JPH05247103A - Production of terminal-modified conjugated diene-based polymer - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for efficiently producing an end-modified conjugated diene polymer at high temperature, which is advantageous in industrial practice. [Constitution] A living polymer is produced by polymerizing a conjugated diene-based monomer in the presence of an organolithium compound, and then capped with an aromatic vinyl compound, and a Lewis base (tertiary monoamine, tertiary diamine, in one molecule And a halogen-containing vinyl compound or a halogen-containing epoxy compound in the presence of a chain ether or a cyclic ether having two or more oxygen atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conjugated diene polymer having a radically polymerizable double bond or an epoxy group at the polymer terminal.

[0002]

2. Description of the Related Art Conjugated diene rubbers having a radically polymerizable double bond at the end of a polymer are functionalized radical polymerization initiators or conjugated diene monomers using a chain transfer agent such as a functional group-containing mercapto compound. By radical polymerization, a conjugated diene polymer having a terminal carboxyl group, a hydroxyl group, a functional group such as an amino group is obtained, and it may be produced by a method of reacting this with a reactive monomer having a vinyl group such as glycidyl methacrylate. It is known (Japanese Patent Publication No. 43-11224).

However, in the synthetic method by radical polymerization,
Since it is difficult to control the molecular weight of the resulting polymer, it is difficult to obtain the target polymer, and since the molecular weight distribution is wide, in the graft copolymer obtained by using this and other monomers, the desired physical properties Expression is difficult.

In addition, a conjugated diene monomer is polymerized in the presence of an anionic polymerization initiator to prepare a living polymer, and the living polymer is reacted with a halogen-containing vinyl compound or a halogen-containing epoxy compound to give a polymer terminal at a polymer terminal. A conjugated diene polymer having a double bond or an epoxy group can be produced, but in the anionic polymerization method, a polymer chain in the reaction is desired to have twice or more the polymer of the initial polymer. Not a side reaction occurs. Therefore, it is known to be produced by a method in which an active lithium terminal is capped with a compound such as alkylene oxide or diphenylethylene and then reacted with a halogen-containing epoxy compound or a halogen-containing vinyl compound (JP-B-54-54). No. 44716).

However, the use of compounds such as ethylene oxide has the potential of exploding and is not preferable in terms of industrial implementation in terms of toxicity. Further, capping with diphenylethylene is not sufficient in suppressing the side reaction.

On the other hand, according to a synthetic method by anionic polymerization, active lithium terminals and halogen-containing compounds are contained at a low temperature of 0 to 25 ° C. in a mixed solvent of tetrahydrofuran or benzene and tetrahydrofuran at 50/50 and 75/25 (vol%). There is an example of synthesizing polystyrene having a radically polymerizable double bond at the end by a method of directly reacting a vinyl compound [Macromolecule
s, 16, 628 (1983)]. However, conducting anionic polymerization in a polar solvent or a mixed solvent of a hydrocarbon solvent and a large amount of polar solvent is not preferable from the viewpoint of controlling the microstructure of the polymer when producing a conjugated diene polymer.

[0007]

Therefore, the inventors of the present invention react a radical polymer to a polymer terminal without causing side reaction by reacting a rebinc polymer with a halogen-containing vinyl compound or a halogen-containing epoxy compound in a hydrocarbon solvent. As a result of intensive research into a method for obtaining a conjugated diene polymer having a polymerizable double bond or an epoxy group, a conjugated diene monomer was polymerized in a hydrocarbon solvent to produce a living polymer, and a specific capping agent was prepared. By capping the terminal active lithium with, and reacting the halogen-containing epoxy compound or the halogen-containing vinyl compound in the slight presence of a specific Lewis base, there is no danger of the raw material used, toxicity, etc. By controlling side reactions, it is possible to increase the efficiency of polymers with radically reactive reactive groups at the ends very efficiently. It found that it is possible to manufacture at a reaction temperature, and have completed the present invention.

That is, the object of the present invention is to solve the conventional problems in industrial practice, in which the Ribinck polymer is capped with a specific capping agent, and a slight amount of a specific Lewis base is present. Provided is a method for safely and efficiently producing a conjugated diene polymer containing a radically polymerizable double bond or an epoxy group at the polymer terminal by reacting with a halogen-containing epoxy compound or a halogen-containing vinyl compound under the conditions below. That is.

[0009]

SUMMARY OF THE INVENTION The present invention comprises at least one
A living polymer is produced by polymerizing a conjugated diene monomer of a kind and a monomer copolymerizable therewith in a hydrocarbon solvent in the presence of an organolithium compound, and then a living polymer is prepared. In the method of reacting with a halogen-containing vinyl compound or a halogen-containing epoxy compound, the living polymer (A) is represented by the general formula (I)

[0010]

[Chemical 2] (In the above formula, R ₁ and R ₂ are each hydrogen, and have 1 to 1 carbon atoms.
8 represents an alkyl group or an aryl group) and is capped with at least one kind of an aromatic vinyl compound represented by

(B) tertiary monoamine, tertiary diamine, 1
Characterized by reacting a living polymer with a halogen-containing vinyl compound or a halogen-containing epoxy compound in the presence of a Lewis base selected from at least one kind of chain ether or cyclic ether having two or more oxygen atoms in the molecule. The present invention relates to a method for producing a conjugated diene-based polymer having at least one radically polymerizable double bond or epoxy group at the polymerization end.

By selecting the specific Lewis base used in the present invention, a living polymer and a halogen-containing vinyl compound or a halogen-containing epoxy compound can be obtained without causing a side reaction even in the presence of a small amount of a Lewis base, which has not been heretofore considered. It is a surprising discovery that the target conjugated diene polymer can be produced by the reaction of. According to the present invention, a conjugated diene-based polymer containing a double bond or an epoxy group capable of being radically polymerized at a polymer terminal at a high temperature which is advantageous in industrial practice without using a toxic substance, a hazardous substance, etc. Can be manufactured safely and efficiently,
It is extremely useful industrially.

The present invention will be described in detail below. The conjugated diene-based polymer having at least one radically polymerizable double bond or epoxy group at the end of the polymer produced by the present invention is copolymerized with at least one conjugated diene-based monomer, if necessary. A living polymer obtained by polymerizing a possible monomer is capped with at least one aromatic vinyl compound, and the living polymer is subjected to a halogen-containing epoxy compound or a halogen-containing vinyl compound in the presence of a Lewis base. It can be obtained by reacting with. The conjugated diene polymer of the present invention is usually produced by using an organic lithium compound in a hydrocarbon solvent.

The organolithium compound used in the present invention may be a monoorganolithium compound or a polyfunctional organolithium compound, or a mixture of a polyfunctional organolithium compound and a monoorganolithium compound. Examples of the organolithium compound include n-propyllithium, iso-propyllithium, n-butyllithium,
sec-butyllithium, tert-butyllithium,
There are penzyl lithium and the like, but n-butyl lithium and sec-butyl lithium are preferably used.

Examples of polyfunctional organolithium compounds include dilithiomethane, 1,4-dilithiobutane, and 1,6.
-Dilithiohexane, 1,4-dilithiocyclohexene, 1,4-dilithio-2-ethylcyclohexane,
1,3-dilithio-4-phenylbutane, 1,2-dilithio-1,2-diphenylethane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,1-dilithiodiphenylene, 1, 4-dilithiobenzene, 1,5
-Dilithionaphthalene, dilithiopolybutadiene, dilithioisoprene, dilithiodiisoprene, dilithiopolyisoprene, 2,2'-2 "-trilithio-p-terphenyl, 1,3,5-trilithiopentene, 1 , 3, 5
-Trilithio-2,4,6-triethylbenzene and the like.

In addition to the above, an organolithium compound substantially containing a polyfunctional organolithium compound by reacting a monoorganolithium compound with another compound may be used. Among these examples, a particularly representative catalyst is
It is a reaction product containing at least two of a monoorganolithium compound and a polyvinyl aromatic compound.

For example, a reaction product of a monoorganolithium compound and a polyvinyl aromatic compound (Japanese Patent Laid-Open No. 48-103).
No. 690), a reaction product obtained by reacting a monoorganolithium compound with a conjugated diene or a monovinylaromatic compound and then reacting a polyvinylaromatic compound, a monoorganolithium compound, a conjugated diene or a monovinylaromatic compound, and polyvinyl. A reaction product (West German Patent No. 2,003,384) in which three aromatic compounds are simultaneously reacted is used.

Further, as shown in Japanese Patent Publication No. 37078/1975, a reaction product of a monoorganolithium compound and a monovinylaromatic compound is reacted with a polyvinylaromatic compound, and then a monovinylaromatic compound is further added. The catalyst obtained by the reaction is also effective.

The term "polyvinyl aromatic compound" as used herein means
Divinylbenzene, 1,2,4-trivinylbenzene,
1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4
-Trivinylbiphenyl and the like, and particularly divinylbenzene is preferable, but divinylbenzene includes o-, m-,
There are p- isomers, which are virtually satisfied with commercially available divinylbenzene, which is a mixture of these isomers. The monovinyl aromatic compound includes styrene, vinyltoluene, vinylethylbenzene, vinylxylene, vinylnaphthalene, etc., and styrene is particularly common.

As the hydrocarbon solvent, aliphatic hydrocarbons such as butane, pentane and hexane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene are used. Preferred examples include hexane and cyclohexane.
In addition, a 1,2-vinyl content adjusting agent such as tetrahydrofuran added to a hydrocarbon solvent may be used.

The conjugated diene monomer used in the present invention is
1,3-butadiene, isoprene, 2,3-dimethyl-
1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene,
Examples of the conjugated diene such as 1,3-hexadiene and the monomer copolymerizable with these conjugated dienes include styrene, α-methyl stymene, p-methyl styrene, divinyl benzene, methyl acrylate, methyl methacrylate and acrylonitrile. Yes, one kind or two or more kinds are used. As the preferred conjugated diene-based monomer, 1,
3-butadiene and isoprene. Further, styrene is mentioned as a preferable example of the monomer copolymerizable with the conjugated diene.

When the polymer having an active lithium terminal of the present invention is a copolymer comprising the conjugated diene and a monomer copolymerizable therewith as described above, the content of the copolymerizable monomer,
Alternatively, the chain distribution of the copolymerizable monomer in the copolymer chain is not particularly limited. The composition distribution of the conjugated diene and the copolymerizable monomer in the copolymer chain may be uniform in the molecular chain, or may be non-uniformly distributed in the molecular chain. It may exist as a block.

The vinyl aromatic compound for capping the active lithium end used in the present invention has the general formula (I).

[Chemical 3] (R ₁ and R ₂ each represent hydrogen, an alkyl group having 1 to 18 carbon atoms, or an aryl group),
For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, p-methylstyrene, diphenylethylene and the like can be mentioned, and these can be used alone or in combination of two or more. Preferred capping agents include styrene and α-methylstyrene.

The amount of these capping agents to be used is usually 1 to 40 per 1 mol of the organolithium compound catalyst used when producing a polymer having an active lithium terminal.
It is preferably in the range of 5 mol to 20 mol, more preferably 5 mol to 20 mol. When it is less than 1 mol, the effect of the present invention is not exhibited, and it may be used in excess of 40 mol, but there is no change in the effect of the present invention and it is not preferable in terms of manufacturing cost.

The reaction of the polymer having an active lithium terminal with the compound occurs immediately when they come into contact with each other, and therefore the reaction time and the reaction temperature can be adjusted over a wide range, but the reaction time is usually several minutes to several hours. The temperature is 15 ℃
Within the range of 120 ° C. The Lewis base used in the present invention is a tertiary monoamine, a tertiary diamine, or a chain or cyclic ether having two or more oxygen atoms in one molecule.

Examples of tertiary monoamines include trimethylamine, triethylamine, methyldiethylamine, 1,
There are compounds such as 1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, N, N-dimethylformamide diisopropylacetal, N, N-dimethylformamide and dicyclohexylacetal; 3
Examples of the primary diamine include N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropanediamine, N, N, N ', N'-tetramethyldiaminobutane, N, N, N', N'-tetramethyldiaminopentane, N, N, N ', N'-tetramethylhexanediamine, dipiperidinomethane , Dipiperidinoethane and other compounds;

Examples of chain ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene dimethyl ether; examples of cyclic ethers include bis (2-oxolanyl) ethane,
2,2-bis (2-oxolanyl) propane, 1,1-
Bis (2-oxolanyl) ethane, 2,2-bis (2-
Oxolananyl) butane, 2,2-bis (5-methyl-)
2-oxolanyl) propane, 2,2-bis (3,4,
Examples thereof include compounds such as 5-trimethyl-2-oxolanyl) propane. One or more of these compounds can be used. As a preferable example, N, N,
N ', N'- tetramethyl ethylene diamine is mentioned.

The amount of the Lewis base used is in the range of 0.7 to 6 mol, preferably 2 to 4 mol, per 1 mol of the organolithium compound catalyst used for producing the polymer having an active lithium terminal. It is in the molar range. If it is less than 0.7 mol, the effect of the present invention will not be exhibited, and if it is used in excess of 6 mol, it is difficult to separate the Lewis base and the polymerization solvent in the solvent recovery step, which is not preferable.

The method of adding the aromatic vinyl compound and the Lewis base is not particularly limited, but it is preferable to add the Lewis base before or during the polymerization of the conjugated diene-based monomer because the proportion of vinyl production increases. Absent. Normal,
After the polymerization is completed, the active lithium end is capped with an aromatic vinyl compound, and then a Lewis base is added, or after the Lewis base is added, the active lithium end is capped, or the aromatic vinyl compound and the Lewis base are added simultaneously. However, the method of capping the active lithium end is preferably used.

These compounds may be used as they are or may be used by dissolving them in a solvent. When a solvent is used, a hydrocarbon solvent which is inactive to active lithium is used. Examples of hydrocarbon solvents are benzene, toluene,
Cyclohexane, n-hexane, etc. can be mentioned.

The halogen-containing epoxy compound and the halogen-containing vinyl compound used in the present invention are not particularly limited, but for example, the general formulas (A) to (I) are used.

[Chemical 4]

[0032]

[Chemical 5]

(In the above formula, R ₁ is an alkylene group having 1 to 6 carbon atoms or an aryl group, and R ₂ , R ₃ , R ₄
Represents hydrogen or an alkylene group having 1 to 6 carbon atoms or an aryl group. A compound represented by the formula (X represents a halogen atom) is generally used.

Examples of (A) include vinyl-2-chloromethyl ether, vinyl-2-chloroethyl ether,
Examples thereof include vinyl-3-chlorobutyl ether, isopropenyl chloromethyl ether, isopropenyl-2-chloroethyl ether, vinyl-2-bromomethyl ether, vinyl-2-bromoethyl ether and the like.

As an example of (B), vinyl chloroacetate,
Bromo vinyl acetate, vinyl 3-chloropropionate, 3
-Vinyl chloroisobutyrate, 4-chloro-vinyl butyrate, 6
Examples thereof include vinyl-chloro-caproate, vinyl 3-bromopropionate, vinyl p-chlorophenylacetate and the like. Examples of (C) include methyl methacrylate, methacrylic acid butyl chloride, methacrylic acid ethyl chloride, acrylic acid methyl chloride, methyl methacrylate bromide and butyl methacrylate bromide. Examples of (D) include vinyl chloride and 4
-Chloro-1-butene, 3-chloro-2-methylpropene, 3-chloropropene, vinyl bromide, 4-bromo-1
-Butene etc. are mentioned.

Examples of (E) are p-chloromethylstyrene, m-chloromethylstyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-chloro-α-methyl. Styrene, m-
Examples thereof include chloro-α-methylstyrene, p-bromomethylstyrene, p-bromostyrene and the like. Examples of (F) include acryloyl chloride, methacryloyl chloride, 2-ethylacryloyl chloride, 2-propylacryloyl chloride, acryloyl bromide, methacryloyl chloride and the like.

Examples of (G) are 2-chloro-3-methylmaleic anhydride, 2-chloro-3-ethylmaleic anhydride, 2-chloro-3-propylmaleic anhydride and 2
-Chloro-3-butyl maleic anhydride, 2-chloromaleic anhydride, 2-bromomaleic anhydride, 2-bromo-
3-methyl maleic anhydride etc. are mentioned. Examples of (H) include dimethyl chloromaleate and 2-chloro-2.
-Diethyl methyl maleate, diethyl 2-chloro-2-methyl maleate, dimethyl 2-chloro-2-ethyl maleate, diethyl 2-chloro-2-ethyl maleate, dimethyl 2-chloro-2-propyl maleate, Examples thereof include dimethyl bromomaleate and dimethyl 2-bromo-2-methyl-maleate.

Examples of (I) are chloroethylene oxide, 3-chloropropylene oxide, 4-chlorobutylene oxide, p-chlorophenylethylene oxide, m-chlorophenylethylene oxide and p-.
Examples thereof include chloromethylphenylethylene oxide, m-chloromethylphenylethylene oxide, bromoethylene oxide, 3-bromopropylene oxide and the like. These compounds (A) to (I) are used alone or in combination of two or more.

The amount of the halogen-containing epoxy compound or halogen-containing vinyl compound to be reacted with the polymer having an active lithium terminal used in the present invention is the organolithium compound catalyst used in producing the polymer having an active lithium terminal. The amount is preferably 0.5 mol or more, and more preferably 0.7 mol or more, per 1 mol. If it is less than 0.5 mol, an undesired side reaction occurs in which the polymer chain becomes twice as much as the initial polymer or more, and the desired polymer cannot be obtained. Although it may be used in an amount of more than 1 mol, the compound introduced into the polymer does not change, and therefore it is usually used in the range of 0.5 mol to 1.0 mol.

The reaction between the polymer having an active lithium terminal and the compound takes place immediately when they come into contact with each other, so that the reaction time can be adjusted over a wide range, but the reaction time is usually several seconds to several hours. The reaction temperature between the living polymer and the compound is in the range of 40 ° C to 120 ° C, preferably 70 ° C to 100 ° C. The reaction temperature may be lower than 40 ° C. and the liping polymer may be reacted with the halogen-containing vinyl compound or the halogen-containing epoxy compound, but there is no change in the ratio of side reaction products due to the reaction,
It requires a special operation for cooling the reaction tank, which is not preferable in industrial practice. Also, the reaction temperature is 12
If the temperature exceeds 0 ° C, the proportion of the side reaction product formed becomes high, which is not preferable.

The compound may be used as it is or may be used by dissolving it in a solvent. When a solvent is used, a hydrocarbon solvent which is inactive to active lithium is used.
Examples of the hydrocarbon solvent include benzene, toluene, cyclohexane, n-hexane and the like.

The living polymer having active lithium at the polymer terminal used in the present invention has a weight average molecular weight (hereinafter referred to as Mw) of 5,000 to 1,000,000. The molecular weight in the present invention is a polystyrene-equivalent molecular weight measured and calculated by GPC. When the Mw of the living polymer is less than 5,000, a large amount of a polar compound is necessary to suppress a side reaction when the living polymer is reacted with the halogen-containing vinyl compound, which is preferable for industrial implementation. Absent. Further, when Mw is larger than 1,000,000, the amount of terminal epoxy groups or double bonds per unit weight of the polymer becomes small, and the effect of the present invention cannot be expected.

The conjugated diene polymer having a reactive group at the terminal produced by the present invention utilizes a double bond or an epoxy group at the terminal to synthesize a graft polymer or a block polymer, an adhesive agent, Raw materials such as coating materials and molding materials, and styrene-based resins (H
It is useful as a rubber used to obtain IPS, ABS, etc.).

[0044]

EXAMPLES Hereinafter, specific examples of the present invention will be shown by some examples, but this is for more specifically explaining the gist of the present invention and does not limit the present invention. .. (Examples 1 to 13) 1,3-as a conjugated diene monomer
Butadiene or 1,3-butadiene and styrene, n-butyllithium as a polymerization initiator, and n-butyl as a solvent.
Using hexane, a living polymer solution having an active lithium terminal was obtained. The living polymer was polymerized as follows.

That is, an autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, 1,3-butadiene which had been previously purified and dried, or
1,3-butadiene, styrene and n-hexane are added,
In some cases, tetrahydrofuran was also added as a 1,2-vinyl containing modifier. Then, a 5 wt% n-hexane solution of n-butyllithium was added to initiate polymerization at 70 ° C. The polymerization temperature rose to about 100 ° C. to obtain a living polymer solution. Then, the styrene monomer was added only to the living polybutadiene solution to cap the living polybutadiene. Then, a Lewis base was added, an end treatment agent was added to the obtained polymer solution, and the reaction was carried out for 30 minutes. This reaction was carried out at the reaction temperatures shown in Tables 1-2.

Tables 1 and 2 show the raw materials, the amount of the raw materials charged, and the properties of the synthetic products. To the polymer solution thus obtained, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol (BHT) was added as a stabilizer per 100 parts by weight of the polymer, and the solvent was removed by heating. A terminal modified polybutadiene rubber of was obtained.

[0047]

[Table 1]

[0048]

[Table 2]

(Note) n-butyllithium: 5% by weight n-
Amount of butyllithium in hexane solution DPE: 1,1-diphenylethylene d-MST-: d-methylstyrene A: N, N, N ', N'-tetramethylethylenediamine B: 1,1-dimethoxytrimethylamine C: triethylamine D: 1,2-dimethoxyethane I: chloromethylstyrene II: vinyl-2-chloroethyl ether III: epichlorohydrin

The weight average molecular weight of the terminal-modified polybutadiene rubber is a polystyrene conversion value in gel permeation chromatography (GPC). The by-product ratio (%) was calculated from the curve obtained by GPC as shown in FIG.

[0051]

[Equation 1] S ₁ : Area of main component obtained from GPC curve S ₂ : Area of by-product (dimer) obtained from GPC curve

(Comparative Examples 1 to 3) Polymerization of 1,3-butadiene was carried out except that the solvent was tetrahydrofuran and the addition amounts of the styrene monomer, the Lewis base, and the terminal treating agent were as shown in Table 3. It carried out by the method similar to Example 1. (Comparative Examples 4 to 7) After the completion of 1,3-butadiene polymerization, the same procedure as in Example 1 was carried out except that the amounts of styrene-based monomer, Lewis base and terminal treating agent were changed to those shown in Table 3. ..

[0053]

[Table 3]

(Note) n-butyllithium: 5% by weight n-
Amount of butyllithium in hexane solution DPE: 1,1-diphenylethylene A: N, N, N ', N'-tetramethylethylenediamine I: chloromethylstyrene

Comparative Examples 14 to 22 Next, an organolithium-based catalyst, which is a reaction product containing at least a monoorganolithium compound and a polyvinylaromatic compound, was prepared, and this was used to terminate the active lithium terminal. A living polybutadiene having the above was obtained. Table 4 shows a method for preparing the organolithium-based catalyst.

[0056]

[Table 4] (Catalyst preparation ratio) (Note) * Divinylbenzene / n-butyllithium (molar ratio)

The catalysts prepared by the method of Table 4 are soluble in n-hexane. The divinylbenzene used was a commercially available divinylbenzene which contained 57% by weight of the isomer mixture, the balance being ethylvinylbenzene and diethylbenzene. The terminal-modified polybutadiene rubbers of Tables 5 to 6 were obtained in the same manner as in the production method of Example 1, except that the two kinds of organolithium-based catalysts thus obtained were used.

[0058]

[Table 5]

[0059]

[Table 6]

(Note) A: N, N, N ', N'-tetramethylethylenediamine B: 1,1-dimethoxytrimethylamine C: 1,2-dimethoxyethane a: chloromethylstyrene b: methacrylic acid chloride C: vinyl -2-chloroethyl ether

The amount of the organolithium-based catalyst used is shown in terms of n-butyllithium. By-product ratio (%) is G
As shown in FIG. 2 from the curve obtained by PC, it is the value calculated by the following equation 2.

[Equation 2] S ₁ : Area of main polymer before reaction with terminal treatment agent determined by GPC curve S ₂ : Area of high molecular weight portion before reaction with terminal treatment agent determined by GPC curve S ₃ : Termination determined by GPC curve Area of main product after reaction with treating agent S ₄ : Area of high molecular weight portion after reaction with terminal treating agent determined by GPC curve

(Reference Example) Chloromethylstyrene-terminated low molecular weight polybutane
Production of diene : An autoclave equipped with a stirrer and a jacket with an internal volume of 2 L was washed and dried, and after purging with nitrogen, purification /
100 g of dried 1,3-butadiene and n-hexane 8
00 g was added. Then, 5.9 ml of a 5 wt% n-hexane solution of n-butyllithium was added and polymerization was initiated at 60 ° C. The polymerization temperature was raised to about 100 ° C to obtain a living polybutadiene solution. Next, 4 ml of styrene was added to the living polybutadiene solution and reacted for 10 minutes to cap the living polybutadiene end.
Then, 1.6 ml of N, N, N ', N'-tetramethylethylenediamine was added, and the mixture was stirred for 5 minutes. Chloromethylstyrene (0.5 ml) was added to the obtained polymer solution and reacted for 30 minutes.

The polymer thus obtained was repeatedly reprecipitated in a THF / methanol system to remove residues of the terminalizing agent and the catalyst for purification, and then vacuum dried at room temperature.
The weight average molecular weight of this polymer is 51,000,
The molecular weight distribution (Mw / Mn) was 1.15. The polymer thus obtained was confirmed by ¹ H-NMR [AC-300P (300 MHz) manufactured by Bruker) to have a double bond introduced at the terminal.

The chemical shift of the proton of the terminal double bond obtained from ¹ H-NMR analysis of this polymer is shown below. ¹ H-NMR (300 MHz: TMS standard):

[Chemical 6]

[0065]

According to the present invention, a conjugated diene copolymer having a radically polymerizable double bond or an epoxy group at the polymer end can be produced at a high temperature which is advantageous in industrial practice, and It can be efficiently produced by using highly safe raw materials, and the industrial significance of the present invention is extremely great.

This conjugated diene polymer is used for producing a graft or block copolymer by reacting with another radically polymerizable monomer by utilizing an epoxy group or a double bond at the molecular end. It is useful as a raw material. Further, it is suitable as a raw material for adhesives, coating materials, molding materials and the like, and is also useful as a resin modifier.

[Brief description of drawings]

FIG. 1 is a GPC curve of the polymer obtained in Comparative Example 3.

FIG. 2 is a GPC curve of the polymer obtained in Example 20 before and after the reaction with the terminating agent.

FIG. 3 is an'H-NMR spectrum of the polymer obtained in Reference Example.

Claims (1)

[Claims] 1. A living polymer obtained by polymerizing at least one conjugated diene-based monomer and optionally a monomer copolymerizable therewith in a hydrocarbon solvent in the presence of an organolithium compound. And then reacting the living polymer with a halogen-containing vinyl compound or a halogen-containing epoxy compound, wherein (A) the living polymer is represented by the general formula (I): (In the above formula, R ₁ and R ₂ are each hydrogen, and have 1 to 1 carbon atoms.
8 represents an alkyl group or an aryl group) and is capped with at least one kind of an aromatic vinyl compound represented by (B) a tertiary monoamine, a tertiary diamine, and a chain having two or more oxygen atoms in one molecule. In the presence of a Lewis base selected from at least one kind of cyclic ether or cyclic ether,
A method for producing a conjugated diene-based polymer having at least one radically polymerizable double bond or epoxy group at a polymerization end, which comprises reacting a living polymer with a halogen-containing vinyl compound or a halogen-containing epoxy compound.