JP2929245B2 - Isobutylene-based polymer having unsaturated group 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 polymer having an unsaturated group and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Isobutylene polymers having an average of more than one unsaturated group per molecule can be crosslinked and cured to form a rubbery cured product. This polymer is also USP 4,904,
732, a moisture-curable polymer can be obtained by introducing a crosslinkable silicon group as disclosed in JP-A-63-6041. Isobutylene-based polymers having an average of more than one unsaturated group per molecule are known from USP 3,6
44,315 and US Pat. No. 4,524,187, this polymer is obtained by copolymerizing isobutylene and a compound having a conjugated double bond, and has a double bond in the main chain. It is a polymer having poor weather resistance, chemical resistance and reactivity.

[0003] Further, USP 4,316,973, US
P 4,758,631 and JP-A-63-10500.
No. 5 discloses a polymer having an unsaturated group at a molecular chain terminal. The polymers disclosed in US Pat. No. 4,316,973 and the like use 1,4-bis (α-chloroisopropyl) benzene (hereinafter referred to as “p-DCC”) as an initiator and chain transfer agent, and use BCl ₃ as a polymer. It is obtained by further reacting a polymer having a chlorine atom at the terminal obtained by the inifer method of cationically polymerizing isobutylene as a catalyst. The polymer disclosed in JP-A-63-105005 is prepared by reacting an isobutylene-based polymer having chlorine atoms at both ends immediately after polymerization obtained by the inifer method or after purification with allyltrimethylsilane to thereby obtain both ends. Obtained as a polymer having an allyl group. However, US Pat. No. 4,316,973, JP-A-63-10
The polymer disclosed in Japanese Patent No. 5005 or the like requires a plurality of steps or requires expensive raw materials.

An object of the present invention is to provide a novel isobutylene-based polymer having an unsaturated group, and a method for producing the isobutylene-based polymer at low cost and easily.

[0005]

A resolution means for] That is, the present invention provides (1) the isobutylene monomer units mainly, 1.05 units of the general formula on average per molecule (1):

[0006]

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[0007] [in the formula, Q is a divalent of 1 to 30 carbon atoms Al
Indicates a kylene group. (2) an isobutylene-based polymer having an unsaturated group, characterized by having a unit represented by the formula:
On average, 1.05 to 10 general formulas (1):

[0008]

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Wherein Q is a divalent organic having 1 to 30 carbon atoms
Represents a group. ] Having a unit represented by the formula
Has an unsaturated group characterized by having no unsaturated bond.
Isobutylene based polymer, (3) a cationically polymerizable monomer and formula containing isobutylene (3):

[0010]

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[0011] [in the formula, Q is a divalent of 1 to 30 carbon atoms Al
Indicates a kylene group. A process for producing an isobutylene-based polymer having an unsaturated group, characterized by polymerizing a non-conjugated diene represented by the formula (1) in the presence of a Lewis acid: (4) a cationically polymerizable monomer containing isobutylene
And general formula (3):

[0012]

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[Wherein Q is a divalent organic compound having 1 to 30 carbon atoms.
Represents a group. With a non-conjugated diene represented by
In a polymerization reaction system to be polymerized in the presence, together with a Lewis acid,
General formula (2) which is an initiator and a chain transfer agent:

[0014]

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[ Wherein, X is a halogen atom, an RCOO- group
(R is a monovalent organic group, the same applies hereinafter) or a RO- group.
R ³ is a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent fat
Represents a group hydrocarbon group. R ¹ and R ² are the same or different
Hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group
Is shown. However, when R ³ is a polyvalent aliphatic hydrocarbon group,
R ¹ and R ² are not simultaneously hydrogen atoms. ]
Having an unsaturated group that further allows an organic compound having a
(5) a method for producing an isobutylene-based polymer, which comprises: (5) polymerizing a cationically polymerizable monomer containing isobutylene in the presence of a Lewis acid;

[0016]

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[0017] [in the formula, Q is a divalent of 1 to 30 carbon atoms Al
Indicates a kylene group. A method for producing an isobutylene-based polymer having an unsaturated group, characterized by reacting with a non-conjugated diene represented by the following formula : and (6) a cationically polymerizable monomer containing isobutylene.
Is polymerized in the presence of a Lewis acid.
(3):

[0018]

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[0019] [in the formula, Q is a divalent of 1 to 30 carbon atoms Al
Indicates a kylene group. Wherein a cationically polymerizable monomer containing isobutylene is polymerized in the presence of a Lewis acid, wherein the initiator and the chain transfer agent are represented by the general formula (2):

[0020]

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[ Wherein, X is a halogen atom, an RCOO- group
(R is a monovalent organic group, the same applies hereinafter) or a RO- group.
R ³ is a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent fat
Represents a group hydrocarbon group. R ¹ and R ² are the same or different
Hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group
Is shown. However, when R ³ is a polyvalent aliphatic hydrocarbon group,
R ¹ and R ² are not simultaneously hydrogen atoms. ]
Using an organic compound having a group
The present invention relates to a method for producing an isobutylene-based polymer having a sum group .

With respect to the general formula (1), Q represents 1 to 3 carbon atoms.
It is a divalent organic group of 0, preferably a linear or branched alkylene group, and hexene is exemplified.

The isobutylene-based polymer having an unsaturated group of the present invention is a polymer having at least a unit represented by the general formula (1), and has a number average molecular weight mainly composed of an isobutylene monomer unit. Is usually 500
~ 500,000, preferably 1,000 ~ 50,000
0, more than one, preferably 1.05 or more, more preferably 1.1 per molecule on average per molecule.
It has at least 10 and at most 10, particularly preferably at least 1.1 and up to 5 units represented by the general formula (1). The unit represented by the general formula (1) is preferably present at the terminal of the polymer. Further, it is preferable that substantially no unsaturated bond is present in the main chain of the polymer of the present invention from the viewpoint of weather resistance and the like.

The method for producing the isobutylene polymer having an unsaturated group of the present invention includes the following two methods. Production method A method of polymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated diene in the presence of a Lewis acid. Production method A method in which a cationically polymerizable monomer containing isobutylene is polymerized in the presence of a Lewis acid, and further reacted with a non-conjugated diene.

In the present specification, the cationically polymerizable monomer containing isobutylene is not limited to a monomer consisting of isobutylene alone, but 50% by weight (hereinafter simply referred to as “%”) of isobutylene is referred to as isobutylene. It means a monomer substituted with a cationically polymerizable monomer that can be copolymerized. Examples of the cationic polymerizable monomer copolymerizable with isobutylene include olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, and vinyl silanes. Among these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferred, but when weather resistance and the like are problematic, olefins other than 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, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl- 1,1,
Examples include 3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.
Among them, for example, propylene, 1-butene, 2-butene, styrene, butadiene, isoprene, cyclopentadiene and the like are preferable. These cationically polymerizable monomers copolymerizable with isobutylene may be used alone or in combination of two or more with isobutylene.

The non-conjugated diene used in the present invention is represented by the general formula (3):

[0028]

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Wherein Q represents a divalent organic group having 1 to 30 carbon atoms. ] Means the compound represented by these. In the present invention, as the compound represented by the general formula (3), 1,4-pentadiene, 1,5-hexadiene, which is α, ω-diene, in terms of the activity of the functional group of the obtained polymer, 1,6-heptadiene, 1,7-octadiene,
1,8-nonadiene, 1,9-decadiene, 1,19-
Dodecadiene and the like are preferred.

The Lewis acid used in the present invention is a component used as a polymerization catalyst in the above-mentioned production method, and as a polymerization catalyst and a reaction reagent in the production method. MX ′ _p (M is a metal atom, X ′ is a halogen atom) ), For example, AlCl ₃ , SnCl ₄ , TiCl ₄ , VCl ₅ ,
FeCl ₃ , BF _3, Et ₂ AlCl, EtAlC
l ₂ organoaluminum compound such as and the like, but not limited thereto. Among these Lewis acids, SnCl ₄ , TiCl ₄ , Et ₂ AlCl, EtA
ICl _{2 and the} like are preferred. The amount of the Lewis acid used is preferably 0.1 to 10 times, more preferably 0.2 to 10 times the amount of the non-conjugated diene to be polymerized with isobutylene in the production method.
It is good to make it 5 times. In the case of the production method, the amount is preferably 0.001 to 0.1 times the isobutylene monomer and 0.01 to 5 times the non-conjugated diene to be reacted.

In the production method of the present invention, it is preferable that an initiator is further present in the polymerization reaction system in both the production method and the production method. As such an initiator, a proton source such as water, which remains in a trace amount in a normal system, can be effectively used, and for example, an initiator / chain transfer agent can be suitably used. Examples of the initiator / chain transfer agent usable in the present invention include, for example, a compound represented by the following general formula (2):

[0032]

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[In the formula, X represents a halogen atom, an RCOO-group (R is a monovalent organic group, the same applies hereinafter) or an RO-group.
R ³ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ¹ and R ² are the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ³ is a polyvalent aliphatic hydrocarbon group,
R ¹ and R ² are not simultaneously hydrogen atoms. And an organic compound having a group represented by the following formula:

Specific examples of the organic compound include, for example, AYn (4) wherein A represents a group having 1 to 4 aromatic rings. Y is a general formula (5):

[0035]

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(In the formula, R ⁴ and R ⁵ are the same or different and each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a halogen atom, an RCOO— group or an RO— group. ) Represents a group bonded to the aromatic ring. n is 1 to
Indicates an integer of 6. A compound represented by the general formula (6): BZm (6) wherein B represents a hydrocarbon group having 4 to 40 carbon atoms. Z represents a halogen atom, an RCOO- group or an RO- group bonded to a tertiary carbon atom. 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 (4), 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,
Anthracene group, phenanthrene group, pyrene group, Ph-
(CH ₂ ) _L- Ph group (Ph is a phenyl group, _L is 1 to 1
And an aromatic ring group having 1 to 20 carbon atoms and a functional group such as a hydroxyl group, an ether group, or a vinyl group. May be substituted with a group having On the other hand, Z in the compound represented by the general formula (6) is a halogen atom such as F, Cl, Br, I bonded to a tertiary carbon atom, RCOO.
And B in the general formula (6) is a hydrocarbon group having 4 to 40 carbon atoms, preferably an aliphatic hydrocarbon group. When the number of carbon atoms is less than 4, a halogen atom; The RCOO- group or the carbon to which the RO- group is bonded is the third
And it is not suitable for use because the polymerization is difficult to proceed.

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 production method of the present invention, a compound having two or more halogen atoms, RCOO— groups, or RO— groups in a bond represented by the general formula (2), or a halogen in a bond represented by the general formula (2) It is very effective to use an atom, an RCOO-group or a compound having an RO-group and another reactive functional group as an initiator and a chain transfer agent since the degree of functionalization of the resulting polymer can be increased.

Specific examples of the initiator and chain transfer agent include, for example,

[0040]

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Examples include, but are not limited to, halogen-containing organic compounds such as oligomers of α-chlorostyrene or RCOO-group-containing organic compounds. Preferred among these compounds are:

[0042]

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A halogen atom-containing organic compound having —C (CH ₃ ) ₂ Cl or —C (CH ₃ ) ₂ Br which easily forms a stable carbon cation,

[0044]

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CH ₃ COO-group-containing organic compounds such as

[0046]

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Organic compounds containing a CH ₃ O-group such as described above.

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 or the amount of residual water. In the present invention, the above-mentioned compound is preferably 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.

In the present invention, a hydrocarbon solvent such as an aliphatic hydrocarbon and a halogenated hydrocarbon is used as a polymerization solvent in the production method and as a polymerization and reaction solvent in the production method. Of these, halogenated hydrocarbons are preferred, and chlorinated hydrocarbons having a chlorine atom are more preferred. Specific examples of such aliphatic hydrocarbons include pentane and hexane, and specific examples of halogenated hydrocarbons include chloromethane, chloroethane, methylene chloride,
Examples thereof include 1,1-dichloroethane, chloroform, and 1,2-dichloroethane. These may be used alone or as a mixture of two or more. Further, a small amount of another solvent, for example, an acetic ester such as ethyl acetate or an organic compound having a nitro group such as nitroethane may be used in combination.

In carrying out the production method of the present invention, there is no particular limitation, and conventional polymerization methods can be widely applied. For example, in the production method, a batch method in which a polymerization solvent, a monomer, a non-conjugated diene, a catalyst, an initiator and a chain transfer agent, etc. are sequentially charged in one container may be used, or a polymerization solvent, a monomer, a non-conjugated diene may be used. Alternatively, a continuous method may be employed in which a catalyst and, if necessary, an initiator / chain transfer agent and the like are continuously charged into a certain system and reacted to be further taken out. The same applies to the production method, and the polymerization may be a batch method or a continuous method, but differs in that a non-conjugated diene is added and reacted after the polymerization.

In the production method of the present invention, the polymerization temperature in both the production method and the production method is + 10-
The temperature is preferably about 80 ° C, more preferably about 0 to -40 ° C, and the polymerization time is usually about 0.5 to 120 minutes, preferably about 1 to 60 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 production method, the reaction time after the addition of the non-conjugated diene is preferably about 10 to 300 minutes.

Further, in the production method of the present invention, in the production method, the non-conjugated diene added to the polymerization system before the polymerization reaction of the cationically polymerizable monomer is 0.01 to 1 times the number of moles of the isobutylene monomer used. It is preferable to add the moles and stir so that the mixture becomes uniform. In the production method, it is preferable that the non-conjugated diene added after the polymerization reaction is added in an amount of 0.01 to 1 mol per mol of the isobutylene monomer to be used, and the mixture is uniformly stirred. In the production method of the present invention, in the production method, it is preferable to terminate the polymerization reaction by adding an alcohol such as methanol from the viewpoint of ease of handling later. Is preferably stopped, but the present invention is not particularly limited thereto, and any conventional means can be applied, and it is not necessary to restart the termination reaction.

According to such a production method or a production method,
A polymer having a number average molecular weight of 500 to 500,000 mainly composed of isobutylene monomer units and having an average of more than one unit represented by the general formula (1) per molecule is produced. Is done. Depending on the production method, the unit represented by the general formula (1) is
It is estimated that one or several have been introduced. The isobutylene-based polymer of the present invention has substantially the same functional groups introduced by any of the production methods and the production method, and this point will be shown in Examples described later. I have. From this fact, the unit represented by the general formula (1) may be introduced at the terminal of the molecular chain also by the production method.

[0054]

The polymer of the present invention is a novel isobutylene polymer having an unsaturated group and can be easily obtained at low cost. Further, since the polymer of the present invention does not require the use of a conjugated diene at the time of production, it can be a polymer having no olefin group due to 1,4-addition in the main chain, and high weather resistance and the like can be expected. The polymer thus obtained is
In addition to being used as a raw material for the crosslinked cured product, the functional group can be converted to a hydroxyl group, an amino group, an alkoxysilyl group, a hydrogensilyl group, or the like. In the method for producing an isobutylene-based polymer of the present invention, more than one unsaturated group on average can be easily introduced into one molecule.

[0055]

Next, the present invention will be further clarified with reference to examples, but the present invention is not limited by the examples.

Example 1 A stirring vessel, a three-way cock, and a vacuum line were attached to a 100 ml pressure-resistant glass autoclave, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while evacuating the vacuum line to room temperature. After cooling, the pressure was returned to normal pressure with nitrogen using a three-way cock. Thereafter, while flowing nitrogen from one of the three-way cocks, 40 ml of a main solvent dried by calcium hydride treatment, methylene chloride, was introduced into the autoclave using a syringe. Then, 20 mmol of distilled and purified 1,9-decadiene was added, and 3 mmol of tricumyl chloride (TCC: compound A described above) was further added.
Was dissolved in a methylene chloride solution (10 ml).

Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 7 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. It was immersed in a dry ice-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 temperature inside the polymerization vessel was raised to -30 ° C.

Then, 3.2 g of TiCl ₄ (17 mm
1) was added from a three-way cock using a syringe to start polymerization, and after 60 minutes, methanol, which had been cooled to 0 ° C. or lower in advance, was added to complete the reaction. Thereafter, the reaction mixture was taken out into an eggplant-shaped flask,
Unreacted isobutylene, methylene chloride, 1,9-decadiene and methanol were distilled off, and the remaining polymer was distilled off to 100%.
After dissolution in ml of n-hexane, the solution was repeatedly washed with water until neutral. Then, the n-hexane solution was added to 2
The solution was concentrated to 0 ml, and the polymer was precipitated and separated by pouring the concentrated solution into 300 ml of acetone.

The polymer thus obtained was again
It was dissolved in 00 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 yield was calculated from the yield of the obtained polymer, and Mn and M
w / Mn was determined by the GPC method, and the terminal structure was defined as ¹ H-NM.
It was determined by measuring and comparing the intensity of the resonance signal of the proton belonging to each structure by the R (300 MHz) method.
Table 2 shows the results.

Examples 2 to 6 A polymer was produced in the same manner as in Example 1 except that the presence / absence of an initiator / chain transfer agent, the type and amount of a non-conjugated diene and the polymerization catalyst were changed as shown in Table 1. And evaluated. The results are shown in Table 2.

Comparative Example 1 A polymer was produced and evaluated in the same manner as in Example 1 except that no non-conjugated diene was used. The results are shown in Table 2.

[0062]

[Table 1]

[0063]

[Table 2]

Example 7 A stirring vessel, a three-way cock, and a vacuum line were attached to a 100 ml pressure-resistant glass autoclave, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while evacuating the vacuum line to room temperature. After cooling, the pressure was returned to normal pressure with nitrogen using a three-way cock. Thereafter, while flowing nitrogen from one of the three-way cocks, 40 ml of a main solvent dried by calcium hydride treatment, methylene chloride, was introduced into the autoclave using a syringe. Then, a methylene chloride solution (10 ml) in which 3 mmol of tricumyl chloride (TCC: the compound A described above) was dissolved was added.

Next, a liquefied gas collection tube made of pressure-resistant glass with a needle valve containing 7 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. It was immersed in a dry ice-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 temperature inside the polymerization vessel was raised to -30 ° C.

Next, 3.2 g of TiCl ₄ (17 mm
l) was added from a three-way cock using a syringe to start polymerization, and after 60 minutes, distilled and purified 1,9-
20 mmol of decadiene are added, and further at
After continuing the reaction for 0 minutes, the reaction was completed by adding methanol which had been cooled to 0 ° C. or less in advance. Thereafter, the reaction mixture was taken out into an eggplant-shaped flask, and unreacted isobutylene, methylene chloride, 1,9-decadiene and methanol were distilled off.
After dissolving in 1 l of n-hexane, washing with water was repeated until the solution became neutral. Then, this n-hexane solution was added to 20
The polymer was precipitated and separated by pouring the concentrated solution into 300 ml of acetone.

The polymer thus obtained was again
It was dissolved in 00 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 yield was calculated from the yield of the obtained polymer, and Mn and M
w / Mn was determined by the GPC method, and the terminal structure was defined as ¹ H-NM.
It was determined by measuring and comparing the intensity of the resonance signal of the proton belonging to each structure by the R (300 MHz) method.
Table 4 shows the results.

Examples 8 to 12 In the same manner as in Example 7 except that the presence / absence of an initiator / chain transfer agent, the type and amount of a non-conjugated diene, the polymerization catalyst and the reaction reagent were changed as shown in Table 3, Polymers were prepared and evaluated. The results are shown in Table 4.

Comparative Example 2 A polymer was produced and evaluated in the same manner as in Example 7 except that no non-conjugated diene was used. The results are shown in Table 4.

Example 13 The isolated and purified tertiary chloro terminal P obtained in Comparative Example 2
After dissolving 5 g of IB in 40 ml of methylene chloride dried by calcium hydride treatment, 1,9-decadiene 2
0 mmol, cooled to −30 ° C., and added TiCl ₄
5 mmol was added and stirring was continued for 60 minutes. The termination, purification, and analysis of the reaction were performed in the same manner as in Example 7. The results are shown in Table 4.

[0071]

[Table 3]

[0072]

[Table 4]

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the isobutylene-based polymer obtained in Example 1.

FIG. 2 is a ¹ H-NMR spectrum (300 MHz) of the isobutylene-based polymer obtained in Example 1.

FIG. 3 is an IR spectrum of the isobutylene-based polymer obtained in Example 7.

FIG. 4 is a ¹ H-NMR spectrum (300 MHz) of the isobutylene-based polymer obtained in Example 7.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) C08F 10/10 C08F 110/10 C08F 210/10 C08F 4/00 CA (STN)

Claims (7)

(57) [Claims] 1. A isobutylene monomer units mainly, 1.05 units of the general formula on average per molecule (1): ## STR1 ## [In the formula, Q represents a divalent alkylene group having 1 to 30 carbon atoms. ] An isobutylene-based polymer having an unsaturated group, characterized by having a unit represented by the formula: Wherein the number average molecular weight mainly comprising isobutylene monomer units is a polymer of 500 to 500,000, 1.05 units of the general formula on average per molecule (1): ## STR2 ] Wherein Q is the same as above. The isobutylene-based polymer according to claim 1, wherein the polymer has a unit represented by the following formula: 3. An isobutylene monomer unit as a main component,
On average, 1.05 to 10 general formulas (1) per molecule: [In the formula, Q represents a divalent organic group having 1 to 30 carbon atoms. ]
Has units represented in, Isobuchi having an unsaturated group, characterized in that has substantially no unsaturated bond in the main chain
Len polymer. 4. A cationically polymerizable monomer containing isobutylene and a compound represented by the general formula (3): [In the formula, Q represents a divalent alkylene group having 1 to 30 carbon atoms. A method for producing an isobutylene-based polymer having an unsaturated group, wherein the non-conjugated diene represented by the formula (1) is polymerized in the presence of a Lewis acid. 5. A cationically polymerizable polymer containing isobutylene.
Monomer and general formula (3): [In the formula, Q represents a divalent organic group having 1 to 30 carbon atoms. ]
Of non-conjugated diene represented by the formula in the presence of Lewis acid
In the polymerization reaction system to be reacted , together with a Lewis acid, an initiator / chain transfer agent represented by the general formula (2): [In the formula, X represents a halogen atom, an RCOO- group (R is a monovalent organic group, the same applies hereinafter) or an RO- group. R ³ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ¹ and R ² are the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ³ is a polyvalent aliphatic hydrocarbon group, R ¹ and R ²
Are not simultaneously hydrogen atoms. Isobuchi having unsaturated groups further the presence of an organic compound having a group represented by]
A method for producing a len-based polymer . 6. After polymerizing a cationically polymerizable monomer containing isobutylene in the presence of a Lewis acid, the polymer further has a general formula (3): [In the formula, Q represents a divalent alkylene group having 1 to 30 carbon atoms. ] The method for producing an isobutylene-based polymer having an unsaturated group, characterized by reacting with a non-conjugated diene represented by the following formula: 7. After the cationically polymerizable monomer containing isobutylene is polymerized in the presence of a Lewis acid, the polymer is further subjected to the following general formula (3): [In the formula, Q represents a divalent alkylene group having 1 to 30 carbon atoms. Wherein the cationically polymerizable monomer containing isobutylene is polymerized in the presence of a Lewis acid, wherein the initiator and the chain transfer agent are represented by the general formula (2): 9] [In the formula, X represents a halogen atom, an RCOO- group (R is a monovalent organic group, the same applies hereinafter) or an RO- group. R ³ represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R ¹ and R ² are the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ³ is a polyvalent aliphatic hydrocarbon group, R ¹ and R ²
Are not simultaneously hydrogen atoms. ] A method for producing an isobutylene-based polymer having an unsaturated group, comprising using an organic compound having a group represented by the formula: