JP2969471B2 - Method for producing isobutylene-based polymer having silyl group at terminal - Google Patents

Description

The present invention relates to a method for producing an isobutylene-based polymer having a terminal silyl group.

[Problems to be solved by conventional technologies and inventions]

A terminal functional polymer, for example, a polymer having a dimethoxysilyl group or a trimethoxysilyl group introduced at both ends of the molecule, is useful as a raw material for an adhesive, a modifier, a coating agent, etc. No. 148895).

A kind of terminal functional polymer, for example, -C
The isobutylene-based polymer having a (CH ₃ ) ₂ C group is 1,4-
Manufactured by an inifer method (US Pat. No. 4,276,394) in which bis (α-chloroisopropyl) benzene (hereinafter simply referred to as “p-DCC”) is used as an initiator / chain transfer agent and BCl ₃ as a catalyst to cationically polymerize isobutylene. Is known to be.

Further, immediately after polymerization obtained by such an inifer method, or to an isobutylene-based polymer having a chloro group at both ends after purification, further allyl groups at both ends by adding allyltrimethylsilane after further adding TiCl ₄ It is known that a polymer can be obtained (JP-A-63-105005).
No.).

Further, the polymer produced by the method using the above-mentioned allyltrimethylsilane is hydrosilylated with dimethoxymethylsilane or trimethoxysilane in the presence of chloroplatinic acid, so that a dimethoxymethylsilyl group or trimethoxysilyl group is present at both ends. An isobutylene-based polymer having a group can be obtained. Terminal methoxysilyl (CH ₃ O-S
i) The group is hydrolyzed by moisture to form a silanol (HO-S
i) to provide a group;

The silanol group reacts with a methoxysilyl group in the presence of a silanol condensation catalyst to form a siloxane bond (Si-O-Si).
(Silanol condensation). As the silanol condensation reaction proceeds, the crosslinking reaction proceeds, and finally, a rubber-like cured product is provided.

However, in the method described in JP-A-63-105005, the number of steps required to obtain an isobutylene-based polymer having a silyl group at a terminal is large, and the invention of a simpler production method is desired. Further, the manufacturing method described in Japanese Patent Application Laid-Open No. 61-148895 also has a considerably large number of steps, and is not a very good method.

An object of the present invention is to provide a simple method for producing an isobutylene-based polymer having a silyl group at a terminal.

In the present invention, the process for producing the isobutylene polymer having the terminal of Si-Cl bonds primarily, which is a polymer equivalent having a Si-OCH ₃ bond at the terminal. Si
-Cl binding can be easily converted into Si-OCH ₃ bond with methanol and orthoformic acid methyl.

[Means for solving the problem]

That is, the gist of the present invention is that (1) the number average molecular weight is 500 to 200,000, and at least 1.1 general formula (II) per molecule: [Wherein, W represents a halogen atom or an R ⁵ COO— group (R ⁵ is a monovalent organic group). And an isobutylene-based polymer having a terminal represented by the general formula (III): [Wherein, R ¹ and R ² are monovalent organic groups or hydrogen atoms, R ³ is a divalent organic group, and R ⁴ is a monovalent organic group or a chlorine atom, which may be the same or different. Characterized by performing a Friedel-Crafts type reaction with an organosilicon compound represented by the formula, the number average molecular weight is 500
~ 200,000, with at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. (2) a number-average molecular weight of from 500 to 200,000, and at least 1.1 of formula (IV) per molecule: Characterized by carrying out a Friedel-Crafts type reaction between an isobutylene-based polymer having a terminal represented by the formula (III) and the organosilicon compound represented by the general formula (III), wherein the number-average molecular weight is 500 to 200,000, and 1 molecule A method for producing at least 1.1 terminally-isobutylene-based polymer represented by the general formula (I), (3) having a number average molecular weight of 500 to 200,000, and at least 1.1 of formula (V) per molecule: Characterized by carrying out a Friedel-Crafts type reaction between an isobutylene-based polymer having a terminal represented by the formula (III) and the organosilicon compound represented by the general formula (III), wherein the number-average molecular weight is 500 to 200,000, and 1 molecule A method for producing at least 1.1 per unit of an isobutylene-based polymer having a terminal represented by the general formula (I), (4) a number-average molecular weight of 500 to 200,000, a terminal represented by the formula (IV) and a terminal represented by the formula A Friedel-Crafts type reaction between an isobutylene-based polymer containing 3% or more of the total terminal amount of the terminal represented by (V) and the organosilicon compound represented by the general formula (III). Having a number average molecular weight of 500 to 200,000 and 1
A method for producing at least 1.1 terminally-isobutylene-based polymer represented by formula (I) per molecule, (5) (A) a cationically polymerizable monomer containing isobutylene, (B) an initiator and a chain transfer agent General formula (VI) as: [In the formula, Y represents a halogen atom or an R ⁹ COO— group (R ⁹ is a monovalent organic group). R ⁶ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ⁷ and R ⁸ are the same or different and each represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ⁶ represents a polyvalent aliphatic hydrocarbon group, R ⁷ and R ⁸ are not both hydrogen atoms. An organic compound having a group represented by the formula: and (C) a Lewis acid are mixed to polymerize the cationic polymerizable monomer containing (A) isobutylene, and then (D) the above-mentioned general formula (D) A Friedel-Crafts type reaction is carried out by adding an organosilicon compound represented by III), wherein the number average molecular weight is from 500 to 200,000, and at least 1.1 per molecule represented by the general formula (I). And (6) (A) a cationically polymerizable monomer containing isobutylene, and (B) a group represented by the above general formula (VI) as an initiator and chain transfer agent. (C) a Lewis acid, and (D) an organosilicon compound represented by the general formula (III) to form a mixture containing the isobutylene of the above (A). And performing Friedel-Crafts reactions and at the same time carry out the polymerization reaction of the polymerizable monomer, the number average molecular weight of 500 to 200,000, at least per molecule
1. a process for producing one terminal isobutylene-based polymer represented by the general formula (I).

The production method of the present invention is a method for producing an isobutylene-based polymer having a terminal represented by the general formula (I),
These include:

(Production method 1) The number average molecular weight is 500 to 200,000, and at least 1.1 general formula (II) per molecule: [Wherein, W represents a halogen atom or an R ⁵ COO— group (R ⁵ is a monovalent organic group). And an isobutylene-based polymer having a terminal represented by the general formula (III): [Wherein, R ¹ and R ² are monovalent organic groups or hydrogen atoms, R ³ is a divalent organic group, and R ⁴ is a monovalent organic group or a chlorine atom, which may be the same or different. And a Friedel-Crafts type reaction with an organosilicon compound represented by the formula:

Here, regarding the general formula (II), W is a halogen atom or
R ⁵ COO- group is shown, but as R ⁵ COO- group, CH ₃ COO- group,
CH ₃ CH ₂ COO— group and the like are exemplified.

In the general formula (III), R ¹ and R ^{2 each} represent a monovalent organic group or a hydrogen atom, and examples of the monovalent organic group include an alkyl group, an alkoxy group, an alkylthio group, and a phenoxy group. Usually, a linear or branched one having 1 to 10 carbon atoms is suitably used. Examples of the alkoxy group include a methoxy group, an ethoxy group, an allyloxy group and the like.

R ³ represents a divalent organic group, for example, -CH ₂ CH ₂ CH _2- , -C
_{H 2 CH (CH 3) CH} 2 - and the like.

R ⁴ represents a monovalent organic group or a chlorine atom, examples of the monovalent organic group include an alkyl group and an alkoxy group,
As the alkyl group, a methyl group, an ethyl group and the like are usually suitably used.

As the organosilicon compound represented by the general formula (III), conventionally known compounds can be widely used as long as they correspond to the general formula (III), but the following can be preferably exemplified.

The organosilicon compound represented by the general formula (III) can be easily obtained by hydrosilylating an aromatic allyl ether using dichloromethylsilane or trichlorosilane.

The Friedel-Crafts type reaction proceeds both in a solvent and without a solvent. As the solvent, those which can be used for ordinary Friedel-Crafts type reactions can be widely used, and specifically, aliphatic hydrocarbon compounds such as n-hexane, n-pentane, n-heptane and cyclohexane, methylene chloride, Halogenated hydrocarbon compounds such as carbon tetrachloride, chloroform, 1,1-dichloroethane, ethyl chloride,
Preferred examples include aromatic compounds such as toluene, chlorobenzene and xylene, organic sulfur compounds such as carbon disulfide, and nitro compounds such as nitromethane, nitroethane and nitrobenzene. These solvents may be used alone or as a mixture of two or more.

In the present invention, as the Lewis acid used in the Friedel-Crafts type reaction, any of those used in ordinary Friedel-Crafts type reaction can be used,
For example, TiCl ₄ , BF ₃ .O (C ₂ H ₅ ) ₂ , SnCl ₄ , AlCl ₃ , BCl ₃
And the like, and particularly preferred are SnCl ₄ and AlCl ₃ .

The amount of the Lewis acid used is preferably about 0.1 to 20 times, more preferably about 0.5 to 8 times, the total amount of the functional groups of the isobutylene polymer.

The Friedel-Crafts type reaction proceeds in a temperature range of −70 to 100 ° C., but is preferably performed at 0 to 40 ° C.
The reaction time of the reaction varies depending on the type and amount of the Lewis acid used, the reaction scale, and the like, and cannot be determined unconditionally, but is usually about 0.1 to 72 hours, preferably about 2 to 24 hours.

(Production Method 2) In the production method of the present invention, the number average molecular weight is 500 to 2
00,000 and at least 1.1 formula (I
V): Can be produced by performing a Friedel-Crafts type reaction between an isobutylene-based polymer having a terminal represented by the following formula and an organosilicon compound represented by the general formula (III).

The conditions for the Friedel-Crafts type reaction are the same as in the above-mentioned Production Method 1.

(Production method 3) Further, the number average molecular weight is 500 to 200,000, and at least 1.1 formula (V) per molecule: Can be produced by performing a Friedel-Crafts type reaction between an isobutylene-based polymer having a terminal represented by the following formula and an organosilicon compound represented by the general formula (III).

The conditions for the Friedel-Crafts type reaction are the same as in the above-mentioned Production Method 1.

(Production Method 4) Further, an isobutylene-based polymer having a number-average molecular weight of 500 to 200,000 and containing a terminal represented by the formula (IV) and a terminal represented by the formula (V) in a total terminal amount of 3% or more, respectively And the organosilicon compound represented by the above general formula (III) to carry out a Friedel-Crafts type reaction.

The conditions for the Friedel-Crafts type reaction are the same as in the above-mentioned Production Method 1.

(Production Method 5) The production method of the present invention also includes the following method.

Method (A) Cationic polymerizable monomer containing isobutylene (B) General formula (VI) as initiator and chain transfer agent: [In the formula, Y represents a halogen atom or an R ⁹ COO— group (R ⁹ is a monovalent organic group). R ⁶ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ⁷ and R ⁸ are the same or different and each represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ⁶ represents a polyvalent aliphatic hydrocarbon group, R ⁷ and R ⁸ are not both hydrogen atoms. An organic compound having a group represented by the formula: and (C) a Lewis acid are mixed to polymerize the cationic polymerizable monomer containing (A) isobutylene, and then (D) the above-mentioned general formula (D) It can be produced by adding an organosilicon compound represented by III) and performing a Friedel-Crafts type reaction.

Method: (A) a cationically polymerizable monomer containing isobutylene, and (B) the above-mentioned general formula (V) as an initiator / chain transfer agent
A cationically polymerizable monomer containing the isobutylene of (A) by mixing an organic compound having a group represented by I), a Lewis acid (C), and an organosilicon compound represented by (D) the general formula (III) And a Friedel-Crafts type reaction at the same time as the polymerization reaction.

Here, (A) the cationically polymerizable monomer containing isobutylene is not limited to a monomer consisting solely of isobutylene, but 50% by weight of isobutylene.
(Hereinafter simply referred to as “%”) means a monomer in which the following is substituted with a cationically polymerizable monomer copolymerizable with isobutylene.

Cationic polymerizable monomers copolymerizable with isobutylene include, for example, olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Among these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferred.

Specific examples of the cationically polymerizable monomer copolymerizable with the isobutylene include, for example, propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, and 4-methyl- 1-pentene,
Hexene, vinylcyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldiene Chlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane , Tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, Trimethylsilane, diallyl dichlorosilane, diallyl dimethoxysilane, diallyl dimethyl silane, .gamma.-methacryloyloxy propyl trimethoxy silane, .gamma.-methacryloyloxy propyl methyl dimethoxysilane and the like. Among these,
For example, propylene, 1-butene, 2-butene, styrene, butadiene, isoprene, cyclopentadiene and the like are suitable. These cationically polymerizable monomers copolymerizable with isobutylene may be used alone or in combination of two or more with isobutylene.

(B) The initiator / chain transfer agent is an organic compound having a group represented by the general formula (VI), and examples thereof include, for example, a general formula (VII): AY'n (VII) A represents a group having 1 to 4 aromatic rings. Y '
Is the general formula (VII) (In the formula, R ⁷ , R ⁸ and Y are the same as above.) n shows the integer of 1-6. General formula (IX): BZm (IX) wherein B represents a hydrocarbon having 4 to 40 carbon atoms. Z is third
Halogen atom or R ⁹ COO— group (R ⁹
Represents the same as described above). m shows the integer of 1-4. And oligomers having an α-halostyrene unit, but are not limited thereto. These compounds may be used alone or 2
More than one species may be used in combination.

A, which is a group having 1 to 4 aromatic rings in the compound represented by the general formula (VII), may be formed by a condensation reaction or may be a non-condensed one. Specific examples of such a group having an aromatic ring include, for example, a monovalent to hexavalent phenyl group, a biphenyl group, a naphthalene group, an anthracene group, a phenanthrene group, a pyrene group, and a Ph- (CH ₂ ) l.
-Ph group (Ph is a phenyl group, l is an integer of 1 to 10) and the like, and these groups having an aromatic ring are a straight-chain and / or branched aliphatic hydrocarbon having 1 to 20 carbon atoms. It may be substituted with a group, a group having a functional group such as a hydroxyl group, an ether group, or a vinyl group, or a halogen atom.

On the other hand, Z in the compound represented by the general formula (IX)
Is a halogen atom such as F, C, Br, I or an R ⁹ COO— group bonded to a tertiary carbon atom, and B in the general formula (IX) is a hydrocarbon group having 4 to 40 carbon atoms; Preferably, it is an aliphatic hydrocarbon group. When the number of carbon atoms is less than 4, the carbon atom to which the halogen atom or the R ⁹ COO— group is bonded is not a tertiary carbon atom, and the polymerization is difficult to proceed, so that it is difficult to use it suitably. Become.

Examples of the oligomer having an α-halostyrene unit that can be used as an initiator / chain transfer agent include, for example, α
Oligomers of α-chlorostyrene and oligomers obtained by copolymerizing α-chlorostyrene with a monomer copolymerizable therewith.

In the method of the present invention, a compound having two or more bonded halogen atoms or R ⁹ COO— groups represented by the general formula (VI), or a bonded halogen atom or R ⁹ COO represented by the general formula (VI) When a compound having a group and another reactive functional group is used as an initiator / chain transfer agent, a polymer having both terminal functionalities, a so-called telechelic polymer can be obtained, and the degree of terminal functionalization can be increased. So very effective.

Specific examples of the initiator and chain transfer agent include, for example, (Y is the same as above.) Examples include, but are not limited to, a halogen atom-containing organic compound such as an oligomer of α-chlorostyrene or an R ⁹ COO— group-containing organic compound. Among these compounds A halogen atom-containing organic compound having —C (CH ₃ ) ₂ C or —C (CH ₃ ) ₂ Br which easily generates a stable carbon cation, Preferred are organic compounds containing a CH ₃ COO— group such as

These compounds are components used as an initiator and a chain transfer agent, and in the present invention, one kind or a mixture of two or more kinds is used. Further, by adjusting the amounts of these compounds used, the molecular weight of the obtained polymer can be controlled. In the present invention, the above compound is used in a proportion of about 0.01 to 20%, preferably about 0.1 to 10%, based on the cationically polymerizable monomer usually containing isobutylene.

The (C) Lewis acid used in the polymerization reaction in the present invention is a component used as a catalyst. As such Lewis acids, conventionally known ones can be widely used, for example, BC
Examples include, but are not limited to, l ₃ , AlCl ₃ , SnCl ₄ , TiCl ₄ , VCl ₅ , FeCl ₃ , BF _{3 and the} like. Of these Lewis acids, AlCl ₃ , SnCl ₄ and TiCl ₄ are preferred. The amount of the Lewis acid to be used is preferably about 0.0001 to 10 times, more preferably about 2 to 5 times, the number of moles of Y in the organic compound having a group represented by the general formula (VI), which is the initiator / chain transfer agent. Is more preferred.

In the present invention, as the polymerization solvent, conventionally known solvents can be widely used as long as they are inert solvents. Specific examples thereof include, for example, chloromethane, chloroform, carbon tetrachloride, chloroethane, methylene chloride, 1,1-dichloroethane. , 1,2-dichloroethane, 1,1,1-trichloroethane,
Halogenated hydrocarbon compounds such as 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane and tetrachloroethylene, aliphatic hydrocarbon compounds such as n-hexane and n-pentane, nitromethane, nitroethane, 1-nitro Examples thereof include compounds having a nitro group such as propane, 2-nitropropane, nitrobenzene, nitrotoluene, o-, m- or p-dinitrobenzene. These may be used alone or as a mixture of two or more.

In carrying out the polymerization reaction of the present invention, in one vessel, an inert solvent as the polymerization solvent, a cationically polymerizable monomer containing the isobutylene, the initiator and chain transfer agent, a Lewis acid used during the polymerization reaction, In some cases, a batch method in which the organosilicon compound represented by the general formula (III) or the like is sequentially charged may be used, or the inert solvent, the cationic polymerizable monomer, the initiator / chain transfer agent, A continuous method in which the Lewis acid or the like to be used is reacted while being continuously charged into a certain system, and then further taken out may be used.

In the method of the present invention, the polymerization temperature is from -120 to
About 0 ° C. is preferable.

The general formula (II) in the present invention: Wherein W is the same as above. In order to obtain the terminal represented by the formula (1) with a high purity of 95% or more of the total terminal functional groups, the polymerization temperature is preferably -50 ° C or lower. When obtaining an isobutylene-based polymer containing 3% or more of each of the terminal represented by the formula (IV) and the terminal represented by the formula (V), the polymerization temperature is -50 to
The temperature should be about -10 ° C.

The polymerization time varies depending on the ability to cool the reaction vessel, the scale of the polymerization, and the like, and cannot be determined unconditionally, but is usually about 1 to 300 minutes, preferably about 5 to 120 minutes. The monomer concentration during the polymerization is preferably about 0.1 to 8 mol / l, more preferably about 0.5 to 5 mol / l.

In the method of the present invention, an isobutylene-based polymer having a silyl group at the end of one pot is obtained by adding the organosilicon compound represented by the general formula (III) to the polymerization system before or after the polymerization. be able to.

Solvents for carrying out the polymerization reaction and the Friedel-Crafts type reaction in one pot include halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, 1,1-dichloroethane and ethyl chloride, and aromatic solvents such as toluene and chlorobenzene. Group compounds, nitro compounds such as nitromethane, nitroethane, and nitrobenzene are preferred. These solvents may be used alone or in combination of two or more.

As the Lewis acid, AlCl ₃ , SnCl ₄ , TiCl _{4 and the} like are preferable.

The organic compound represented by the general formula (III) may be added before the start of the polymerization or after the end of the polymerization. However, in the yarn added before the start of the polymerization, a polymer having a more uniform molecular weight is used. Tend to be obtained.

Further, when producing an isobutylene yarn polymer having a silyl group at a terminal in one pot, the polymerization reaction is carried out at -60 ° C to -10 ° C.
C. and then run the Friedel-Crafts type reaction at 0-40 ° C.
It is preferably carried out in the polymerization, depending on the polymerization conditions -60 ~
It is also possible to complete the Friedel-Crafts type reaction at the same time as conducting the polymerization reaction at -10 ° C to obtain an isobutylene-based polymer having an allyl group at the terminal.

Usually, the polymerization reaction is preferably performed for about 5 to 120 minutes, and the Friedel-Crafts type reaction is preferably performed for about 2 to 24 hours.

〔The invention's effect〕

By using the method of the present invention, it has become possible to produce an isobutylene-based polymer having a silyl group at a terminal by a simple and low-cost method.

In the method of the present invention, a silyl group can be introduced into a terminal in one pot, and in a system in which the organosilicon compound represented by the general formula (III) is added before the start of polymerization, the molecular weight is more uniform. The obtained polymer can be obtained.

〔Example〕

Hereinafter, the present invention will be further clarified with reference to examples.

Example 1 General formula (X): (Where R ¹⁰ is (A is 0 or an integer of 1 to 100). R ¹¹ (B is 0 or an integer of 1 to 100). R ¹² is (C is 0 or an integer of 1 to 100). ] An isobutylene-based polymer (n = 5000, w /
n = 1.5) 2.0 g, compound (1) (see the following structural formula) 6
Millimol and 10 ml of methylene chloride were added to a 50 ml eggplant flask, and stirred using a magnetic stirrer. After 6 mmol of tin tetrachloride was added to the homogeneous solution thus obtained, the mixture was stirred at room temperature under a nitrogen atmosphere for 6 hours.

Thereafter, methylene chloride, tin tetrachloride, and the like were distilled off from the system under reduced pressure, and then 20 mmol of methanol and 20 mmol of methyl orthoformate were added, and the mixture was stirred at 80 ° C. for 2 hours.
It was converted to the group to Si-OCH ₃ groups.

Then, after the volatile components were distilled off under reduced pressure, the polymer was dissolved in 3 ml of hexane and poured into 100 ml of acetone to precipitate and separate the polymer. The polymer thus obtained was dissolved again in 30 ml of hexane, dried over anhydrous magnesium sulfate, filtered, and then hexane was distilled off under reduced pressure.
The desired isobutylene polymer was obtained.

While calculating the yield from the yield of the obtained polymer,
by GPC n and w / n, also a terminal structure ¹ H-N
The intensity was obtained by measuring and comparing the intensity of the resonance signal of the proton belonging to each structure by the MR (300 MHz) method or the like. The results are shown in Table 1 below.

Example 2 An isobutylene-based polymer as a raw material was represented by the following general formula (XI): (Where R ¹³ is (D is 0 or an integer of 1 to 100). R ¹⁴ is (E is 0 or an integer of 1 to 100). R ¹⁵ is (F is 0 or an integer of 1 to 100). ] An isobutylene-based polymer (n = 5000, w /
The reaction was carried out in the same manner as in Example 1 except that n = 1.5), and the obtained isobutylene-based polymer was purified and evaluated. The results are shown in Table 1.

From the results of Examples 1 and 2, when the compound (1) is used, the terminal having a chlorine atom and the terminal represented by the formula (IV) can be almost quantitatively converted into the terminal having a silyl group. It was revealed.

Example 3 A three-way cock was attached to a 200 ml pressure-resistant glass container, and the polymerization container was dried by heating at 100 ° C. for 1 hour while being evacuated by a vacuum line.
The pressure was returned to normal pressure with nitrogen using a three-way cock.

Then, while flowing nitrogen from one of the three-way cocks, use a syringe to autoclave the formula. A solution prepared by dissolving 1 mmol of tricumyl chloride represented by the formula in 40 ml of methylene chloride dried by calcium hydroxide treatment was added.

Next, after connecting a pressure-resistant glass liquefied gas sampling tube with a needle valve containing 5 g of isobutylene dehydrated by passing through a column filled with barium oxide to a three-way cock, the container body was dried at -70 ° C. It was immersed in an acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the pressure inside was reduced by a vacuum line, then the needle valve was opened, and isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three cocks, and cooling was further continued for 1 hour with stirring to cool the inside of the polymerization vessel to -70 ° C.

Next, a solution (−30 ° C.) obtained by diluting 10 mmol of tin tetrachloride with 20 ml of methylene chloride was added from a three-way cock using a syringe to start polymerization. When 60 minutes had elapsed, 10 mmol of compound (1) was added. Was added from a three-way cock using a syringe.

Thereafter, the reaction solution was stirred at room temperature for 6 hours, and then methylene chloride, tin tetrachloride, unreacted monomers and the like were distilled off from the system under reduced pressure, and then 30 mmol of methanol and 30 mmol of oil methyl formate were added. Stir at 80 ° C for 2 hours, Si-C
It was converted to the group to Si-OCH ₃ groups. After the volatile components were distilled off under reduced pressure, the polymer was dissolved in 5 ml of hexane and then added to 300 ml of acetone with stirring to precipitate and separate the polymer.

The polymer thus obtained was dissolved in 80 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered,
The n-hexane was distilled off under reduced pressure to obtain an isobutylene-based polymer.

The isobutylene polymer thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 4 An isobutylene-based polymer was produced and evaluated in the same manner as in Example 3 except that the temperature during the polymerization reaction was changed to -30 ° C. The results are shown in Table 2.

Comparative Example 1 An isobutylene-based polymer was prepared in the same manner as in Example 4 except that the polymerization was stopped by adding methanol cooled to −40 ° C. or lower instead of the compound (1) at the point of time 60 minutes after the start of weight. Was manufactured and evaluated. The results are shown in Table 2.

Example 5 An isobutylene-based polymer was produced and evaluated in the same manner as in Example 4 except that 10 mmol of the compound (1) was added before the start of the polymerization, and was not added after the start of the polymerization. The results are shown in Table 2.

Example 6 An isobutylene-based polymer was produced and evaluated in the same manner as in Example 5, except that the compound (2) was used instead of the compound (1). The results are shown in Table 2. The structure of compound (2) is shown below.

From Table 2, it is clear that according to the method of Example 3, an isobutylene-based polymer having a silyl group at a terminal can be obtained in one pot.

From Table 2, it is apparent that the method of Example 4 allows the polymerization reaction to be carried out at a relatively high temperature of -30 ° C. and to provide an isobutylene-based polymer having a silyl group at a terminal in one pot. The method of Example 4 does not require a particularly large-scale cooling device as a method for producing an isobutylene-based polymer having a silyl group at a terminal.
Quite low cost and practical.

From the results of Example 4 and Comparative Example 1, it was clarified that the terminals represented by the formulas (IV) and (V) once formed were respectively reacted with the compound (1).

From the results of Example 4 and Example 5, it is clear that by adding the compound (1) before the start of polymerization, an isobutylene-based polymer having a more uniform molecular weight (that is, a smaller w / n value) can be obtained. Became.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-20501 (JP, A) JP-A-4-103606 (JP, A) JP-A-64-38407 (JP, A) JP-A-64-38407 22904 (JP, A) JP-A-63-254149 (JP, A) JP-A-63-6041 (JP, A) JP-A-63-6003 (JP, A) JP-A-1-247402 (JP, A) JP-A-54-66993 (JP, A) WO 90/15081 (WO, A1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 8/42 C08F 10/10

Claims (6)

(57) [Claims] (1) a number average molecular weight of 500 to 200,000 and at least 1.1 general formula (II) per molecule: [Wherein, W represents a halogen atom or an R ⁵ COO— group (R ⁵ is a monovalent organic group). And an isobutylene-based polymer having a terminal represented by the general formula (III): [Wherein, R ¹ and R ² are monovalent organic groups or hydrogen atoms, R ³ is a divalent organic group, and R ⁴ is a monovalent organic group or a chlorine atom, which may be the same or different. Characterized by performing a Friedel-Crafts type reaction with an organosilicon compound represented by the formula, the number average molecular weight is 500
~ 200,000, with at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. ] The manufacturing method of the isobutylene-type polymer which has a terminal represented by these. 2. A compound having a number average molecular weight of from 500 to 200,000 and at least 1.1 of formula (IV) per molecule: And an isobutylene-based polymer having a terminal represented by the general formula (III): Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. Characterized by performing a Friedel-Crafts type reaction with an organosilicon compound represented by the formula, the number average molecular weight is 500
~ 200,000, with at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. ] The manufacturing method of the isobutylene-type polymer which has a terminal represented by these. 3. The number average molecular weight is from 500 to 200,000, and at least 1.1 formula (V) per molecule: And an isobutylene-based polymer having a terminal represented by the general formula (III): Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. Characterized by performing a Friedel-Crafts type reaction with an organosilicon compound represented by the formula, the number average molecular weight is 500
~ 200,000, with at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. ] The manufacturing method of the isobutylene-type polymer which has a terminal represented by these. 4. A compound of the formula (IV) having a number average molecular weight of from 500 to 200,000. And a terminal represented by the formula (V): And an isobutylene-based polymer containing 3% or more of the total amount of the terminal represented by the general formula (III): Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. Characterized by performing a Friedel-Crafts type reaction with an organosilicon compound represented by the formula, the number average molecular weight is 500
~ 200,000, with at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. ] The manufacturing method of the isobutylene-type polymer which has a terminal represented by these. 5. A cationic polymerizable monomer containing (A) isobutylene, and (B) a general formula (VI) as an initiator / chain transfer agent: [In the formula, Y represents a halogen atom or an R ⁹ COO— group (R ⁹ is a monovalent organic group). R ⁶ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ⁷ and R ⁸ are the same or different and each represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ⁶ represents a polyvalent aliphatic hydrocarbon group, R ⁷ and R ⁸ are not both hydrogen atoms. An organic compound having a group represented by the formula: and (C) a Lewis acid are mixed to polymerize the isobutylene-containing cationic polymerizable monomer of the above (A), and then (D) a compound of the formula (III) ): Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. Characterized by performing a Friedel-Crafts type reaction by adding an organosilicon compound represented by
500 to 200,000, and at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. ] The manufacturing method of the isobutylene-type polymer which has a terminal represented by these. 6. A cationic polymerizable monomer containing (A) isobutylene, and (B) a general formula (VI) as an initiator / chain transfer agent: Wherein Y, R ⁶ , R ⁷ and R ⁸ are the same as above. An organic compound having a group represented by the formula: (C) a Lewis acid, and (D) a general formula (III): Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. And a Friedel-Crafts-type reaction at the same time as the polymerization reaction of the isobutylene-containing cationically polymerizable monomer (A) by mixing the organosilicon compound represented by the formula (A) with a number average molecular weight of 500 to 200,000 and at least 1.1 general formula (I) per molecule: Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. ] The manufacturing method of the isobutylene-type polymer which has a terminal represented by these.