JPH0853514A - Production of isobutene-based polymer - Google Patents

Abstract

PURPOSE:To produce a polymer suppressed in subsidiary reaction and having controlled molecular weight and reduced subsidiary product by reacting a reactional liquid containing isobutene monomer, an aromatic initiator, a catalyst and a specific solvent while controlling permittivity and solubility. CONSTITUTION:This method for producing an isobutene-based polymer comprises carrying out polymerization of isobutene monomer while controlling the reaction liquid so that the permittivity of a reactional liquid is 1-5 and solubility parameter is 7.5-9.0 using a solvent comprising a chlorinated hydrocarbon or aromatic hydrocarbon or a mixture of the hydrocarbon with an aliphatic hydrocarbon when the isobutene monomer is polymerized using an aromatic initiator and a catalyst. In the producing method, a compound having a vinyl group is preferably introduced into the terminal of the polymer by addition reaction or substitution reaction, followed by the polymerization reaction. 1,4-Bis(alpha-chloroisopropyl) benzene is used as an initiator and 1,9-decadiene or allyltrimethylsilane is used as the vinyl group compound. Isobutene is charged in an amount of 1-30wt.%. The reaction temperature is -30 to -60 deg.C as the toluene reaction solvent. A mixed solvent of toluene with an aliphatic hydrocarbon is used as the solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an isobutene polymer. More specifically, it relates to a method for producing an isobutene polymer using an initiator. Materials made from such polymers are used in coating materials, sealing materials for construction, sealing materials for electronic materials, etc. by utilizing their excellent properties such as viscoelasticity, weather resistance, and gas permeation barrier properties. It

[0002]

2. Description of the Related Art It is known that the polymerization reaction of isobutene proceeds by cationic polymerization, and a method of starting from a protic acid in the presence of a Lewis acid catalyst has been developed. As a method for efficiently carrying out the polymerization initiation reaction, polymerization of 1,4-bis (α-chloroisopropyl) benzene (p-DCC: abbreviated as dicumyl chloride) having a chlorine terminal bonded to a tertiary carbon, etc. The inifer method used as an initiator was developed (US Pat. No. 4,276,394).
issue). It is considered that an aromatic compound having a chlorine-terminated tertiary carbon is preferable for forming a highly active cation at the initiation point of polymerization. In the inifer method, the degree of polymerization of the product polymer is controlled by the ratio of the initiator and the isobutene monomer, so that an appropriate molecular weight can be produced in order to express the physical properties according to the application. When the reaction temperature is high, the chain transfer reaction occurs in parallel with the growth reaction in the polymerization reaction to increase the number of polymers, which may make it difficult to set the molecular weight, but at a low temperature of -30 ° C to -100 ° C. It exhibits reactivity similar to living polymerization and suppresses the chain transfer reaction, and the number of polymer molecules can be determined by the initiator.

One of the problems in the conventional inifer method is a decrease in the initiator efficiency due to the indanylation side reaction when using the initiator p-DCC. The molecular weight of the product polymer varies according to the decrease in the initiator due to this side reaction. Another problem is to influence the physical properties by widening the distribution of polymer molecular weight. In order to solve these problems, there is a method of using an additive such as an electron donor (JP-A-2-245004, JP-A 1-3).
18014, JP-A-3-174403).

As a method of using the isobutene polymer as a practical material, a reactive functional group can be introduced into the molecule or at the terminal and cured by means such as vulcanization or crosslinking. Above all, when a bifunctional initiator such as p-DCC is used,
Since both ends of the polymer chain can be made reactive in the chlorinated state of tertiary carbon, it is useful as a cross-linked polyisobutylene rubber. Such a polymer in which a reactive functional group is introduced at the polymer terminal is known as a telechelic polymer. A method has been developed in which a non-conjugated diene represented by the general formula CH ₂ ═CH (CH ₂ ) _n CH═CH ₂ is added in order to introduce a vinyl group at the polymer terminal (JP-A-4-103606). If 1,9-decadiene is used at this time, there is a problem that a low molecular weight product is produced by a side reaction at the same time when the vinyl group is introduced into the polymer terminal. Even if the amount of this low-molecular-weight impurity is small, the content of vinyl groups derived from decadiene is high, so the density of cross-linking points is increased and the physical properties of the product are greatly affected.

It is also known to use allyltrimethylsilane to introduce vinyl groups into polymers. It is considered that the respective problems in producing a telechelic polymer by utilizing the inifer method for living cationic polymerization of isobutene as described above are closely related to the conditions of chemical reaction. In cationic polymerization, it is important that a carbocation is stably formed at the growth end. The cationic polymerization rate tends to increase as the dielectric constant of the reaction solvent increases, and a method using a halogenated hydrocarbon such as dichloromethane or a compound having a nitro group is known (Japanese Patent Laid-Open No. 205304/1988). Kaisho 63-20530
5). To carry out the polymerization reaction in a hydrocarbon solvent, hexane,
A method using pentane, butane, propane, etc. is known (Japanese Patent Publication No. 5-32409).

The rate of isobutene polymerization in halogenated hydrocarbon solvents is relatively fast, generating about 13 kcal / mol of heat of polymerization. Rapid heat generation occurs under the condition that the polymerization reaction is completed in a short time of about 1 to 10 minutes, and especially when the production amount of the polymer becomes large, it becomes a problem to remove the reaction heat and control the temperature. . One of the causes of the distribution of the polymer molecular weight seems to be related to the rate ratio of the initiation reaction and the growth reaction. The indanylation reaction seems to be related to the reactivity of the growing end to attack the aromatic ring of the initiator itself. It is also considered that the side reaction derived from decadiene is due to a mechanism similar to that of cationic polymerization.

Since the temperature condition for carrying out the cationic polymerization is relatively low, the produced polymer may precipitate in the form of gel or solid. In this case, it may adhere to the reaction vessel and cause difficulty in operation, and
To carry out the reaction of introducing a functional group to the polymer terminal, solid-
Since the reaction is between liquids, the reaction rate may decrease. From this viewpoint, it is preferable to select a reaction solvent in which the produced polymer is dissolved.

[0008]

DISCLOSURE OF THE INVENTION The present invention aims to control the molecular weight, improve the efficiency of an initiator, by controlling the synthetic reaction rate of an isobutene polymer and suppressing side reactions.
It is intended to provide a method capable of efficiently producing an isobutene-based polymer having a uniform molecular weight by reducing by-products.

[0009]

The inventors of the present invention have made extensive studies on various factors that govern the reaction with the aim of solving the problems in the production of isobutene polymers.
The invention was completed by finding suitable reaction conditions. That is, the present invention has the following configurations. (1) When polymerizing an isobutene monomer using an aromatic initiator and a catalyst, either a chlorinated hydrocarbon or an aromatic hydrocarbon is used alone or in a solvent mixed with an aliphatic hydrocarbon, Dielectric constant of reaction liquid is 1-5
And a solubility parameter of 7.5 to 9.0, which is a method for producing an isobutene-based polymer. (2) The method for producing an isobutene-based polymer as described in (1), wherein the compound having a vinyl group is introduced into the terminal of the polymer by an addition reaction or a substitution reaction subsequent to the polymerization reaction. (3) The initiator is 1,4-bis (α-chloroisopropyl) benzene, and the vinyl group compound is 1,9-
The method for producing an isobutene-based polymer as described in (1), characterized in that decadiene or allyltrimethylsilane is used. (4) The method for producing an isobutene-based polymer as described in (1), wherein isobutene is charged in the range of 1% by weight to 30% by weight. (5) As a toluene reaction solvent, the reaction temperature is −30 to −
The method for producing an isobutene-based polymer according to (1), wherein the temperature is 60 ° C. (6) The method for producing an isobutene-based polymer according to (1), wherein a reaction solvent obtained by mixing toluene and an aliphatic hydrocarbon in a volume ratio of 9: 1 to 6: 4 is used. (7) Dichloromethane and aliphatic hydrocarbon 2: 8-5:
The method for producing an isobutene-based polymer according to (1), characterized in that a reaction solvent mixed in a volume ratio of 5 is used. (8) A feature of adding an electron donor (1)
A method for producing the isobutene polymer described above. (9) The method for producing an isobutene-based polymer according to (1), wherein the reaction temperature is 0 to -100 ° C.

In the present invention, an initiator (polymerization initiator) is added to the reaction system.
To exist. As the polymerization initiator, it is preferable to use a compound having an aromatic tertiary carbon. It is preferable to use a tertiary carbon having a structure in which a halogen, an ether or an ester is bonded. p-DCC, tricumyl chloride, etc. can be used. The amount of the initiator used can be adjusted so that the weight ratio of isobutene monomer to 1 mol of the initiator is 500 to 500,000 depending on the molecular weight of the polymer to be produced. For example, in order to produce a polymer having a molecular weight of about 10,000, the amount of isobutene may be 10,000 g per mol of the initiator.

The catalyst is TiCl ₄ , AlCl ₃ , BC
Lewis acids such as l ₃ , ZnCl ₂ , SnCl ₄ , ethylaluminum chloride (C ₂ H ₅ AlCl ₂ ), and SnBr ₄ can be used. The amount of the catalyst used may be 0.1 to 1000 times the number of moles of the polymerization initiator. Alternatively, the amount can be 0.0001 to 10 times the number of moles based on the isobutene monomer.

Pyridine, 2-methylpyridine (abbreviated as picoline), trimethylamine, dimethylacetamide (abbreviated as DMAc), DMS as an electron donor.
O, EtOAc, etc. can be used. When the electron donor is added, it is preferably used in an amount smaller than that of the catalyst, and can be in the range of 0.01 to 10 times the molar amount based on the amount of the polymerization initiator.

The reaction temperature can be in the range of 0 to -100 ° C. At relatively high temperature conditions, the reaction rate is slow, and side reactions such as chain transfer reactions occur.
It is preferable to select a temperature lower than 30 ° C. When the reaction temperature is low, the solubility of the polymer decreases and the polymer precipitates. Therefore, a more preferable reaction temperature is -30 ° C to -70.
° C.

By mixing a chlorinated hydrocarbon or an aromatic hydrocarbon with an aliphatic hydrocarbon as a reaction solvent,
It is a major feature of the present invention that the induction ratio of the reaction solution at room temperature is 1 to 5 and the solubility parameter is 7.5 to 9.0. As the chlorinated hydrocarbon, methane dichloride, methane chloride, ethane dichloride, propane chloride and butane can be used. As the aromatic hydrocarbon, benzene, toluene, biphenyl, xylene, ethylbenzene can be used. As the aliphatic hydrocarbon, octane, heptane, hexane, pentane, butane, propane and the like can be used.

Chlorinated hydrocarbons have a high induction rate and a large solubility parameter value. For example, the specific induction rate of methane dichloride at room temperature is 7.7 and the solubility parameter is 9.7. By mixing with a hydrocarbon, it is possible to obtain a specific induction and a solubility parameter. For example, it is preferable to use a reaction solvent in which methane dichloride and an aliphatic hydrocarbon are mixed in a volume ratio of 2: 8 to 5: 5.

Since the aromatic hydrocarbon has a moderate induction rate and a large solubility parameter, a small amount of the aliphatic hydrocarbon may be mixed as compared with the case of the chlorinated hydrocarbon. Conventionally, the method of using chlorinated hydrocarbon as a reaction solvent is well known, and there has been a method of adding a small amount of hexane to it, but the induction rate is substantially limited to a range larger than 5, and the cation The method emphasized the reaction activity of the polymerization.

In the present invention, it has been newly found that a polymer having a more uniform molecular weight distribution can be obtained by suppressing the reaction rate of the polymerization under the condition of a lower induction rate, and its solvent composition is focused. is there. On the other hand, the induction rate of toluene is 2.2 at 20 ° C., which is far lower than that of methane dichloride, so a method of substantially using it as a reaction solvent was not known, but the reaction temperature was −30 to − It has been found that good polymerization of isobutene can be achieved at 60 ° C. It can also be used as a mixed solvent with an aliphatic hydrocarbon. It is preferable to mix toluene and the aliphatic hydrocarbon in a volume ratio of 9: 1 to 6: 4. As the aliphatic hydrocarbon, octane, heptane, hexane, pentane, butane, propane and the like are used. The main purpose of mixing toluene and an aliphatic hydrocarbon is to dissolve the polymer because toluene alone precipitates the polymer at -50 ° C or lower. When the reaction is carried out only with the aliphatic hydrocarbon, the chain transfer reaction becomes dominant and the desired polymer cannot be obtained. Therefore, the respective solvents are mixed in the above ratio.

The amount of isobutene monomer charged into the reaction solvent is 15 mol / L or less, but the polymer is precipitated at a high concentration. Since the productivity decreases when the charged amount is small, it is preferable to set it to 1 to 50 wt%, but 5 to 30 wt
It is more preferable to handle the polymer in a dissolved state in%. It is also possible to produce the isobutene-based polymer of the present invention by adding another cationically polymerizable monomer and performing copolymerization. Other cationically polymerizable monomers include 2-
Aliphatic olefins such as butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, hexene, cyclohexene, vinylcyclohexane, 5-ethylidene norbornene, indene, β-pinene; cyclopentadiene, dicyclopentadiene Dienes such as styrene; styrenes such as styrene, α-methylsterene, p-chlorostyrene and the like, and these may be used in an amount of 50% by weight or less based on the isobutene monomer.

The terminal of the isobutene polymer may have a structure in which chlorine is bonded to the tertiary carbon, but the function according to the purpose can be exhibited by introducing other functional group. Examples of the reactive functional group introduced at the end include an allyl group, a hydroxyl group, an allyl phenyl ether group, and a phenol group. To form such an end group, a phenol is bonded by a Friedel-Crafts reaction, a substitution reaction with allylsilane, or a general formula CH ₂ ═CH (CH ₂ )
_n CH═CH ₂ (wherein the hydrogen of (CH ₂ ) _n may be substituted with an alkyl group, preferably a methyl group, etc. 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) may be additionally bound. Can be vinyl terminated.

These compounds having a functional group can be used in an amount of 100 times or less mol based on the isobutene polymer.

[0021]

According to the reaction conditions of the present invention, the effect of making the molecular weight distribution of the polymer uniform can be obtained. For example, when methane dichloride alone is used as a reaction solvent, the growth rate in the polymerization is fast, and since the initiation reaction requires a relatively long time, a large polymer that continued to grow for a long time from the beginning and a slow start and a low polymer. It is considered that the difference between the molecular weight and the molecular weight remaining is large, and the molecular weight distribution becomes broad. On the other hand, when methane dichloride is mixed with hexane or toluene is used as a reaction solvent as in the present invention, the growth reaction rate is slowed down, so that the initiation reaction is completed at the beginning of the reaction and the molecules are evenly distributed. It is believed to grow and the molecular weight distribution becomes more uniform.

In the method of the present invention, since the polymerization reaction rate becomes slow, the heat generation rate accompanying the polymerization also becomes slow. Therefore, it becomes relatively easy to control the reaction temperature by heat removal cooling. When p-DCC is used as an initiator, an indanylation reaction of an aromatic ring may occur, which reduces the efficiency of the initiator and makes it difficult to set the molecular weight of the polymer. By using the reaction solvent conditions of the present invention, the side reaction of indanylation is significantly suppressed.

When a diene such as decadiene or octadiene is additionally reacted in order to introduce a vinyl group as a reactive functional group at the terminal of the polymer, a side reaction derived from the diene occurs to cause impurities. There is a problem that will generate.
By using the reaction solvent conditions of the present invention, the production of the impurities can be significantly suppressed.

[0024]

EXAMPLES Specific examples of the present invention will be described. Example 1: A reaction vessel is charged with 276 mL of toluene, 28 mL of isobutene monomer, 0.289 g of p-DCC, and 0.047 g of picoline. Place a dry ice-ethanol bath on the outer periphery of the reaction vessel and stir to mix the temperature at -7
Set to 0 ° C. The reaction is initiated by adding 3.95 mL TiCl ₄ with 4 mL toluene to the reactor. After completion of the reaction, the reaction solution is poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase are separated to remove the catalyst. The volatile components of the organic phase were removed by an evaporation operation to obtain a polymer product.

The molecular weight of the product polymer and its distribution were measured by GPC analysis. The result was a number average molecular weight Mn = 14.
636, distribution Mw / Mn = 1.12 (Mw: weight average molecular weight). As a result of NMR analysis, the ratio of indanylation (Fn (indanyl)) in the aromatic ring of p-DCC was 0.17.

Example 2: 112 mL of isobutene monomer, 1.156 g of p-DDC, 0.1 picoline in a reaction vessel.
86 g was charged, and other conditions were the same as in Example 1. The reaction was carried out by dissolving 3.95 mL of the catalyst in 4 mL of toluene and pouring it into the reactor to obtain a polymer product.

The molecular weight of the product polymer and its distribution were measured by GPC analysis. The result was that the number average molecular weight was Mn = 15.
987, distribution Mw / Mn = 1.13. NMR
As a result of analysis, the rate of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.16. Example 3: The same conditions as in Example 1 were carried out except that the reaction temperature was -50 ° C, and 9.95 g of decadiene was added after the polymerization reaction to introduce a functional group.

The molecular weight of the product polymer and its distribution were measured by GPC analysis. The result was a number average molecular weight Mn = 14.
312, distribution Mw / Mn = 1.2. No small molecule by-products were detected. As a result of NMR analysis, p-
The ratio of indanylation in the aromatic ring of DCC was Fn (indanyl) = 0.18.

Example 4: Toluene 248 m in a reaction vessel
L and 28 mL of hexane were charged, and other conditions were the same as in Example 1. The result of measuring the molecular weight of the product polymer and its distribution by GPC analysis is the number average molecular weight Mn.
= 16084, distribution Mw / Mn = 1.10.

As a result of NMR analysis, the ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) =
It was 0.14. Example 5: 76 mL of methane dichloride, 196 mL of hexane, 28 mL of isobutene monomer, p-DCC in a reaction vessel.
Charge 0.289 g and picoline 0.047 g. A dry ice-ethanol bath is placed on the outer periphery of the reaction vessel and the temperature is brought to -70 ° C while stirring and mixing. TiCl ₄ 3.9
The reaction is started by adding 5 mL of a mixture of 8 mL of methane dichloride to the reactor. After completion of the reaction, the reaction solution is poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase are separated to remove the catalyst. The volatile components of the organic phase were removed by an evaporation operation to obtain a polymer product. The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis were: number average molecular weight Mn = 18549 and distribution Mw / Mn = 1.07. Results of NMR analysis: The ratio of indanylation (Fn (indanyl)) in the aromatic ring of p-DCC was 0.

Example 6: 56 m of dichloromethane in a reaction vessel
L and 216 mL of hexane were charged, and other conditions were the same as in Example 1. 3.95 mL of catalyst is added to 8 m of hexane
A polymer product was obtained by carrying out the reaction by dissolving it in L and pouring it into the reactor. The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis are: number average molecular weight Mn
= 15802, distribution Mw / Mn = 1.08. Results of NMR analysis: The ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.

Example 7: Methane dichloride 104 in a reaction vessel
mL and 168 mL of hexane were charged, and the other conditions were the same as in Example 1 to carry out the reaction to obtain a polymer product. However, 9.95 g of decadiene was added to introduce a functional group. The reaction temperature is -50 ° C.

The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis are: number average molecular weight Mn = 18
479, distribution Mw / Mn = 1.2. No small molecule by-products were detected. Results of NMR analysis: The ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.

Example 8: Methane dichloride 132 in a reaction vessel
mL and hexane 140 mL were charged, and other conditions were the same as in Example 3 to carry out the reaction to obtain a polymer product. However, 0.044 g of DMAc was added instead of picoline. The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis are: number average molecular weight Mn = 1600
0, distribution Mw / Mn = 1.33.

The low molecular by-product was detected in a molar ratio of 0.05. Results of NMR analysis: The ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.13. Example 9: A reaction vessel is charged with 280 mL of toluene, 112 mL of isobutene monomer, 1.156 g of p-DCC, and 0.186 g of picoline. Place a dry ice-ethanol bath on the outer periphery of the reaction vessel with stirring and mixing at -50 ° C.
Cool to. The reaction is started by adding 2.74 mL of TiCl ₄ to the reactor. After the polymerization reaction, 1.71 g of trimethylallylsilane is added and reacted.

After the completion of the reaction, the reaction solution is poured into a large amount of water and washed by stirring to separate the organic phase from the aqueous phase to remove the catalyst. The volatile components of the organic phase were removed by an evaporation operation to obtain a polymer product.

The molecular weight of the product polymer and its distribution were measured by GPC analysis. The result was a number average molecular weight Mn = 15.
393, distribution Mw / Mn = 1.21. NMR
As a result of analysis, the ratio of indanylation (Fn (indanyl)) in the aromatic ring of p-DCC was 0. Example 10: Toluene 196 mL, hexane 84 mL, isobutene monomer 112 mL, p-DCC in a reaction vessel.
Charge 1.156 g and picoline 0.186 g. A dry ice-ethanol bath is placed on the outer periphery of the reaction vessel and the temperature is brought to -70 ° C while stirring and mixing. TiCl ₄ 2.7
The reaction is started by adding 4 mL to the reaction vessel. After completion of the reaction, the reaction solution is poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase are separated to remove the catalyst. The volatile components of the organic phase were removed by an evaporation operation to obtain a polymer product.

The molecular weight of the product polymer and its distribution were measured by GPC analysis. The result was number average molecular weight Mn = 19.
209, distribution Mw / Mn = 1.2. As a result of NMR analysis, the ratio of indanylation in the aromatic ring of p-DCC (28 mL of methane dichloride and 244 mL of hexane was charged into the Fn reaction vessel, and other conditions were the same as in Example 1. Catalyst 3.95 mL Was dissolved in 8 mL of hexane and poured into a reactor to carry out a reaction to obtain a polymer product.

The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis are: number average molecular weight Mn = 20
64, distribution Mw / Mn = 7.44. Results of NMR analysis: The ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.

Comparative Example 1: 160 Methane dichloride in a reaction vessel
mL, hexane 112 mL, and p-DCC 0.578 g were charged, and the conditions were the same as in Example 3 except that the catalyst was dissolved in methylene chloride 8 mL and poured into the reactor to carry out the reaction, to obtain a polymer product.

The molecular weight of the product polymer and its distribution were measured by GPC analysis. The result was that the number average molecular weight was Mn = 93.
10, distribution Mw / Mn = 1.75. A low molecular by-product was detected in a molar ratio of 0.2 with the main product. N
As a result of MR analysis, the ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.21.

Comparative Example 2: Methane dichloride 188 in a reaction vessel
mL and hexane 84 mL were charged, and other conditions were the same as in Comparative Example 1 to carry out the reaction to obtain a polymer product. G
The results of measuring the molecular weight of the product polymer and its distribution by PC analysis are: number average molecular weight Mn = 9266, distribution M
It was w / Mn = 1.6.

A low molecular by-product was detected in a molar ratio of 0.4 with respect to the main product. As a result of NMR analysis, the ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.26. Comparative Example 3: The reaction vessel was charged with 28 mL of methane dichloride and 244 mL of hexane, and other conditions were the same as in Example 1. The reaction was carried out by dissolving 3.95 mL of the catalyst in 8 mL of hexane and pouring it into the reactor to obtain a polymer product.

The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis are: number average molecular weight Mn = 20
64, distribution Mw / Mn = 7.44. Results of NMR analysis: The ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.

Comparative Example 4: 276 mL of hexane in the reaction vessel
Was charged without using methane dichloride, and the other conditions were the same as in Example 1. The polymer product was obtained by dissolving 7.9 mL of the catalyst TiCl ₄ in 8 mL of hexane and pouring it into the reactor. The results of measuring the molecular weight of the product polymer and its distribution by GPC analysis are: number average molecular weight Mn = 1552, distribution
It was Mw / Mn = 7.02. Results of NMR analysis: The ratio of indanylation in the aromatic ring of p-DCC was Fn (indanyl) = 0.87.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shun Wachi 3-2-2 Nishihata, Takasago City, Hyogo Prefecture

Claims (9)

[Claims] 1. When polymerizing an isobutene monomer using an aromatic initiator and a catalyst, a solvent in which either a chlorinated hydrocarbon or an aromatic hydrocarbon is used alone or in combination with an aliphatic hydrocarbon is used. The method for producing an isobutene-based polymer is characterized in that the reaction liquid has a dielectric constant of 1 to 5 and a solubility parameter of 7.5 to 9.0. 2. The method for producing an isobutene-based polymer according to claim 1, wherein the compound having a vinyl group is introduced into the terminal of the polymer by an addition reaction or a substitution reaction subsequent to the polymerization reaction. 3. The isobutene according to claim 1, wherein the initiator is 1,4-bis (α-chloroisopropyl) benzene, and 1,9-decadiene or allyltrimethylsilane is used as the vinyl group compound. Of producing a base polymer. 4. The method for producing an isobutene polymer according to claim 1, wherein isobutene is charged in the range of 1% by weight to 30% by weight. 5. A reaction temperature of -3 as a toluene reaction solvent.
The method for producing an isobutene-based polymer according to claim 1, wherein the temperature is 0 to -60 ° C. 6. Toluene and an aliphatic hydrocarbon 9: 1 to
The method for producing an isobutene-based polymer according to claim 1, wherein a reaction solvent mixed in a volume ratio of 6: 4 is used. 7. The methane dichloride and the aliphatic hydrocarbon are 2: 8.
The method for producing an isobutene-based polymer according to claim 1, wherein a reaction solvent mixed in a volume ratio of 5: 5 is used. 8. The method for producing an isobutene-based polymer according to claim 1, wherein an electron donor is added. 9. The method for producing an isobutene polymer according to claim 1, wherein the reaction temperature is 0 to −100 ° C.