JP2001181306A - Method for manufacturing isobutylene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for economically manufacturing an isobutylene polymer having a good molecular weight distribution by satisfying mixing performance necessary for keeping catalyst dispersion and heat exchange with a small mixing power and decreasing a load on a refrigerator to increase an energy efficiency in polymerizing an isobutylene monomer using an initiator and a catalyst. SOLUTION: There is used a cylindrical mixing vessel in the central portion of which a rotary mixing axis having broad width plate blades is rotatably mounted from outside the vessel in polymerizing an isobutylene monomer in the mixing vessel using an aromatic-based initiator and a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an isobutylene-based polymer, and more particularly to a method for producing an isobutylene-based polymer in an agitation tank using an aromatic initiator.

[0002]

2. Description of the Related Art Materials based on isobutylene polymers obtained by polymerizing isobutylene monomers using an aromatic initiator and a catalyst have excellent properties such as viscoelasticity, weather resistance and gas-passing properties. It is used for applications such as coating materials, sealing materials for buildings, and sealing materials for electronic materials. (Note that the aromatic initiator in the present invention refers to a polymerization initiator having an aromatic ring in the molecule.)

As a method for producing such an isobutylene-based polymer, Japanese Patent Application Laid-Open No. Hei 7-292038 discloses a method for controlling the dielectric constant of a solvent to carry out polymerization while balancing the polymerization rate and the polymer solubility. JP-A-53514 discloses a method of polymerizing either a chlorinated hydrocarbon or an aromatic hydrocarbon alone or in a solvent mixed with an aliphatic hydrocarbon using an aromatic initiator and a catalyst. ing.

In general, when producing an isobutylene-based polymer, a solvent, an isobutylene monomer, and an initiator are charged in a stirring tank in advance, and if necessary, an electron donor is mixed, a catalyst is added, and a polymerization reaction is carried out. Subsequently, a compound having a vinyl group is introduced into the terminal of the polymer by an addition or substitution reaction. At this time, the added catalyst is uniformly stirred and dispersed in a short time in order to suppress a side reaction and secure a good weight average molecular weight / number average molecular weight ratio (hereinafter referred to as a molecular weight distribution) in the polymerization. There is a need.

Further, isobutylene monomer is 13 kcal.
/ Mol of polymerization heat, and the polymerization is a large exothermic reaction and a rapid exothermic reaction. Therefore, in order to suppress a side reaction and obtain a polymer having a good molecular weight distribution, the temperature of the reaction solution due to the reaction must be increased. Therefore, the stirring tank needs to have sufficient heat removal performance. The reaction temperature is usually -100 to-
Since the temperature is extremely low at 30 ° C., it is necessary to perform cooling using a large-sized refrigerator. In addition, since a large-sized refrigerator at a very low temperature consumes a large amount of power, it is economically possible to minimize the heat input by stirring. desirable.

In general, as a stirring reaction tank for producing an isobutylene-based polymer, a stirring tank having one to three stages of paddle blades, inclined paddle blades, turbine blades, squid blades, or the like has been used. I've been. However, in the conventional stirring tank, the mixing performance required for dispersing the catalyst,
In order to obtain the heat transfer performance required for heat removal, it is necessary to increase the power required for stirring. In addition, since the polymerization of isobutylene has a high heat generation rate and a large heat generation amount, one is placed in a stirring tank to remove heat.
In some cases, a triple cooling coil is provided. However, when such a coil is provided, the mixing performance required for dispersing the catalyst and ensuring the heat transfer performance is reduced. As a result, the heat input by the stirring increases, the load on the refrigerator increases, and eventually the energy efficiency of the refrigerator decreases, which is economically disadvantageous.

[0007]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention relates to a method for polymerizing isobutylene monomer in a stirring tank using an initiator and a catalyst. Provide a method for economically producing an isobutylene-based polymer having a good molecular weight distribution by satisfying the mixing performance required for ensuring performance, reducing the load on the refrigerator, and improving the energy efficiency of the refrigerator. It is assumed that.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a method for polymerizing isobutylene monomer using an aromatic initiator and a catalyst in a stirring vessel, wherein a rotary stirring shaft having wide flat blades is provided in a cylindrical stirring vessel. This is a method for producing an isobutylene-based polymer using a stirring tank installed at the center so as to be drivable from outside the tank.

In a preferred aspect of the present invention, the rotary stirring shaft provided with the wide flat plate blade has a paddle blade made of a wide flat plate disposed at the bottom of the stirring tank at the lowest stage, and further has a comb-like shape. The wings are mounted in the middle and upper stages, and the middle comb-shaped wing adjacent to the paddle wing located at the lowermost stage is arranged ahead of the rotation direction at an intersection angle of less than 90 degrees, and , The lowermost paddle blade and the upper middle comb-shaped wing overlap in the axial direction, and the upper-stage comb wing adjacent to the middle-stage comb-shaped wing Wings are arranged ahead of the direction of rotation at an intersection angle of less than 90 degrees, and the middle comb wing and the upper comb wing adjacent above have an overlap in the axial direction Things.

In another preferred embodiment of the present invention, in the polymerization reaction, either a chlorinated hydrocarbon or an aromatic hydrocarbon alone or a mixture of any of these and an aliphatic hydrocarbon, preferably toluene A single reaction or a mixture of toluene and an aliphatic hydrocarbon is used, and the reaction temperature is -100 to -30C.

In still another preferred embodiment of the present invention, the terminal vinyl group is introduced into the polymer by adding or substituting a compound having a vinyl group following the polymerization reaction. It is preferable that the introduction of the terminal vinyl group into the polymer is carried out in the same stirring tank or another stirring tank of the same type after the polymerization reaction under stirring, when the stationary reaction in which stirring is stopped is performed. Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a stirring tank is
A stirring shaft that can be driven from outside the tank is installed in the center of the stirring tank,
A cylindrical stirring tank having a wide flat blade on the shaft can be used.

As the flat blade, a conventionally known flat plate can be used without limitation, and the stirring blade may have a wavy structure. As the flat blade, for example, a flat bottom paddle described in Japanese Patent Application Laid-Open No. 9-108557 is mounted on the bottom, and a lattice blade composed of a vertical member and a horizontal member is mounted on the bottom, and Japanese Patent Application Laid-Open No. 5-49890. JP-A-5-247199, in which an upper paddle wing described in Japanese Patent Application Laid-Open No. 5-247199 is arranged ahead of an upper and lower adjacent paddle wing at an intersection angle of 45 to 75 degrees in the rotation direction.
No. JP-A 10-242
No. 30, a paddle blade made of a wide flat plate arranged at the bottom of the tank of the stirring tank is mounted on the lowermost stage, and a comb-shaped blade is mounted on the middle and upper stages on the stirring shaft provided at the center of the stirring tank. The middle comb-shaped wing adjacent to the uppermost paddle wing is positioned ahead of the paddle wing located at an intersection angle of less than 90 degrees with respect to the rotation direction, and The middle comb-shaped wing adjacent to the wing has an overlap in the axial direction, and the upper comb-shaped wing adjacent to the middle wing is less than 90 degrees with respect to the middle-shaped comb-shaped wing. The comb-shaped blade in the middle stage and the upper comb-shaped blade in the upper stage adjacent to the upper stage are overlapped in the axial direction at the intersection angle, and the comb-shaped blade in the middle stage is overlapped in the axial direction. JP 1
No. 0-24230) can be suitably used. Specifically, for example, Soken Chemical Co., Ltd. Hi-F mixer (trade name), Shinko Pantech Co., Ltd. Full Zone (trade name), Sumitomo Heavy Industries, Ltd. Max Blend (trade name) and the like can be mentioned. . In the present invention, among them,
The stirring blade described in the above publication is preferable because it has good mixing characteristics and requires less power even if it is a highly viscous liquid.

FIG. 1 illustrates a specific embodiment of a stirring vessel provided with a stirring blade described in Japanese Patent Application Laid-Open No. 10-24230. In FIG. 1, a stirring shaft 2 is provided at the center of the stirring tank 1. Reference numeral 3 denotes two paddle blades, which are attached to the lower end of the stirring shaft 2. 4 is the paddle wing 3 located at the bottom
, A middle comb-shaped wing adjacent thereto is shown.
The comb-shaped wing 4 is arranged ahead of the paddle wing 3 with respect to the rotational direction at an intersection angle of 45 degrees, and the lowermost paddle wing 3 is located at the lowermost stage with respect to the axial direction. It has an overlap of 3.9% with respect to the axial height from the lower end of the stirring blade to the upper end of the uppermost blade. 5 is the middle comb-shaped wing 4
And the upper comb-shaped wing adjacent to the upper. The upper comb-shaped wing 4 is arranged ahead of the middle comb-shaped wing 4 in the rotational direction at a crossing angle of 45 degrees with respect to the middle comb-shaped wing 4. 2. With respect to the axial height from the lower end of the lowermost stirring blade to the upper end of the uppermost blade.
It has 9% overlap. The shape of the uppermost blade 5 is different from the shape of the middle comb blade 4, and has a shape in which the blade 4 is halved in the axial direction at the center of the blade.

In the above publications, examples of application of the above-described stirring blades to various polycondensation processes are disclosed. However, there is no disclosure or suggestion of application to an isobutylene-based polymer. However, by applying the present invention, it is possible to solve the problems of the present invention as described below.

In the present invention, an initiator (polymerization initiator) is present in the reaction system. As the polymerization initiator, it is preferable to use a compound in which tertiary carbon is added to an aromatic compound. It is preferable to use a tertiary carbon having a structure in which a halogen, an ether or an ester is bonded. As such a material, for example, 1,4-bis-α-chloroisopropylbenzene (hereinafter referred to as p-DCC), 1,3,5-tris-α-chloroisopropylbenzene, or the like can be used.
Depending on the molecular weight of the polymer to be produced, the amount of the initiator used can be such that the ratio of the weight of the isobutylene monomer to 1 mol of the initiator is 500 to 500,000 g.
For example, in order to produce a polymer having a molecular weight of about 10,000, the ratio of isobutylene may be 10,000 g per mol of the initiator.

In the present invention, examples of the catalyst include:
TiCl ₄ , AlCl ₃ , BCl ₃ , ZnCl ₂ , Sn
Cl ₄ , ethyl aluminum chloride (C ₂ H ₅ Al
Lewis acids such as Cl ₂ ) and SnBr ₄ can be used. The amount of the catalyst used is 0.1 to 10% based on the polymerization initiator.
A molar number of 100 times, preferably 1 to 10 times can be used. Alternatively, the molar number can be usually 0.001 to 1 times based on the isobutylene monomer.

In the present invention, an electron donor may be used. Examples of the electron donor include pyridine,
2-methylpyridine (also referred to as picoline), trimethylamine, dimethylacetamide (abbreviated as DMAc), DMSO, ethyl acetate, and the like can be used. When an electron donor is added, the amount is preferably smaller than that of the catalyst, and the amount is preferably 0.1 to 10% based on the amount of the polymerization initiator.
The molar amount can be in the range of 01 to 10 times the molar amount.

In the method of the present invention, the reaction temperature is -10
It can be in the range of 0 to 0 ° C. Under a relatively high temperature condition, the reaction rate is low and side reactions such as a chain transfer reaction may occur. Therefore, it is preferable to select a range of -100 to -30C. Under conditions where the reaction temperature is low, the solubility of the polymer may be reduced to cause precipitation. Therefore, a more preferable reaction temperature is -90 ° C to -30 ° C.

In the method of the present invention, the reaction solvent includes
For example, by using a chlorinated hydrocarbon or an aromatic hydrocarbon alone or as a mixture of any of these and an aliphatic hydrocarbon, the dielectric constant of the reaction solution at room temperature is 1 to 5, and the solubility parameter is 7 0.5-9.0
It is preferred that As the chlorinated hydrocarbon, for example, methane dichloride, methane chloride, ethane dichloride, propane chloride, butane chloride and the like can be used. As the aromatic hydrocarbon, for example, benzene, toluene, biphenyl, xylene, ethylbenzene and the like can be used. As the aliphatic hydrocarbon, for example, octane, heptane, hexane, pentane, butane, propane and the like can be used. Chlorinated hydrocarbons have a high dielectric constant and a large solubility parameter value. For example, the relative dielectric constant of methane dichloride at room temperature is 7.7 and the solubility parameter is 9.7. By mixing, predetermined relative permittivity and solubility parameters can be obtained. For example, it is preferable to use a reaction solvent in which methane dichloride and aliphatic hydrocarbon are mixed at a volume ratio of 2: 8 to 5: 5.

Since aromatic hydrocarbons have a medium dielectric constant and a large solubility parameter, a smaller amount of aliphatic hydrocarbons may be mixed than in the case of chlorinated hydrocarbons. Further, by controlling the polymerization reaction rate under a condition of a low dielectric constant, a polymer having a narrower molecular weight distribution can be obtained. When the reaction temperature is -60 to -30C, good polymerization of isobutylene can be performed. Further, it can be used as a mixed solvent with an aliphatic hydrocarbon. For example, toluene and an aliphatic hydrocarbon are 9: 1.
It is preferable to mix at a volume ratio of up to 6: 4. As the aliphatic hydrocarbon, those described above can be used. The main purpose of mixing toluene and the aliphatic hydrocarbon is to dissolve the polymer because it precipitates at −50 ° C. or lower with toluene alone. When the reaction is carried out only with an aliphatic hydrocarbon, the chain transfer reaction becomes dominant, and a desired polymer may not be obtained. In such a case, the respective solvents may be mixed at the above ratio. .

The amount of isobutylene monomer charged into the reaction solvent is preferably 15 mol / L or less. If the concentration is high, the polymer may be precipitated. On the other hand, if the charged amount is small, the productivity is reduced. Therefore, the charged concentration of the isobutylene monomer is preferably set to 1 to 50% by weight. It is more preferable to handle the union in a dissolved state.

The isobutylene-based polymer of the present invention is one containing 50% by weight or more of an isobutylene unit. That is, in the present invention, other cationically polymerizable monomers may be added for copolymerization. Other cationically polymerizable monomers include, for example, 2-butene and 2-butene.
Aliphatic olefins such as methyl-1-butene, 3-methyl-2-butene, pentene, hexene, cyclohexene, vinylcyclohexane, 5-ethylidene norbornene, indene and β-pinene; dienes such as cyclopentadiene and dicyclopentadiene Styrenes such as styrene, α-methylstyrene, p-chlorostyrene and the like, which can be used in less than 50% by weight based on the isobutylene monomer.

In the method of the present invention, the terminal of the isobutylene-based polymer may have a structure in which chlorine is bonded to tertiary carbon. By performing a reaction for introducing another functional group following the polymerization reaction, It is also possible to obtain a polymer exhibiting a function according to the purpose. Examples of the reactive functional group introduced to the terminal include an allyl group, a hydroxyl group, an allylphenyl ether group, a phenol group, and the like. In order to introduce such a terminal group, a phenol is bonded by a Friedel-Crafts reaction, a substitution reaction with a compound having a vinyl group, for example, allylsilane such as allyltrimethylsilane, or a general formula CH ₂ ＣＨCH (CH ₂ ) _n CH
A compound represented by ＝ CH ₂ [where the hydrogen of (CH ₂ ) _n may be substituted with an alkyl group, preferably a methyl group or the like. n is an integer, preferably an integer of 1 to 30. Particularly preferably, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 3-methyl-1,7-octadiene, 4-methyl-1,9-decadiene, 5-methyl -1,9-decadiene] to give a vinyl end. The compound having such a functional group can be used in an amount of 100 times or less based on the isobutylene-based polymer.

The introduction of the vinyl group can be carried out at the time of carrying out the stationary reaction with the stirring stopped after the polymerization reaction with stirring. At this time, the static reaction may be performed in the same stirred tank in which the polymerization reaction has been performed, or may be transferred to another reactor of the same type or another type of stirred tank, or a tank without a stirrer, and then statically reacted. It is also possible to carry out a substitution reaction. It is preferable that the introduction of the vinyl group is carried out by allowing the vinyl group to stand in a tank different from the stirring tank in which the polymerization reaction has been carried out. The introduction of the vinyl group is carried out under a known condition, for example, at a temperature of 0 ° C. to the boiling point of the solvent for a few minutes to several hours.

By applying the production method of the present invention, it is possible to increase the conversion of a monomer to a polymer with a small power required for stirring and obtain an isobutylene-based polymer having a good molecular weight distribution. Further, since the power required for stirring is small, the load on the refrigerator is reduced, and the production can be performed economically. Furthermore, when a vinyl group is introduced at the terminal, a polymer having a high terminal introduction ratio can be obtained.

[0027]

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

Example 1 To a 2 L stirring tank equipped with a stirring blade and a single cooling coil described in Japanese Patent Application Laid-Open No. H10-24230, 766.5 m of toluene was added.
l, hexane 328.5 ml, isobutylene monomer 4
38 ml, p-DCC 4.52 g, picoline 727 mg
Was charged. A dry ice-ethanol bath was placed on the outer periphery of the reactor, and the temperature was adjusted to -70 ° C while stirring and mixing.
The reaction was started by adding 10.71 g of titanium tetrachloride to the reactor while stirring at 35 rpm. After completion of the reaction, 6.69 g of allyltrimethylsilane was added and reacted. After the completion of the reaction, the reaction solution was poured into a large amount of water or warm water and stirred to wash, and the organic phase and the aqueous phase were separated to remove the catalyst. The organic phase volatile component was removed by an evaporation operation to obtain a polymer product. The organic phase was dried and the conversion of the product polymer, measured by weight of the polymer, was 100%. As a result of measuring the molecular weight and distribution of the product polymer by GPC analysis, the number average molecular weight (Mn) was obtained.
= 16500, molecular weight distribution = 1.2. According to NMR analysis, the terminal introduction ratio of the product polymer was 1.9. If the molecular weight distribution is 1.2 or less, it can be said that the polymer is a good polymer, and it was confirmed that a good polymer was obtained. Table 1 shows the evaluation results of the polymers. In addition,
The determination criteria for the polymers in Table 1 are as follows. ：: Polymer having a molecular weight distribution of 1.2 or less (good polymer) △: Polymer having a molecular weight distribution exceeding 1.2 and 1.3 or less (poor polymer) ×: Polymer having a molecular weight distribution exceeding 1.3 ( Bad polymer)

Example 2 Using the same stirring tank as in Example 1, the same raw materials were charged and reacted at a rotation speed of 100 rpm. The evaluation results of the obtained polymer are shown in Table 1.

Comparative Example 1 In a 2 L stirring tank equipped with three inclined pitched paddle blades and a single cooling coil, 766.5 ml of toluene, 328.5 ml of hexane, 438 ml of isobutylene monomer, p
4.52 g of DCC and 727 mg of picoline were charged.
A dry ice-ethanol bath was placed on the outer periphery of the reactor, and the temperature was adjusted to -70 ° C while stirring and mixing. The reaction was started by adding 10.71 g of titanium tetrachloride to the reactor while stirring at 35 rpm. After completion of the reaction, 6.69 g of allyltrimethylsilane was added and reacted. After the completion of the reaction, the reaction solution was poured into a large amount of water or warm water and stirred to wash, and the organic phase and the aqueous phase were separated to remove the catalyst. The organic phase volatile component was removed by an evaporation operation to obtain a polymer product. The organic phase was dried and the conversion of the product polymer, measured by weight of the polymer, was 81%. As a result of measuring the molecular weight and distribution of the product polymer by GPC analysis, the number average molecular weight (Mn) was 13,400,
When the molecular weight distribution was 1.4, the terminal introduction ratio of the product polymer by NMR analysis was 1.43, which was a defective product, and the conversion was 81%.
Was low. The evaluation results of the polymers are summarized in Table 1. As described above, when the rotation speed was the same as that in Example 1, the mixing was insufficient with the stirring blade, and thus the obtained polymer was defective.

Comparative Example 2 The same raw material was charged into the same 2 L stirring tank as in Comparative Example 1,
The reaction was performed at 0 rpm. The evaluation results of the obtained polymer are shown in Table 1. Although the molecular weight distribution and the conversion of the polymer were improved, they were not as high as in Example 1, and the required power was increased to 3.8 times that of Example 1.

Comparative Example 3 The same raw material was charged into the same 2 L stirring tank as in Comparative Example 1, and
The reaction was performed at a rotation speed of 00 rpm. The evaluation results of the obtained polymer are shown in Table 1. Although the molecular weight distribution and the conversion of the polymer were improved, it was not as high as in Example 1, and the required power was increased 18 times as compared with Example 1.

Comparative Example 4 The same raw material was charged into the same 2 L stirring tank as in Comparative Example 1,
The reaction was performed at a rotation speed of 00 rpm. The evaluation results of the obtained polymer are shown in Table 1. Although the molecular weight distribution and conversion of the polymer were improved, they were not as high as in Example 1, and the required power was increased 480 times as compared with Example 1.

From the results shown in Table 1, according to the stirring tank using the stirring blade described in Japanese Patent Application Laid-Open No. 10-24230 using wide flat blades (Example 1), the same rotation speed and the conventional stirring blade were used. Is higher than in the case of applying (Comparative Example 1). Further, according to Example 1, a polymer having a good molecular weight distribution could be obtained. On the other hand, in the comparative example, a good molecular weight distribution cannot be obtained. That is, even if the required power is increased by setting the rotational speed to 60 or 100 rpm, the molecular weight distribution is not improved to a favorable range (Comparative Example 2 or 3), and when the rotational speed is further increased, the tendency is likely to deteriorate (Comparative Example). Example 4). On the other hand, when the reaction was carried out using a stirring blade described in JP-A-10-24230 and further increasing the number of revolutions, a better molecular weight distribution than in Example 1 was obtained (Example 2).

[0035]

[Table 1]

[0036]

According to the present invention, the isobutylene-based polymer having a good molecular weight distribution and satisfying the mixing performance required for dispersing the catalyst and securing the heat transfer performance with less power required for stirring than the prior art is used. Coalescence can be obtained. Further, according to the present invention, the load on the refrigerator can be reduced, the energy efficiency of the refrigerator can be improved, and the isobutylene-based polymer can be produced economically.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a stirring tank provided with a stirring blade described in Japanese Patent Application Laid-Open No. 10-24230.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Stirring tank 2 Stirring shaft 3 Lower paddle blade 4 Middle comb-shaped blade 5 Upper comb-shaped blade 6 Baffle plate

Continued on front page F-term (reference) 4J011 DA04 DB12 DB16 DB19 HA03 HA06 HB02 HB03 HB06 HB18 HB22 4J015 DA13 DA14 DA16 DA24 4J100 AA05Q AA06P AA07Q AA08Q AA16Q AA20Q AB02Q AB03Q AB08Q AR05Q AR09Q AR10 FA04 FA47 HA35 HA62 HC01 HC80 HE14 JA01 JA43 JA67

Claims (9)

[Claims] 1. When an isobutylene monomer is polymerized using an aromatic initiator and a catalyst in a stirring tank, a rotary stirring shaft having wide flat blades can be driven to the center of the cylindrical stirring tank from outside the tank. A method for producing an isobutylene-based polymer, characterized by using a stirring tank installed in a plant. 2. A rotary stirring shaft having a wide flat plate blade has a paddle blade made of a wide flat plate disposed at the bottom of a stirring tank, and a comb-shaped blade mounted at the middle and upper stages. Then, with respect to the paddle wing located at the lowermost stage, the comb-shaped wing of the middle stage adjacent above is arranged ahead of the rotation direction at an intersection angle of less than 90 degrees, and the paddle wing of the lowermost stage is arranged. The middle comb-shaped wing adjacent above has an overlap in the axial direction, and the comb-shaped wing adjacent to the middle is smaller than the comb-shaped wing adjacent to the middle by less than 90 degrees. 2. The intermediate comb-shaped wing and the upper adjacent comb-shaped wing which are arranged ahead of the rotation direction at the intersection angle of, and overlap with each other in the axial direction. Manufacturing method. 3. The process according to claim 1, wherein in the polymerization reaction, either a chlorinated hydrocarbon or an aromatic hydrocarbon is used alone, or a mixture of any of these and an aliphatic hydrocarbon is used as a solvent. Method. 4. Use of toluene alone or a mixture of toluene and an aliphatic hydrocarbon as a solvent at a reaction temperature of -10
The method according to claim 3, wherein the temperature is 0 to -30 ° C. 5. The method according to claim 1, further comprising using an electron donor.
5. The production method according to any one of 4. 6. Isobutylene is added to the polymerization reaction solution in an amount of 1 to 50.
The production method according to any one of claims 1 to 5, wherein the preparation is performed in a range of% by weight. 7. The method according to claim 1, wherein the vinyl group is introduced to the terminal of the polymer by adding or substituting a compound having a vinyl group following the polymerization reaction. 8. The introduction of a vinyl group is carried out in the same stirring tank or another stirring tank of the same type following the polymerization reaction under stirring.
The production method according to claim 7, which is carried out when performing a stationary reaction with stirring stopped. 9. The catalyst is a Lewis acid and the initiator is 1,4.
9. The method according to claim 8, wherein the compound is -bis (α-chloroisopropyl) benzene, and allyltrimethylsilane or 1,9-decadiene is used as the compound having a vinyl group.