further, for that purpose, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the gel permeation chromatography (GPC) method is 1.0 to 1.5. It is preferably within the range, and more preferably within the range of 1.0 to 1.3.

The above halogenated hydrocarbon group-containing polymer (III) is obtained by reacting the diarylethylene-terminated polymer (II) with a carbanion-terminated polymer, and then
By reacting the obtained product with a dihalogenated hydrocarbon compound (V), it can be produced with good operability and reproducibility.

The above diarylethylene-terminated polymer (I
The reaction of I) with carbanion-terminated polymers is
The diarylethylene-terminated polymer (II) was added to the polymer (I
It proceeds easily by dissolving in a solvent that is soluble in I) and does not deactivate the carbanion, and mixing with a solution of a polymer having a carbanion terminal. The ratio of the diarylethylene-terminated polymer (II) and the carbanion-terminated polymer used is such that the number of moles of the group represented by the general formula (II) in the diarylethylene-terminated polymer (II) is the carbanion-terminated polymer. The ratio is preferably in the range of 1 to 2 mol, and more preferably in the range of 1 to 1.2 mol, based on 1 mol of the carbanion in the polymer. It is more preferable to be present, and it is particularly preferable that the proportion is about 1 mol. The solvent to be used may be appropriately selected according to the type of polymer, etc., but generally, aromatic hydrocarbons such as benzene, toluene, xylene; ethers such as THF and dioxane; hexane, heptane, Aliphatic hydrocarbons such as cyclohexane are suitable. The reaction is preferably carried out under the condition that oxygen, carbon dioxide, water or the like is not mixed in the system in order not to deactivate the carbanion.
It is preferable to use a solvent that has been degassed and dehydrated under high vacuum or in an atmosphere in which water is removed as much as possible (for example, in a dry nitrogen atmosphere). The reaction temperature is -100 ° C to +.
Temperatures within the range of 150 ° C. are preferred.

The polymer having a carbanion terminal is a polymer having a carbanion at the end of at least one molecular chain, as described above, and is a linear polymer having a carbanion at only one terminal of the molecular chain. A linear polymer having a polymer and a carbanion at both ends of the molecular chain is exemplified. The carbanion-terminated polymer can be produced by a conventional method such as an anionic polymerization method or a method in which a polymer having a halogen atom at the molecular chain terminal is lithiated. For the purpose of producing a graft polymer having a controlled molecular structure, it is preferable that the molecular structure of the polymer having a carbanion terminal be controlled as much as possible. From this viewpoint, it is preferable to use, as the polymer having a carbanion terminal, a polymer having a carbanion obtained by the anion living polymerization method at at least one molecular chain terminal, that is, a so-called living polymer. The living polymer solution obtained by the anionic living polymerization method in a solvent can be used for the reaction with the diarylethylene-terminated polymer (II).

The above diarylethylene-terminated polymer (I
The reaction of I) with the carbanion-terminated polymer forms an addition reaction product having carbanions in the reaction mixture. The reaction of the obtained product with the dihalogenated hydrocarbon compound (V) is carried out after the reaction of the diarylethylene-terminated polymer (II) with the carbanion-terminated polymer is completed, and then a reaction mixture containing the reaction product. Can be carried out by adding a dihalogenated hydrocarbon compound (V) to deactivate the carbanion. Examples of the dihalogenated hydrocarbon compound (V) include bromochloromethane, iodochloromethane and 1-bromo-2.
-Chloroethane, 1-bromo-3-chloropropane, 2
-Bromochlorobenzene, 2-bromo-5-chlorotoluene and the like can be mentioned. The dihalogenated hydrocarbon compound (V) is a diarylethylene-terminated polymer (II)
It is preferably used in a proportion of 1 mol or more, more preferably in a ratio of 1 to 5 mol, based on 1 mol of the carbanion of the polymer having a carbanion terminal used for the reaction with preferable. The reaction temperature is −
Temperatures in the range 100 ° C to + 150 ° C are preferred. After the reaction with the dihalogenated hydrocarbon compound (V), the halogenated hydrocarbon group-containing polymer (III) can be isolated and purified from the obtained reaction mixture by, for example, the following method. . That is, the solvent is removed from the reaction mixture by evaporation, and the obtained crude product is subjected to a fractionation operation such as a fractionation method using a solvent (for example, Soxhlet extraction) or a GPC fractionation fractionation method to obtain a halogenated hydrocarbon group. A purified product of the contained polymer (III) can be obtained. In addition,
When the halogenated hydrocarbon group-containing polymer (III) is used in the reaction with the below-described carbanion-terminated polymer, use of a purified product as the halogenated hydrocarbon group-containing polymer (III). Is not always necessary, and the above crude product can also be used.

The graft polymer (IV) is a polymer having at least one branched structure represented by the above-mentioned general formula (IV) as a graft point in the molecular chain, but other than the branched structure constituting the polymer. Part (that is, the main body of the molecular chain)
Is preferably a fragment of a polymer composed of an anionically polymerizable monomer. Preferable examples of the polymer composed of an anion-polymerizable monomer include the same as those described above for the diarylethylene-terminated polymer (II). The molecular weight of the graft polymer (IV) is not particularly limited and may be appropriately set according to the purpose of use. When importance is attached to the control of the molecular structure, the number average molecular weight is preferably in the range of 1000 to 2500000, and 1500 to 1000000.
It is particularly preferable that it is within the range. Further, in that case, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the gel permeation chromatography (GPC) method is 1.0 to
It is preferably within the range of 1.7, and 1.0 to 1.5
Is more preferably within the range.

The graft polymer (IV) can be produced with good operability and reproducibility by reacting the halogenated hydrocarbon group-containing polymer (III) with a polymer having a carbanion terminal. . The reaction between the halogenated hydrocarbon group-containing polymer (III) and the carbanion-terminated polymer is such that the halogenated hydrocarbon group-containing polymer (III) is soluble in the polymer (II). Further, the reaction proceeds easily by dissolving it in a solvent that does not deactivate the carbanion and mixing it with a solution of a polymer having a carbanion terminal. Polymers containing halogenated hydrocarbon groups (II
I) and the carbanion-terminated polymer are used in such a manner that the number of moles of carbanion in the carbanion-terminated polymer is the same as in the general formula (III) in the halogenated hydrocarbon group-containing polymer (III). The ratio is preferably in the range of 1 to 3 moles, more preferably in the range of 1 to 1.2 moles, and more preferably about 1 mole of the group shown. It is particularly preferable that the ratio be 1 mol. The solvent to be used may be appropriately selected according to the type of polymer, etc., but generally, aromatic hydrocarbons such as benzene, toluene, xylene; ethers such as THF and dioxane; hexane, heptane, Aliphatic hydrocarbons such as cyclohexane are suitable. The reaction is preferably carried out under the condition that oxygen, carbon dioxide, water or the like is not mixed in the system in order not to inactivate the carbanion, and for example, under high vacuum or in an atmosphere in which water is removed as much as possible (for example, dry nitrogen). It is preferable to use a solvent that has been degassed and dehydrated under an atmosphere). The reaction temperature is preferably within the range of -100 ° C to + 150 ° C.

The polymer having a carbanion terminal is a polymer having a carbanion at the end of at least one of the molecular chains, as described above, and has a linear structure having the carbanion at only one terminal of the molecular chain. A linear polymer having a polymer and a carbanion at both ends of the molecular chain is exemplified. The carbanion-terminated polymer can be produced by a conventional method such as an anionic polymerization method or a method in which a polymer having a halogen atom at the molecular chain terminal is lithiated. For the purpose of producing a graft polymer having a controlled molecular structure, it is preferable that the molecular structure of the polymer having a carbanion terminal be controlled as much as possible. From this viewpoint, it is preferable to use, as the polymer having a carbanion terminal, a polymer having a carbanion obtained by the anion living polymerization method at at least one molecular chain terminal, that is, a so-called living polymer. The solution of the living polymer obtained by the anionic living polymerization method in a solvent can be used for the reaction with the halogenated hydrocarbon group-containing polymer (III).

After the reaction of the above-mentioned halogenated hydrocarbon group-containing polymer (III) with a polymer having a carbanion terminal, isolation / purification of the graft polymer (IV) from the obtained reaction mixture is carried out. For example, it can be performed by the following method. That is, the solvent is removed from the reaction mixture by evaporation,
By subjecting the obtained crude product to a fractionation operation such as a solvent fractionation method (for example, Soxhlet extraction) and a GPC fractionation fractionation method, a purified product of the graft polymer (IV) can be obtained.

The graft polymer (IV) of the present invention can have high uniformity in graft chain length, spacing and number of graft points, and overall average molecular weight and molecular weight distribution. The graft polymer (IV) of the present invention is not only useful per se as various plastics, soft resins and elastomers, but also polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; nylon 66 and the like. Polyamides; (meth) acrylic resins; elastomers such as styrene block copolymers; modifiers to other polymers, such as polyvinyl chloride, or compatibilization in compositions containing two or more of these other polymers. It is also useful as an agent.

[0055]

The present invention will be described below in detail with reference to examples. Note that the present invention is not limited by these examples. In a high vacuum (absolute pressure 0.001 Pa)
The following reaction (1) was carried out using a glass apparatus equipped with a break seal.

Example 1 [Synthesis of 1- [3-[(3-chloropropyl) dimethylsilyl] phenyl] -1-phenylethylene] 2 liters three equipped with a stirring motor, dropping funnel and reflux condenser. The inside of the one-necked flask was thoroughly dried and replaced with nitrogen gas. 12.0 g of scraped magnesium in the flask
(0.50 mol), and a solution of 72 g (0.47 mol) of bromobenzene dissolved in 300 ml of THF was added dropwise from the dropping funnel into the flask over 30 minutes.
A Grignard reagent (phenylmagnesium bromide) was synthesized by reacting with stirring. Then, in the dropping funnel,
A solution of 70 g (0.35 mol) of m-bromoacetophenone dissolved in 200 ml of THF was added, and this was allowed to react with stirring while being added dropwise to the Grignard reagent-containing mixture in the flask over 15 minutes. The resulting reaction mixture was treated (hydrolyzed) with 20% dilute sulfuric acid, extracted with ether, and the extract was evaporated to 1
-(3-Bromophenyl) -1-phenylethane-1-
Got an oar. A dehydration reaction is performed by heating and stirring this with 120% dilute sulfuric acid at 120 ° C. for 2 hours to give 1-
(3-Bromophenyl) -1-phenylethylene was produced. The obtained 1- (3-bromophenyl) -1-phenylethylene was purified by vacuum distillation (boiling point 14
8 ° C / 3.5 mmHg). 1- (3-bromophenyl)
The yield of -1-phenylethylene was 62 g and the yield was 68.
%Met.

2.3 g (0.96 mol) of scraped magnesium was placed in the reactor and kept under high vacuum, and then the reaction system was sealed. Then THF (120 ml) and the above 1
-(3-Bromophenyl) -1-phenylethylene 1
The solution with 5.5 g was transferred into the reactor by breaking the break seal and stirred at room temperature for 6 hours to give 1-
A Grignard reagent of (3-bromophenyl) -1-phenylethylene was prepared. 102 g (0.6 g) of (3-chloropropyl) (chloro) dimethylsilane was added to the obtained mixture of Grignard reagent and THF under a nitrogen stream.
0 mol = equimolar amount to Grignard reagent) was added and reacted. After reacting for 12 hours or more, THF was distilled off. The residue in the reactor is mainly 1- [3-
[(3-chloropropyl) dimethylsilyl] phenyl]
It was -1-phenylethylene (crude yield: 100
%). The above residue was dissolved in THF and the solution was -7
While cooling to 8 ° C., a THF solution of a dilithium salt of diphenylethylene dimer was added dropwise until a red color indicating the presence of carbanions was developed. The solution was stirred at that temperature for a few more hours, and after confirming that the red color did not disappear, when the temperature was raised to room temperature, the red color of the solution disappeared. THF was distilled off from this solution, and then the residue was distilled to obtain a purified product of 1- [3-[(3-chloropropyl) dimethylsilyl] phenyl] -1-phenylethylene.

Example 2 [Synthesis of polystyrene having 3-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl group at one molecular chain end] sec-Butyllithium was used as an initiator. 50 g of living polystyrene (Mn = 5000, Mw / Mn = 1.10) having a carbanion at one molecular chain end by polymerizing styrene in toluene at room temperature
A toluene solution containing (0.01 mol) was prepared, and 1.8 g (0.01 mol) of 1,1-diphenylethylene was added thereto.
5 mol) was added to add 1,1-diphenylethylene unit to the end of the molecular chain. To a toluene solution of living polystyrene having the 1,1-diphenylethylene type carbanion at one end of the molecular chain, 1- [3
A THF solution containing 18.0 g (0.05 mol) of-[(3-chloropropyl) dimethylsilyl] phenyl] -1-phenylethylene was added dropwise for reaction. The reaction proceeded immediately and the red color of the solution disappeared, indicating the presence of living anions. The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried. From the GPC measurement of the product thus obtained, side reactions such as dimerization of polystyrene did not occur,
Further, from the proton NMR measurement, it was confirmed that the 3-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl group was introduced almost quantitatively at one end of the polystyrene molecular chain.

Example 3 [Synthesis of polymethylmethacrylate having 3-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl group at one molecular chain end] sec-butyllithium and 1,1 -Methylmethacrylate in THF using an initiator consisting of diphenylethylene
A living polymethylmethacrylate (Mn = 4000, Mw / Mn = 1.06) having a carbanion at one molecular chain end by polymerizing at −78 ° C. in a medium 2
A THF solution containing 0 g (0.005 mol) was prepared, and 1,1-diphenylethylene 1.4 g (0.
075 mol) to add 1,1 to the end of the chain.
-Diphenylethylene units were added. This 1,1-
9.0 g of 1- [3-[(3-chloropropyl) dimethylsilyl] phenyl] -1-phenylethylene was added to a THF solution of living polymethylmethacrylate having a diphenylethylene type carbanion at one end of the molecular chain.
A THF solution of (0.025 mol) was added dropwise to cause a reaction.
The reaction proceeded immediately and the red color of the solution disappeared, indicating the presence of living anions. The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried. From the GPC measurement of the product thus obtained, side reactions such as dimerization of polymethylmethacrylate did not occur, and from the proton NMR measurement, it was found that 3 at one end of the polymethylmethacrylate molecular chain.
It was confirmed that the-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl group was introduced almost quantitatively.

Example 4 [Synthesis of polystyrene having 3-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl groups at both molecular chain ends] THF using dilithionaphthalene as an initiator Medium,-
25 g of living polystyrene (Mn = 5000, Mw / Mn = 1.08) having carbanions at both molecular chain ends by polymerizing styrene at 78 ° C.
A THF solution containing (0.005 mol) was prepared, and 2.7 g (0.01
5 mol) was added to add 1,1-diphenylethylene unit to the end of the molecular chain. In a THF solution of living polystyrene having the 1,1-diphenylethylene type carbanion at both ends of the molecular chain, 1- [3-
[(3-chloropropyl) dimethylsilyl] phenyl]
A THF solution of 18.0 g (0.05 mol) of -1-phenylethylene was added dropwise and reacted. The reaction proceeds immediately,
The red color of the solution disappeared, indicating the presence of living anions.
The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried.
From the GPC measurement of the product thus obtained, side reactions such as dimerization of polystyrene did not occur, and from the proton NMR measurement, 3-[[3- (1 It was confirmed that the -phenylvinyl) phenyl] dimethylsilyl] propyl group was introduced almost quantitatively.

Example 5 [1- [3- (trimethylenedimethylsilyl) phenyl] -5-chloro-1-phenyl diblock copolymer consisting of polystyrene block and polyisoprene block linked by a pentyl group Synthesis of] Living polyisoprene having a carbanion at one molecular chain end by polymerizing isoprene in toluene at room temperature using sec-butyllithium (Mn = 5000, Mw / Mn = 1.10) ) 50g
A toluene solution containing (0.01 mol) was prepared, and the 3-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl group obtained in Example 2 was added to one end of the molecular chain. Polystyrene (Mn = 5000,
A toluene solution of 50 g (0.01 mol) of Mw / Mn = 1.10 was added dropwise, and the mixture was reacted at room temperature for 60 minutes. Then, to this, 1-bromo-3-chloropropane 1.57
When g (0.01 mol) was added dropwise, the reaction immediately proceeded and the red color of the solution indicating the presence of living anions disappeared. The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried. The GPC measurement of the product thus obtained showed no side reaction, and the proton NMR measurement showed that 1- [3- (trimethylenedimethylsilyl) phenyl] -5-chloro-1-phenyl. A diblock copolymer (Mn = 10000, Mw) composed of a polystyrene block and a polyisoprene block connected by a pentyl group.
It was confirmed that /Mn=1.10) was obtained.

Example 6 [Polyisoprene block on both ends, polystyrene block on the middle, each block 1- [3- (trimethylenedimethylsilyl) phenyl] -5-chloro-1-phenyl Synthesis of triblock copolymer linked with pentyl group] THF using sec-butyllithium as an initiator
In the middle, living polyisoprene (Mn = 5000, Mw / Mn = 1.08) having a carbanion at one molecular chain end by polymerizing isoprene at −78 ° C. 1
A THF solution containing 00 g (0.02 mol) was prepared and the 3-[[3- (1-phenylvinyl) phenyl] dimethylsilyl] propyl group obtained in Example 4 was added to both molecular chains. Polystyrene having an end (Mn = 50
00, Mw / Mn = 1.08) 50 g (0.01 mol)
The THF solution of was added dropwise at 0 ° C., and further reacted at that temperature for 3 hours. Then add 1-bromo-3-to this at 0 ° C.
When 3.14 g (0.02 mol) of chloropropane was added dropwise, the reaction immediately proceeded and the red color of the solution indicating the presence of living anions disappeared. The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried. The GPC measurement of the product thus obtained showed no side reaction, and the proton NMR measurement showed that it had a polyisoprene block at both ends and a polystyrene block in the middle. -[3- (trimethylenedimethylsilyl)
Phenyl] -5-chloro-1-phenylpentyl group-linked triblock copolymer (Mn = 1500
It was confirmed that 0, Mw / Mn = 1.08) was obtained.

Example 7 [One each of a polystyrene block, a polyisoprene block and a polymethylmethacrylate block is linked by a 1- [3- (trimethylenedimethylsilyl) phenyl] -1-phenylpentamethylene group. Synthesis of Star-Shaped Graft Polymer] By using a initiator composed of sec-butyllithium and 1,1-diphenylethylene in THF at −78 ° C. to polymerize methyl methacrylate, one end of a molecular chain has a carbanion. Living polymethylmethacrylate (Mn = 4000, Mw / Mn = 1.06) 20
a THF solution containing g (0.005 mol) was prepared,
In addition to this, a diblock copolymer composed of a polystyrene block and a polyisoprene block, which were linked in 1- [3- (trimethylenedimethylsilyl) phenyl] -5-chloro-1-phenylpentyl group, obtained in Example 5 Coalescence (M
n = 10000, Mw / Mn = 1.10) 50 g (0.
THF solution of (005 mol) was added dropwise at -78 ° C. Further, the reaction was carried out at that temperature for about 12 hours. The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried. No side reaction has occurred from the GPC measurement of the product thus obtained, and from the proton NMR measurement, an ABC star type having one polymethylmethacrylate chain at the connection site between the polystyrene chain and the polyisoprene chain Graft polymer (140
00, Mw / Mn = 1.10) was obtained.

Example 8 [Trunk is made of a triblock copolymer having a polyisoprene block at both ends and a polystyrene block in the middle, and a connecting portion 2 of each block is used.
Of a graft polymer having 1- [3- (trimethylenedimethylsilyl) phenyl] -5-chloro-1-phenylpentyl group present at each of the sites as a grafting point and two polymethylmethacrylate blocks as a graft chain. Synthesis] Living polymethylmethacrylate (Mn = 4000, Mw) having a carbanion at one molecular chain end by polymerizing methylmethacrylate in THF at −78 ° C. using an initiator composed of sec-butyllithium and diphenylethylene. /Mn=1.06) 40 g
A THF solution containing (0.01 mol) was prepared, and the polyisoprene block obtained at both ends and the polystyrene block in the middle were prepared, and each block had 1- [3- (Trimethylenedimethylsilyl) phenyl] -5-chloro-1-phenylpentyl group-linked triblock copolymer (Mn = 15000, Mw
/Mn=1.08) 75 g (0.005 mol) of THF
The solution was added dropwise at -78 ° C. Further, the reaction was carried out at that temperature for about 12 hours. The obtained reaction mixture was put into methanol and reprecipitation was performed. The precipitate was dissolved in benzene and freeze-dried. GPC of the product thus obtained
No side reaction has occurred from the measurement, and the proton NM
From the R measurement, the trunk was composed of a triblock copolymer having polyisoprene blocks at both ends and a polystyrene block in the middle, and one polymethylmethacrylate chain was bonded to each of the two connecting portions of each block. Graft polymer (Mn = 23000, Mw / Mn = 1.1)
It was confirmed that 0) was obtained.

[0065]

According to the present invention, there is provided a graft polymer in which the molecular structure such as the length of the graft chain, the number of graft points, the chain length between the graft points, etc .; the average molecular weight and the molecular weight distribution are uniformly controlled. It According to the present invention, a graft polymer having such characteristics can be easily prepared by adopting a method of sequentially binding each polymer corresponding to the block in the trunk and the block of the graft chain which are divided at the graft point. And a method that can be manufactured with good reproducibility. Further, according to the present invention, there are provided a low molecular weight compound and a polymer useful as a raw material compound or an intermediate in the method, and a method capable of easily and reproducibly producing the polymer.

Claims (7)

[Claims] 1. A compound of the general formula (In the formula, Ar ¹ represents an aryl group, Ar ² represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, R ³ represents an alkylene group or an arylene group, and X ¹ represents halogen. A silane compound represented by an atom. 2. A compound of the general formula (In the formula, Ar ¹ represents an aryl group, Ar ² represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, and R ³ represents an alkylene group or an arylene group.). A polymer having a group at the end of at least one molecular chain. 3. A compound represented by the general formula: (In the formula, Ar ¹ represents an aryl group, Ar ² represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, R ³ and R ⁴ each represent an alkylene group or an arylene group, X ² represents a halogen atom), and is a polymer having at least one group represented by the formula: 4. A compound represented by the general formula: (In the formula, Ar ¹ represents an aryl group, Ar ² represents an arylene group, R ¹ and R ² each represent an alkyl group or an aryl group, and R ³ and R ⁴ represent an alkylene group or an arylene group, respectively. ) A graft polymer having at least one branched structure represented by 5. A ratio of the silane compound according to claim 1 and the polymer having a carbanion terminal in an amount of 1 mol or more per 1 mol of the carbanion in the polymer having the carbanion terminal. 3. The method for producing a polymer according to claim 2, wherein the polymer is used for the reaction. 6. The polymer according to claim 2 is reacted with a polymer having a carbanion end, and the product obtained is then represented by the general formula: ^4. A dihalogenated hydrocarbon compound represented by the formula: wherein R ⁴ represents an alkylene group or an arylene group, and X ³ and X ⁴ represent mutually different halogen atoms. The method for producing the polymer. 7. The method for producing a graft polymer according to claim 4, wherein the polymer according to claim 3 is reacted with a polymer having a carbanion terminal.