JP3092875B2 - Isobutylene polymer having vinyl group at terminal and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isobutylene-based polymer having a terminal vinyl group and a method for producing the same.

[0002]

2. Description of the Related Art Terminal-functional polymers, for example, polymers having vinyl groups introduced at both ends of the molecule, include photo-curable resins, UV-curable resins, and electron beam-curable resins. It is useful as a raw material for modified silicone addition-curable resins, adhesives, modifiers, coating agents and the like. A kind of terminal functional polymer, for example, -C (CH ₃ ) at the terminal
_The isobutylene-based polymer having a ₂ Cl group is 1,4-bis (α-chloroisopropyl) benzene (hereinafter simply referred to as “p
-DCC) is known to be produced by an inifer method (US Pat. No. 4,276,394) in which isobutylene is cationically polymerized using BCl ₃ as an initiator and a chain transfer agent as a catalyst.

[0003] Further, to the isobutylene-based polymer having a chloro group at both terminals immediately after polymerization obtained by the inifer method or after purification, further adding TiCl ₄ and then adding allyltrimethylsilane to the allyl terminal to form an allyl at both terminals. It is known that a polymer having a group can be obtained (JP-A-63-105005; hereinafter, this production method is referred to as an allylsilane method). However, in the above-mentioned allylsilane method, since an expensive Lewis acid called BCl ₃ is used in the polymerization step, the obtained polymer is expensive as a product. Further, in the above allylsilane method, the polymerization reaction is carried out at a very low temperature of -80 ° C. However, when assuming actual production, a considerably large-scale cooling device is required, and the temperature of -80 ° C is not practical. is not. However, it is impossible to raise the polymerization temperature by the allylsilane method. For example, when a polymerization reaction is performed at a relatively realistic temperature of about −30 ° C., a terminal group having low reactivity with allylsilane (—CH ₂ C (CH ₃ ) = CH ₂ group or —CH ＝ C (CH ₃ )) ₂ ) is a by-product.

[0004] A method of curing an isobutylene-based polymer produced by an allylsilane method using a hydrosilylation reaction is known (JP-A-3-200807). This curing reaction is hereinafter referred to as an addition-type curing reaction. Do). Example 19 in the above-mentioned JP-A-3-200807 describes that the snap-up time in the addition-type curing reaction of the polymer produced by the allylsilane method is 50 seconds at 100 ° C. However, in view of the application of additional curing to line production, it is desirable that the curing speed be even faster. In addition, the durability (heat resistance, weather resistance, etc.) of the addition-type cured product is still insufficient compared with the addition-type silicone resin, etc., and the emergence of a more durable isobutylene-based polymer is expected. It is rare.

[0005] A first object of the present invention is to provide an isobutylene-based polymer having a vinyl group at a terminal having good properties. A second object of the present invention is to provide a method for producing the isobutylene-based polymer.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, using a general-purpose Lewis acid, obtain an isobutylene-based polymer having a vinyl group at a terminal. Found a way. Furthermore, using the method of the present _{invention, -CH 2 C (CH 3)} = CH 2 group or -CH = C
It was revealed that the (CH ₃ ) ₂ group can be easily converted to a vinyl group terminal. That is, the present invention provides: (1) a compound having a number average molecular weight of 500 to 200,000, and at least 0.2 of the general formula (I):

[0007]

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[Wherein, n is an integer of 1 to 30, R ¹
And R ² represent a monovalent organic group or a hydrogen atom, which may be the same or different. An isobutylene-based polymer having a vinyl group at the terminal represented by the formula:

(2) The number average molecular weight is from 500 to 200,000, and at least 1.1 general formula (II) per molecule:

[0010]

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Wherein W is a halogen atom or R ³ COO
A group (R ³ is a monovalent organic group). And an isobutylene-based polymer having a terminal represented by the general formula (III):

[0012]

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Wherein n, R ¹ and R ² are as defined above. A method for producing an isobutylene-based polymer according to the above (1), wherein a Friedel-Crafts type reaction is performed with an organic compound represented by the following formula:

(3) The number-average molecular weight is from 500 to 200,000, and at least 1.1 terminals per molecule represented by the formula (IV): -CH ₂ -C (CH ₃ ) = CH ₂ (IV): A method for producing an isobutylene-based polymer according to the above (1), wherein a Friedel-Crafts type reaction between the isobutylene polymer having the polymer and the organic compound represented by the general formula (III) is performed;

(4) An isobutylene-based polymer having a number-average molecular weight of 500 to 200,000 and having at least 1.1 terminals per molecule of the formula (V): —CH ＝ C (CH ₃ ) ₂ (V): The method for producing an isobutylene-based polymer according to the above (1), wherein a Friedel-Crafts type reaction between the coalesced compound and the organic compound represented by the general formula (III) is performed;

[0016] (5) The number average molecular weight of 500 to 200,000, formula _{(IV): -CH 2 -C (} CH 3) = CH 2 (IV): represented by the terminal or the formula with (V): -CH = C (CH ₃ ) ₂ (V): Friedel-Crafts type reaction between an isobutylene-based polymer containing 3% or more of the total terminal amount represented by the following formula and an organic compound represented by the general formula (III) The method for producing an isobutylene-based polymer according to the above (1),

(6) (A) a cationically polymerizable monomer containing isobutylene,
(B) General formula (VI) as initiator and chain transfer agent:

[0018]

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Wherein Y is a halogen atom or R ⁷ COO
-R (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. Where R
^{When 4} represents a polyvalent aliphatic hydrocarbon group, R ⁵ and R
⁶ cannot be both hydrogen atoms. An organic compound having a group represented by the formula (C) and a Lewis acid,
(A) The isobutylene-containing cationic polymerizable monomer is polymerized, and then (D) a compound of the general formula (III)
Wherein the Friedel-Crafts type reaction is carried out by adding an organic compound represented by the formula (1);

(7) (A) a cationically polymerizable monomer 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) are mixed and mixed. (A)
(1) The method for producing an isobutylene-based polymer according to the above (1), wherein the polymerization reaction of the cationically polymerizable monomer containing isobutylene is performed simultaneously with the Friedel-Crafts type reaction.

In the present specification, n is an integer of 1 or more and 30 or less. However, from the viewpoint of availability of raw materials, n is preferably 1 to 8, for example, 1, 4 or 8 is suitably used. . Here, the monovalent organic group for R ¹ and R ² includes an alkyl group, an alkoxy group, an alkylthio group,
Phenoxy groups and the like. As the alkyl group in the alkyl group, the alkoxy group and the alkylthio group, a linear or branched one having 1 to 10 carbon atoms is usually preferable, and methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Examples are tert-butyl, hexyl, allyl, 1-hexenyl group and the like. Examples of the alkoxy group include methoxy, ethoxy, allyloxy and the like. The isobutylene polymer of the present invention has a number average molecular weight of 500 to 200,00.
0, preferably 2,000 to 15,000. Further, the terminal represented by the general formula (I) should be at least 0.
Although it has two, it is preferable that it has 1.1 or more per molecule.

The method for producing the isobutylene polymer of the present invention includes the following methods. Production Method 1 A polymer having a number-average molecular weight of 500 to 200,000 and having at least 1.1 terminal isobutylene-based polymer represented by the general formula (II) per molecule and an organic compound represented by the general formula (III) And a Friedel-Crafts type reaction with The organic compound represented by the general formula (III) used in the Friedel-Crafts type reaction can be used without particular limitation as long as it corresponds to the general formula (III), and is preferably a specific compound. The following are exemplified.

[0023]

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The Friedel-Crafts type reaction proceeds both in a solvent and without a solvent. As the solvent, those that can be used in ordinary Friedel-Crafts type reactions can be widely used, and specifically, n-hexane, n-pentane,
aliphatic hydrocarbon compounds such as n-heptane and cyclohexane, methylene chloride, carbon tetrachloride, chloroform, 1,
Preferred examples include halogenated hydrocarbon compounds such as 1-dichloroethane and ethyl chloride, 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 the usual 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 particularly, SnC
l ₄ and AlCl ₃ are preferred. The amount of the Lewis acid used is 0.1 to 20 of the total functional group amount of the isobutylene-based polymer.
The ratio is preferably about 0.5 times, and more preferably about 0.5 to 8 times. 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 According to the same method as Production method 1, the number average molecular weight is 500 to
200,000 and at least 1.1 formulas (I
_{V): -CH 2 -C (CH} 3) = be prepared by carrying out the Friedel-Crafts reaction of an organic compound represented by the isobutylene polymer and the general formula (III) having a terminal represented by CH ₂ Can be. The conditions for the Friedel-Crafts type reaction are the same as in the above-mentioned Production Method 1.

Production method 3 According to the same method as Production method 1, the number average molecular weight is 500 to
Is 200,000, at least 1.1 units of formula per molecule (V): - CH = C Friedel Crafts and (CH ₃₎ an organic compound represented by the isobutylene polymer and the general formula (III) having a terminal represented by ₂ It can be produced by performing a mold reaction. The conditions for the Friedel-Crafts type reaction are the same as in the above-mentioned Production Method 1.

Production Method 4 In the production method of the present invention, the number average molecular weight is 500 to 20.
0,000 and a Friedel-Crafts of an isobutylene-based polymer containing the terminal represented by the formula (IV) or (V) in an amount of 3% or more of the total terminal and an organic compound represented by the general formula (III) It can be produced by performing a mold reaction. The conditions for the Friedel-Crafts type reaction are the same as in the above-mentioned Production Method 1.

Manufacturing Method 5 The manufacturing method of the present invention also includes the following method. Method (A) Cationic polymerizable monomer containing isobutylene,
(B) an organic compound having a group represented by the general formula (VI) as an initiator / chain transfer agent, and (C) a Lewis acid are mixed to polymerize the cationic polymerizable monomer containing (A) isobutylene. Then, (D) an organic compound represented by the general formula (III) is added to the reaction solution to carry out a Friedel-Crafts type reaction.

Method (A) Cationic polymerizable monomer 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) mixing the organic compound represented by the general formula (III) and carrying out the Friedel-Crafts type reaction simultaneously with the polymerization reaction of the cationically polymerizable monomer containing isobutylene of (A). Can be. Here, the (A) cationically polymerizable monomer containing isobutylene is not limited to a monomer consisting solely of isobutylene, and 50% by weight (hereinafter simply referred to as “%”) of isobutylene and isobutylene are mixed together. It means a monomer substituted with a polymerizable cationic polymerizable monomer. Examples of the cationically polymerizable monomer copolymerizable with isobutylene include olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, and vinyl silanes. Among them, carbon number 3-12
Olefins and conjugated dienes are preferred.

Specific examples of the cationically polymerizable monomer copolymerizable with isobutylene include, for example, propylene,
1-butene, 2-butene, 2-methyl-1-butene, 3
-Methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene , Dichlorostyrene, p-hydroxystyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, ,
3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane,
Allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallylmethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, etc. Can be Among these, for example, propylene, 1-butene, 2-butene, styrene, butadiene, isoprene,
Cyclopentadiene and the like are preferred. 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 represented by the general formula
And an organic compound having a group represented by the formula (VI), for example, AY'p (VII) wherein A represents a group having 1 to 4 aromatic rings. . Y '
Is the general formula (VIII)

[0033]

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(In the formula, R ⁵ , R ⁶ and Y are the same as described above.) p is 1
Represents an integer of from 6 to 6. A compound represented by the general formula (I
X): BZm (IX) wherein B represents a hydrocarbon group having 4 to 40 carbon atoms. Z is a halogen atom bonded to a tertiary carbon atom or R ⁷ COO—
A group (R ⁷ is as defined above). m shows the integer of 1-4. And an oligomer having an α-halostyrene unit, but are not limited thereto. These compounds may be used alone or in combination of two or more.

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 type.
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,
Anthracene group, phenanthrene group, pyrene group, Ph-
(CH ₂ ) _L -Ph group (Ph is a phenyl group, L is 1 to 10
And the group having an aromatic ring is a straight-chain and / or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a functional group such as a hydroxyl group, an ether group, or a vinyl group. May be substituted with a group having a halogen atom or the like. on the other hand,
Z in the compound represented by the general formula (IX) is a halogen atom such as F, Cl, Br or I bonded to a tertiary carbon atom or an R ⁷ COO— group, and B in the general formula (IX) is a carbon atom. A hydrocarbon group of the number 4 to 40, preferably an aliphatic hydrocarbon group, and when the number of carbon atoms is less than 4, the carbon atom to which the halogen atom or R ⁷ COO— group is bonded is not a tertiary carbon atom; The polymerization does not easily proceed, and it becomes difficult to use it suitably.

Examples of the oligomer having an α-halostyrene unit which can be used as an initiator / chain transfer agent include, for example, an oligomer of α-chlorostyrene and a copolymer of α-chlorostyrene and a monomer copolymerizable therewith. Polymerized oligomers and the like can be mentioned. 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 represented by the general formula (VI)
When a compound having a COO- group and another reactive functional group is used as an initiator and a 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. It is very effective because it can. Specific examples of the initiator and chain transfer agent include, for example,

[0037]

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[0038]

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[Y is the same as above. Examples thereof include, but are not limited to, a halogen atom-containing organic compound such as an oligomer of α-chlorostyrene or an R ⁷ COO— group-containing organic compound. Among these compounds

[0040]

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[0041]

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A halogen atom-containing organic compound which easily generates a stable carbon cation,

[0043]

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Preferred are organic compounds containing a CH ₃ COO— group. These compounds are components used as an initiator and a chain transfer agent.
Used as a mixture of more than one species. 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 an amount of about 0.01 to 20%, preferably about 0.1 to 20%, based on the cationically polymerizable monomer usually containing isobutylene.
It is better to use it at a rate of about 10%.

In the present invention, it is used at the time of the polymerization reaction.
(C) Lewis acid is a component used as a catalyst. As the Lewis acid, conventionally known ones can be widely used, for example, AlCl ₃ , SnCl ₄ , TiCl ₄ , V
Examples include, but are not limited to, Cl ₅ , FeCl ₃ , BF _{3, and the} like. Of these Lewis acids, A
ICl 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, and specific examples thereof include chloromethane, chloroform and the like.
Carbon tetrachloride, chloroethane, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane,
Halogenated hydrocarbon compounds such as 1,1,2,2-tetrachloroethane and tetrachloroethylene, n-hexane,
aliphatic hydrocarbon compounds such as n-pentane, nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, nitrotoluene, o-, m-
Alternatively, a compound having a nitro group, such as p-dinitrobenzene, may be used. 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 container, the polymerization solvent is an inert solvent, the isobutylene-containing cationic polymerizable monomer, the initiator / chain transfer agent, the Lewis acid used in the polymerization reaction, and in some cases, the compound represented by the general formula (III). A batch method of sequentially charging the organic compound represented by the formula may be used, or the inert solvent, the cationic polymerizable monomer, the initiator / chain transfer agent, the organic compound represented by the general formula (III), the polymerization reaction A continuous method may be used in which a Lewis acid or the like sometimes used is allowed to react while being continuously charged into a certain system and then taken out.

In the method of the present invention, the polymerization temperature is preferably about -120 to 0 ° C, more preferably about -60 to -10 ° C. In order to obtain the terminal represented by the general formula (II) in the present invention with a high purity of 95% or more of all terminal functional groups, the polymerization temperature is preferably -50 ° C or lower. Further, the terminal represented by the above formula (IV) or the above formula
When obtaining an isobutylene-based polymer containing 3% or more of the terminal represented by (V), the polymerization temperature is preferably about -30 to -10 ° C. The polymerization time varies depending on the cooling capacity of the reaction vessel, the scale of the polymerization, and the like, and cannot be determined unconditionally. The monomer concentration during 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, before the start of the polymerization or after the end of the polymerization, an organic compound represented by the above general formula (III) is added to the polymerization system, whereby an isobutylene-based polymer having a terminal vinyl group in one pot is obtained. Coalescence can be obtained. 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 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. Also, as the Lewis acid, AlC
l 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, the molecular weight becomes more uniform. There is a tendency for polymers to be obtained. Also,
When producing an isobutylene-based polymer having a vinyl group at a terminal in one pot, it is preferable to carry out a Friedel-Crafts type reaction at 0 to 40 ° C. after conducting the polymerization reaction at −60 ° C. to −10 ° C. However, depending on the polymerization conditions, it is also possible to complete the Friedel-Crafts type reaction at the same time as performing the polymerization reaction at −60 to −10 ° C. to obtain an isobutylene-based polymer having a vinyl group at a terminal. Usually, the polymerization reaction is 0.1 ~
It is preferable to carry out the Friedel-Crafts type reaction for about 120 minutes and for about 0.5 to 24 hours.

[0051]

The present invention will be further clarified with reference to the following examples. The number average molecular weight and the number of functional groups per molecule in the examples were determined by the following methods. (1) The number average molecular weight (Mn) was determined by GPC measurement (polystyrene conversion). Column: Showdex K804 (manufactured by Showa Denko); Column temperature:
Solvent: chloroform; flow rate: 1.0 ml / min; data processing program; MAXIMA 820 (manufactured by Waters) (2) The number of functional groups per molecule is based on the number average molecular weight (Mn) obtained from GPC measurement. , ¹ H-NMR spectrum (300 MHz) was obtained by comparing the integrated value of the peak of the main chain skeleton and the peak of the terminal vinyl group. ¹ H-NMR measurement conditions Solvent: A mixture of carbon tetrachloride and heavy acetone (Lock solvent), based on TMS. Example 1 General formula (X):

[0052]

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Wherein R ⁸ , R ⁹ and R ¹⁰ are each independently

[0054]

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(Wherein a represents 0 or an integer of 1 to 100). 2.0 g of an isobutylene-based polymer (Mn = 5000, Mw / Mn = 1.5) represented by the general formula (III)

[0056]

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6 mmol and 10 ml of methylene chloride were added to 50 m
and stirred with a magnetic stirrer. After 6 mmol of tin tetrachloride was added to the homogeneous solution thus obtained, the mixture was stirred at room temperature for 3 hours in a closed system. Thereafter, the methylene chloride solution was shaken together with a saturated aqueous sodium hydrogen carbonate solution (20 ml), and further tap water (20 m).
1 × twice. 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 dissolved again in 30 ml of hexane, dried over anhydrous magnesium sulfate, filtered, and then hexane was distilled off under reduced pressure to obtain a target isobutylene polymer. The yield was calculated from the yield of the obtained polymer, and Mn and M
w (weight average molecular weight) / Mn was determined by measuring and comparing the intensity of the resonance signal of the proton belonging to each structure by the GPC method and the terminal structure by the ¹ H-NMR (300 MHz) method or the like. Table 1 shows the results.

Examples 2-5 Compounds Instead of Compounds

[0059]

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The reaction was carried out in the same manner as in Example 1 except that the above was used, and the obtained isobutylene polymer was purified and evaluated. The results are shown in Table 1.

Example 6 The starting material isobutylene-based polymer was converted to a compound represented by the general formula (XI):

[0062]

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Wherein R ¹¹ , R ¹² and R ¹³ are each independently

[0064]

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(Where b represents 0 or an integer of 1 to 100. P represents —CH ＝ C (CH ₃ ) ₂ or —CH ₂ —C
(CH ₃ ) = CH ₂ is shown. ] [Mn = 5000, Mw / Mn = 1.5, Fn (-C
H = C (CH ₃ ) ₂ ) = 1.2, Fn (—CH ₂ C (C
The reaction was carried out in the same manner as in Example 1 except that H ₃ ) = CH ₂ ) = 1.8], and the obtained isobutylene polymer was purified and evaluated. The results are shown in Table 1.

Examples 7 to 10 The reaction was carried out in the same manner as in Example 6 except that Compound 1 was used in place of the compound, and the obtained isobutylene polymer was purified and evaluated. The results are shown in Table 1.

[0067]

[Table 1]

Example 11 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 evacuating 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.

[0069]

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A solution prepared by dissolving 1 mmol of tricumyl chloride represented by the following formula in 40 ml of methylene chloride dried by calcium hydride treatment was added. Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 5 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. 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. Mmol was added via a three-way cock using a syringe. Thereafter, the reaction solution was stirred at room temperature for 6 hours, shaken with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate, and 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. 80 ml of n-
Dissolved in hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure.
An isobutylene polymer was obtained. The isobutylene polymer thus obtained was evaluated in the same manner as in Example 1. Table 2 shows the results.

Examples 12 to 15 The reaction was carried out in the same manner as in Example 11 except that Compound 1 was used in place of the compound. The obtained isobutylene polymer was purified and evaluated. The results are shown in Table 2.

Example 16 An isobutylene-based polymer was produced and evaluated in the same manner as in Example 11, except that the temperature during the polymerization reaction was -30 ° C. The results are shown in Table 2.

Examples 17 to 20 The reaction was carried out in the same manner as in Example 16 except that the compound was used instead of the compound, and the obtained isobutylene-based polymer was purified and evaluated. The results are shown in Table 2.

Example 21 An isobutylene-based polymer was produced and evaluated in the same manner as in Example 16 except that 10 mmol of the compound 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. From the results of Example 16 and Example 21, it was revealed that by adding the compound before the start of polymerization, an isobutylene-based polymer having a more uniform molecular weight (that is, a smaller Mw / Mn value) can be obtained. . Examples 22 to 25 The reaction was carried out in the same manner as in Example 21 except that Compound 1 was used instead of the compound, and the obtained isobutylene-based polymer was purified and evaluated. The results are shown in Table 2.

[0076]

[Table 2]

Example 26 As in Example 5 in JP-A-3-200807, a polymer having an allyl group at the terminal (by the allylsilane method)
And polyhydrogensiloxane (L made by Shin-Etsu Chemical Co., Ltd.)
S8600) to synthesize Si-H-terminated polyisobutylene. Further, in the same manner as in Example 19 in JP-A-3-200807, an addition-type curing reaction of the polymer produced in Example 1 of the present specification was carried out using the Si-H-terminated polyisobutylene. Table 3 shows the measurement results of the snap-up time.

Comparative Example 1 An isobutylene-based polymer (Mn = 380) produced by the allylsilane method was used instead of the polymer produced in Example 1 above.
0, Mw / Mn = 1.20, Fn (allyl) = 3.0 It was produced in the same manner as in Synthesis Example 4 in JP-A-3-200807. A curing reaction was carried out in the same manner as in Example 26, except that) was used. Table 3 also shows the measurement results of the snap-up time.

[0079]

[Table 3]

Example 27 In the same manner as in Example 9 in JP-A-3-95266,
A hydrocarbon-based addition-type curing agent was synthesized from 9-decadiene and polyhydrodienesiloxane (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) as raw materials. A cured product of the isobutylene-based polymer produced in Example 2 of the present specification was prepared in the same manner as in Example 11 in JP-A-3-95266 using the above-mentioned hydrocarbon-based addition-type curing agent. A heat resistance test was performed at ℃. Table 4 shows the results.

Comparative Example 2 The procedure of Example 2 was repeated, except that the polymer used in Comparative Example 1 was used instead of the isobutylene polymer.
A cured product was prepared in the same manner as in Example 27, and a heat resistance test was performed. The results are shown in Table 4.

[0082]

[Table 4]

Example 28 The isobutylene polymer represented by the general formula (X) used in Example 1 (Mn = 5000, Mw / Mn = 1.5) 2.0
g, 6 mmol of allyl phenyl ether and 10 ml of methylene chloride were added to a 50 ml eggplant-shaped 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 in a closed system for 6 hours. Subsequent operations are described in Example 1.
An isobutylene-based polymer was obtained in the same manner as described above. The yield is calculated from the yield of the obtained polymer, and Mn and Mw are calculated.
/ Mn by GPC method and ¹ H-NMR
The intensity was determined by measuring and comparing the intensity of the resonance signal of the proton belonging to each structure by the (300 MHz) method or the like. Table 5 shows the results.

Example 29 In a compound represented by the general formula (XI), R ¹¹ , R ¹² and R ¹³ were each independently

[0085]

Embedded image

(In the formula, d represents 0 or an integer of 1 to 100.) Example 2 except that an isobutylene-based polymer (Mn = 5000, Mw / Mn = 1.5) represented by
The reaction was carried out in the same manner as in Example 8, and the obtained isobutylene-based polymer was purified and evaluated. The results are shown in Table 5. From the results of Example 28 and Example 29, when allyl phenyl ether was used, the terminal having a chlorine atom and the above-mentioned formula (IV)
It was found that the terminal represented by was quantitatively converted to a terminal having an allyl group.

[0087]

[Table 5]

Example 30 An isobutylene-based polymer was produced in the same manner as in Example 11 except that allyl phenyl ether was used instead of the compound in Example 11. The isobutylene polymer thus obtained was evaluated in the same manner as in Example 28. Table 6 shows the results. Example 31 An isobutylene-based polymer was produced and evaluated in the same manner as in Example 30 except that the temperature during the polymerization reaction was changed to -30 ° C. The results are shown in Table 6.

Comparative Example 3 An isobutylene-based compound was prepared in the same manner as in Example 31 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. Polymers were prepared and evaluated. Table 6 shows the results
Are shown together. From the results of Example 31 and Comparative Example 3, it was clarified that the terminals once formed and represented by the formulas (IV) and (V) were respectively reacted with allyl phenyl ether.

Example 32 Example 31 was repeated except that 10 mmol of allyl phenyl ether was added before the start of the polymerization and was 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 6. Example 31 and Example 32
According to the results, the addition of allyl phenyl ether prior to the initiation of polymerization resulted in a more uniform molecular weight (ie, Mw
/ (Mn value is small) It became clear that the isobutylene type polymer can be obtained. From Table 6, it is clear that according to the method of Example 30, an isobutylene-based polymer having an allyl group at the terminal can be obtained in one pot. Further, from Table 6, according to the method of Example 31, the polymerization reaction was-
It is apparent that an isobutylene-based polymer having an allyl group at the terminal can be obtained at a relatively high temperature of 30 ° C. and in one pot. The method of Example 31 is a practical method for producing an isobutylene-based polymer having an allyl group at a terminal, which does not particularly require a large-scale cooling device, is considerably low cost, and is practical. .

[0091]

[Table 6]

[0092]

The addition-type curing rate of the isobutylene-based polymer of the present invention is faster than that of the polymer obtained by the allylsilane method. Further, from the result of the heat resistance test at 150 ° C., The polymer of the invention has better heat resistance than that obtained by the allylsilane method. Production method of the present invention, it is possible to use unsaturated terminated polymer as a raw material polymer, rather than the expensive Lewis acid of BCl ₃ as a polymerization catalyst in the polymerization of isobutylene, inexpensive to byproduct unsaturated terminated polymer Can be used.
There is also an advantage that a good polymer can be obtained even at a relatively high temperature of -30 ° C. Furthermore, in the production method of the present invention,
In one pot, it is possible to obtain an isobutylene-based polymer having a vinyl group at a terminal, and the above-mentioned general formula (III)
In a system in which an organic compound represented by
A polymer having a more uniform molecular weight can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-11102 (JP, A) JP-A-4-183702 (JP, A) JP-A-60-248704 (JP, A) JP-A-63-1988 105005 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (7)

(57) [Claims] (1) a number average molecular weight of 500 to 200,000;
At least 0.2 general formula (I) per molecule: [In the formula, n is an integer of 1 or more and 30 or less, R ¹ and R ² represent a monovalent organic group or a hydrogen atom, and may be the same or different. And an isobutylene-based polymer having a vinyl group at the terminal. (2) a number average molecular weight of 500 to 200,000;
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 n, R ¹ and R ² are the same as above. 2. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with the organic compound represented by the formula (1) is carried out. (3) a number average molecular weight of 500 to 200,000;
At least 1.1 per-molecule-terminated isobutylene polymer represented by the formula (IV): —CH ₂ —C (CH ₃ ) 2CH ₂ (IV): and a compound represented by the general formula (III): Wherein n, R ¹ and R ² are the same as above. 2. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with the organic compound represented by the formula (1) is carried out. (4) a number average molecular weight of 500 to 200,000;
At least 1.1 units per molecule of an isobutylene-based polymer having a terminal represented by the formula (V): -CH = C (CH ₃ ) ₂ (V): and a general formula (III): Wherein n, R ¹ and R ² are the same as above. 2. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with the organic compound represented by the formula (1) is carried out. (5) a number average molecular weight of 500 to 200,000;
Formula _{(IV): -CH 2 -C (} CH 3) = CH 2 (IV): represented by the terminal or the formula with (V): -CH = C ( CH 3) 2 (V): the terminal represented by An isobutylene-based polymer containing 3% or more of the total terminal amount, and a compound represented by the general formula (III): Wherein n, R ¹ and R ² are the same as above. 2. The method for producing an isobutylene-based polymer according to claim 1, wherein a Friedel-Crafts type reaction with the organic compound represented by the formula (1) 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 formula (C) and a Lewis acid (C) are mixed to polymerize the cationically polymerizable monomer containing (A) isobutylene, and then (D) a compound represented by the general formula (III) ): Wherein n, R ¹ and R ² are the same as above. 3. 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, and (B) a general formula (VI) as an initiator / 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 n, R ¹ and R ² are the same as above. 2. The isobutylene-based compound according to claim 1, wherein 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 (A) cationically polymerizable monomer containing isobutylene. A method for producing a polymer.