JP2969470B2 - Isobutylene polymer having allyl group at terminal and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an isobutylene-based polymer having an allyl group at a terminal and a method for producing the same.

[Problems to be solved by conventional technologies and inventions]

Terminal functional polymers, for example, polymers having vinyl groups introduced at both molecular ends, include photo-curable resins, UV-curable resins, electron beam-curable resins, modified silicone addition-curable resins, adhesives, and modifiers. It is useful as a raw material for agents and coating agents.

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

In addition, 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 having allyl groups at both ends by adding allyltrimethylsilane after adding TiCl ₄ It is known that a polymer can be obtained (JP-A-63-105005).
No.).

Further, the polymer produced by the above method using allyltrimethylsilane is hydrosilylated using dimethoxymethylsilane in the presence of chloroplatinic acid to obtain an isobutylene-based polymer having a dimethoxymethylsilyl group at both ends. be able to. Terminal methoxysilyl (CH ₃ O
-Si) group is hydrolyzed by moisture to form silanol (HO
—Si) 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.

Isobutylene-based polymers having a dimethoxymethylsilyl group at both terminals are useful as raw materials for sealing agents, coating agents and the like (JP-A-61-148895).

However, the method described in JP-A-63-105005 has a problem that an expensive Lewis acid such as BCl ₃ is used in the polymerization step, and the product becomes considerably expensive. If a Lewis acid other than BCl ₃ is used, a large amount of unsaturated terminal polymer will be generated in addition to the chloro terminal polymer.

Further, when a dimethoxymethylsilyl group is introduced into an isobutylene-based polymer having an allyl group at both ends (the structure of the end is shown below) produced by the method using the allyltrimethylsilane, the obtained polymer is easily obtained. There is a problem of gelation (that is, poor storage stability).

Further, a polymer obtained by hydrosilylation of an isobutylene-based polymer having an allyl group at both ends (the structure of the end is shown below) obtained by another method (JP-A-62-166199) was also compared. It gelled easily.

Further, as an isobutylene-based polymer having a dimethoxymethylsilyl group at both ends, there is one described in JP-A-61-148895, which is a polymer having a low-activity isopropenyl group at the end. After hydrosilylation using highly corrosive methyldichlorosilane, it must be converted to a dimethoxysilyl group, which is complicated and not economical. Further, an addition-type curing system (Japanese
63-022949), it is considered that an allyl group is more preferable as a terminal functional group in consideration of the fact that the reactivity of the isopropenyl group is low and curing is often delayed.

An object of the present invention is to provide an isobutylene-based polymer which has an allyl group at a terminal and does not easily gel even after introduction of a dimethoxymethylsilyl group, and a method for producing the isobutylene-based polymer.

[Means for solving the problem]

The present inventors have conducted intensive studies in order to solve the above problems, synthesized an isobutylene-based polymer having an allyl phenyl ether group at the terminal, and performed hydrosilylation, thereby introducing a dimethoxymethylsilyl group at the terminal. Even after this, it was found that the gelation did not occur easily, leading to the present invention.

That is, the gist of the present invention is as follows: (1) The number average molecular weight is 500 to 200,000, and at least 1.1 general formula (I) per molecule: Wherein R ¹ and R ² represent a monovalent organic group or a hydrogen atom,
They may be the same or different. (2) 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 ³ COO— group (R ³ 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 the same as above. A method for producing an isobutylene-based polymer according to the above (1), wherein the compound has a Friedel-Crafts type reaction with an organic compound represented by the following formula (1): (3) a number average molecular weight of 500 to 200,000; At least 1.1 per formula (IV): Wherein a Friedel-Crafts type reaction of an isobutylene-based polymer having a terminal represented by the formula with an organic compound represented by the formula (III) is carried out.
(4) a number average molecular weight of from 500 to 200,000, and at least 1.1 formula (V) per molecule: Wherein a Friedel-Crafts type reaction of an isobutylene-based polymer having a terminal represented by the formula with an organic compound represented by the formula (III) is carried out.
(5) The number average molecular weight is 500 to 200,000, and the terminal represented by the formula (IV) and the terminal represented by the formula (V) are each 3% of the total terminal amount. The method for producing an isobutylene-based polymer according to (1), wherein a Friedel-Crafts-type reaction between the isobutylene-based polymer contained above and the organic compound represented by the general formula (III) is performed. 6) (A) a cationically polymerizable monomer containing isobutylene; (B) a general formula (VI) as an initiator / chain transfer agent: [In the formula, Y represents a halogen atom or an R ⁷ COO— group (R ⁷ is a monovalent organic group). R ⁴ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ⁵ and R ⁶ are the same or different and each represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ⁴ represents a polyvalent aliphatic hydrocarbon group, R ⁵ and R ⁶ 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) (3) The method for producing an isobutylene-based polymer according to the above (1), wherein the organic compound represented by (III) is added to carry out a Friedel-Crafts type reaction. (7) (A) Cationic polymerization containing isobutylene (B) an organic compound having a group represented by the general formula (VI) as an initiator / chain transfer agent, (C) a Lewis acid, and (D) an organic compound represented by the general formula (III). The method according to (1), wherein the mixture is subjected to the Friedel-Crafts-type reaction at the same time as the polymerization reaction of the cationically polymerizable monomer containing isobutylene of (A). And a method for producing an isobutylene-based polymer.

When a crosslinkable silyl group-terminated polymer such as dimethoxymethylsilyl group is obtained by using the allyl-terminated polymer of the present invention, this polymer has an excellent feature that it does not gel easily.

In the method for producing an allyl-terminated polymer of the present invention, polymerization and introduction of an allyl group can be carried out in one pot. And a polymer having a more uniform molecular weight.

Furthermore, in the method for producing an allyl-terminated polymer of the present invention, an unsaturated terminal polymer can be used as a raw material polymer. Can be used, -30
There is also an advantage that a good polymer can be obtained even at a relatively high temperature of ° C.

The isobutylene-based polymer of the present invention has a number average molecular weight of 50.
0-200,000, with at least 1.1 general formula (I) per molecule: Wherein R ¹ and R ² represent a monovalent organic group or a hydrogen atom,
They may be the same or different. ] It has a terminal represented by these.

Here, examples of the monovalent organic group for R ¹ and R ² include an alkyl group, an alkoxy group, an alkylthio group, a phenoxy group and the like. The alkyl group usually has 1 carbon atom.
-10 to 10 straight-chain or branched ones are preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an allyloxy group.

The isobutylene-based polymer of the present invention has a number average molecular weight of 50.
It is 0 to 200,000, preferably 2,000 to 15,000.
It has at least 1.1 terminals represented by the general formula (I) per molecule.

The method for producing the isobutylene-based polymer of the present invention includes the following method.

(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 ³ COO— group (R ³ 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 the same as above. And a Friedel-Crafts type reaction with an organic compound represented by the following formula:

Here, regarding the general formula (II), W is a halogen atom or
R ³ COO— represents a group.

As the organic compound represented by the general formula (III) used in the Friedel-Crafts type reaction, conventionally known compounds can be widely used as long as they correspond to the general formula (III), and preferably, Specifically, the following are exemplified.

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 in combination 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 and the} like are preferable, and SnCl ₄ and AlCl ₃ are particularly preferable.

The amount of the Lewis acid to be used is preferably about 0.1 to 20 times, more preferably about 0.5 to 8 times, the total amount of functional groups of the isobutylene-based 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 formula (I) and the organic compound represented by the formula (III).

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

(Production Method 3) In the same manner as in Production Method 2, the number average molecular weight was 500 to 20.
0,000 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 formula (I) and the organic compound represented by the formula (III).

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

(Production Method 4) Furthermore, the production method of the present invention has a number average molecular weight of 500 to 20.
An isobutylene-based polymer containing 3% or more of the total amount of the terminal represented by the formula (IV) and the terminal represented by the formula (V);
It can be produced by performing a Friedel-Crafts type reaction with the organic compound represented by I).

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 ⁷ COO— group (R ⁷ is a monovalent organic group). R ⁴ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ⁵ and R ⁶ are the same or different and each represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ⁴ represents a polyvalent aliphatic hydrocarbon group, R ⁵ and R ⁶ 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 carrying out a Friedel-Crafts type reaction by adding an organic compound represented by III).

Method: (A) a cationically polymerizable monomer containing isobutylene, and (B) the above-mentioned general formula (V) as an initiator / chain transfer agent
A mixture of an organic compound having a group represented by I), (C) a Lewis acid, and (D) an organic compound represented by the general formula (III) is used to form the (A) isobutylene-containing cationic polymerizable monomer. It can be produced by performing a Friedel-Crafts type reaction simultaneously with 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.

Examples of the cationic polymerizable monomer copolymerizable with isobutylene include olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. 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, Zia Ruri dimethylsilane, .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 (VIII) (In the formula, R ⁵ , R ⁶ and Y are the same as above.) n shows the integer of 1-6. General formula (IX): BZm (IX) [In the formula, B represents a hydrocarbon group having 4 to 40 carbon atoms. Z is a halogen atom bonded to a tertiary carbon atom or an R ⁷ COO— group (R
⁷ is 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,
Two or more kinds 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 ⁷ 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 ⁷ 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 ⁷ COO— groups represented by the general formula (VI), or a bonded halogen atom or R ⁷ 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, Examples include, but are not limited to, halogen-containing organic compounds such as oligomers of α-chlorostyrene or R ⁷ COO-group-containing organic compounds. 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. The molecular weight of the obtained polymer can be controlled by adjusting the amount of these compounds used. 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 at the time of the polymerization reaction in the present invention is a component used as a catalyst. As the Lewis acid, conventionally known ones can be widely used, for example,
Examples include, but are not limited to, 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 used is preferably about 0.0001 to 10 times, more preferably 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. The degree 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 organic compound represented by the general formula (III) or the like is sequentially charged may be used, or the inert solvent, the cationically polymerizable monomer, the initiator and chain transfer agent, and used during the polymerization reaction. A continuous method in which a Lewis acid or the like is allowed to react while continuously charged in 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 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) is obtained, the polymerization temperature is -50 to -50.
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 an allyl group at a terminal is obtained in one pot by adding an organic compound represented by the general formula (III) to the polymerization system before or after the start of polymerization. be able to.

Solvents for performing the above polymerization reaction and Friedel-Crafts type reaction in one pot include halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, 1,1-dichloroethane and ethyl chloride, and aromatics 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 system added before the start of the polymerization, a polymer having a more uniform molecular weight is obtained. Tend to be obtained.

When producing an isobutylene-based polymer having an allyl group at one end 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 obtain an isobutylene-based polymer having an allyl group at the terminal and not easily gelling even after the terminal is converted to a dimethoxymethylsilyl group.

Furthermore, in the method of the present invention, it is possible to obtain an isobutylene-based polymer having an allyl group at the terminal in one pot, and in a system in which the organic compound represented by the general formula (III) is added before the start of polymerization. And a polymer having a more uniform molecular weight.

Furthermore, when the method of the present invention is compared with the above-mentioned JP-A-63-105005, there is no need to use an expensive Lewis acid such as BCl _{3 and} a good polymer can be obtained even at a relatively high temperature of −30 ° C. There are many advantages in cost.

〔Example〕

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

Example 1 General formula (X): (Where R ⁸ is (A is 0 or an integer of 1 to 100). R ⁹ is (B is 0 or an integer of 1 to 100). R ¹⁰ is (C is 0 or an integer of 1 to 100). ] An isobutylene-based polymer (n = 5000, w /
n = 1.5) 2.0 g, 6 mmol of allyl phenyl ether and 10 ml of methylene chloride were added to a 50 ml eggplant flask,
The mixture was 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 in a closed system for 6 hours. Thereafter, the methylene chloride solution was shaken with 20 ml of a saturated aqueous sodium hydrogen carbonate solution, and further washed twice with 20 ml of tap water. The methylene chloride solution was further concentrated to 5 ml, and the concentrated solution was poured into 100 ml of acetone to precipitate and separate the polymer. The polymer thus obtained was again dissolved in 30 ml of hexane,
After drying over anhydrous magnesium sulfate and filtration, hexane was distilled off under reduced pressure to obtain the desired isobutylene polymer.

While calculating the yield from the yield of the obtained polymer,
by GPC n and w / n, also a terminal structure ¹ H-N
Measuring the intensity of the resonance signals of protons attributable to the structure by MR (30MH _Z) method, it was determined by comparison. The results are shown in Table 1.

Example 2 An isobutylene-based polymer as a raw material was represented by the following general formula (XI): (Where R ¹¹ is (D is 0 or an integer of 1 to 100). R ¹² is (E is 0 or an integer of 1 to 100). R ¹³ 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 Example 1 and Example 2, it is apparent that when allyl phenyl ether is used, the terminal having a chlorine atom and the terminal represented by the formula (IV) are quantitatively converted to the terminal having an allyl group. became.

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 hydride 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-way cocks. Further, cooling was continued for 1 hour with stirring, and the inside of the polymerization vessel was cooled 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 allyl phenyl ether was added. It was added from a three-way cock using a syringe.

Then, after stirring the reaction solution at room temperature for 6 hours, 100 ml
After shaking with saturated aqueous sodium hydrogen carbonate solution, the organic layer was washed twice with 100 ml of water. The organic layer was concentrated to 10 ml and the polymer was precipitated by adding it to 300 ml of acetone with stirring.

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

The isobutylene-based polymer thus obtained was used in Example 1
The evaluation was performed in the same manner as described above. 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 at 60 minutes after the start of the polymerization, methanol cooled to -40 ° C or lower was added instead of allylphenyl ether to terminate the polymerization. Manufactured and evaluated. Second result
It is also shown in the table.

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

Example 5 Example 4 except that 10 mmol of allyl phenyl ether was added before the start of the polymerization and not added after the start of the polymerization.
An isobutylene-based polymer was produced and evaluated in the same manner as described above. The results are shown in Table 2.

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

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

From Table 2, it is clear that according to the method of Example 4, the polymerization reaction is carried out at a relatively high temperature of -30 ° C, and an isobutylene-based polymer having an allyl group at the terminal can be obtained 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 an allyl group at a terminal.
Quite low cost and practical.

Example 6 About 0.5 g of a polymer obtained by converting the terminal allyl group into a dimethoxymethylsilyl group in the polymer obtained by the method of Example 5 was used in an amount of 5 ml.
The sample was placed in a closed sample bottle and left at room temperature in a closed system, and the number of days until gelation was determined. The results are shown in Table 3.

Comparative Example 2 The procedure of Example 6 was repeated except that the isobutylene-based polymer having an allyl group at the terminal was manufactured by the method described in JP-A-63-105005 until gelation. The number of days was examined. The results are shown in Table 3.

Comparative Example 3 Except that an isobutylene-based polymer having an allyl group at the terminal was prepared by the method described in JP-A-62-166199, the procedure until gelation was carried out in the same manner as in Example 6. The number of days was examined. The results are shown in Table 3.

From the results shown in Table 3, it was clarified that the isobutylene-based polymer produced by the method of the present invention gave a dimethoxymethylsilyl group-terminated oligomer which was most difficult to gel.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-20501 (JP, A) JP-A-64-11102 (JP, A) JP-A-63-105005 (JP, A) JP-A-1- 247402 (JP, A) JP-A-54-66993 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 8 / 02,10 / 10,210 / 10

Claims (7)

(57) [Claims] (1) a number average molecular weight of from 500 to 200,000 and at least 1.1 general formula (I) per molecule: Wherein R ¹ and R ² represent a monovalent organic group or a hydrogen atom,
They may be the same or different. ] An isobutylene polymer having a terminal represented by the formula: 2. A compound having 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 ³ COO— group (R ³ 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 the same as above. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with an organic compound represented by the following formula is carried out. 3. 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 and R ² are the same as above. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with an organic compound represented by the following formula is carried out. 4. A compound having a number average molecular weight of from 500 to 200,000 and having 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 and R ² are the same as above. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with an organic compound represented by the following formula is carried out. 5. A compound of the formula (IV) having a number average molecular weight of 500 to 200,000. And a terminal represented by the formula (V): An isobutylene-based polymer containing 3% or more of the total terminal amount represented by the following general formula (III): Wherein R ¹ and R ² are the same as above. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with an organic compound represented by the following formula is carried out. 6. 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 ⁷ COO— group (R ⁷ is a monovalent organic group). R ⁴ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ⁵ and R ⁶ are the same or different and each represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ⁴ represents a polyvalent aliphatic hydrocarbon group, R ⁵ and R ⁶ 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 and R ² are the same as above. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction is carried out by adding an organic compound represented by the following formula: 7. A cationic polymerizable monomer containing (A) isobutylene, (B) a general formula (VI) as an initiator and a chain transfer agent: Wherein Y, R ⁴ , R ⁵ and R ⁶ 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 and R ² are the same as above. (1) The organic compound represented by the formula (1) is mixed to carry out the Friedel-Crafts-type reaction simultaneously with the polymerization reaction of the cationic polymerizable monomer containing isobutylene (A). A method for producing an isobutylene-based polymer.