JPH0687915A - Unsaturated group-containing isobutylene-based polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a new simply producible isobutylene-based polymer containing one or more unsaturated groups in one molecule on the average without using an expensive raw material by reacting a specific isobutylene-based polymer with an unsaturated group-containing compound. CONSTITUTION:An isobutylene-based polymer having >1.0 unit of formula I (R1 is H, methyl or ethyl; R2 is 1-20C bifunctional organic group; R3 is H or 1-10C monofunctional organic group; (n) is 14) in one molecule on the average. The isobutylene-based polymer is obtained by reacting a isobutylene-based polymer containing a phenolic unit of formula II (R4 is H, methyl, etc.) with an unsaturated group-containing compound of formula III (R5 is 1-20C organic group; R6 is H or 1-10C monofunctional organic group; X is halogen). The isobutylene-based polymer consists essentially of an isobutylene monomer unit and has preferably 1,000-50,000 number-average molecular weight. The number of the unit of formula I is 1.1-5 and the unit preferably exists as side chains.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an isobutylene polymer having an unsaturated group and a method for producing the same.

[0002]

2. Description of the Related Art Isobutylene-based polymers having an average of more than one functional group per molecule have a crosslinking effect as they are or under various functional group conversion conditions. A rubbery cured product can be produced. Also, this polymer is USP 4,90
No. 4,732, a moisture-curable polymer can be obtained by introducing a crosslinkable silicon group as disclosed in JP-A-63-6041.

Isobutylene polymers having an average of more than one functional group per molecule are described in USP 3,644.
315, USP 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. , A polymer having poor weather resistance, chemical resistance and reactivity.

USP 4,316,973, USP
4,758,631 and JP-A-63-105005 disclose polymers having a functional group at the terminal of the molecular chain. The polymer disclosed in USP 4,316,973 and the like uses 1,4-bis (α-chloroisopropyl) benzene (hereinafter referred to as “p-DCC”) as an initiator / chain transfer agent, and BC13 as a catalyst. Is obtained by further reacting a polymer having a chlorine atom at the terminal, which is obtained by the inifer method of cationically polymerizing isobutylene.
The polymer disclosed in Japanese Unexamined Patent Publication No. 63-105005 is obtained by the inifer method by reacting an isobutylene-based polymer having a chlorine atom at both ends immediately after polymerization or after purification with allyltrimethylsilane. Obtained as a polymer having an allyl group.

However, USPUSP 4,316,97
3, the polymers disclosed in JP-A-63-105005 and the like required expensive raw materials. An object of the present invention is to provide a novel isobutylene-based polymer having an unsaturated group in the molecular chain, and a method for easily producing the isobutylene-based polymer.

[0006]

That is, in the present invention, the average number of general formulas (1) exceeds 1.0 per molecule:

[0007]

[Chemical 5]

[In the formula, R ₁ represents a hydrogen atom, a methyl group or an ethyl group. R ₂ represents a divalent organic group having 1 to 20 carbon atoms, and R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. n represents an integer of 1 to 4. ] An isobutylene-based polymer having an unsaturated group, which has a unit represented by the following general formula (2): average of more than 1.0 per molecule:

[0009]

[Chemical 6]

[In the formula, R ₄ represents a hydrogen atom, a methyl group or an ethyl group. ] An isobutylene-based polymer having a phenol group, which has a unit represented by the following general formula (3):

[0011]

[Chemical 7]

[In the formula, R ₅ represents a divalent organic group having 1 to 20 carbon atoms, and R ₆ represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. ] The method for producing an isobutylene-based polymer having an unsaturated group as described above, which comprises reacting with an unsaturated group-containing compound.

In the general formula (1), R ₁ is preferably a hydrogen atom, a methyl group or an ethyl group. R ₂ may have a known structure as long as it is a divalent organic group having 1 to 20 carbon atoms, or may have an unknown structure. As a concrete example,

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

And the like. In addition to carbon, hydrogen, oxygen, nitrogen, silicon and the like may be present in R ₂ as constituent elements. As a specific example

[0018]

[Chemical 11]

And the like. 1 carbon in R ₃
Specific examples of the monovalent organic group of 10 to 10 include a methyl group, an ethyl group, a propyl group and the like. A hydrogen atom is most preferable as R ₃ . In addition, n is an integer from 1 to 4 and changes depending on the reaction conditions.

The isobutylene-based polymer having an unsaturated group of the present invention is a polymer characterized by having at least a unit represented by the above-mentioned general formula (1), and is a number average mainly composed of isobutylene monomer units. The molecular weight is usually 500-
500,000, preferably 1,000 to 50,000
Of more than 1, preferably 1.05 or more, and more preferably 1.1 per molecule.
One or more and 10 or less, and particularly preferably 1.1 or more and 5 or less units represented by the general formula (1). The unit represented by the general formula (1) is preferably present as a side chain of the polymer, but may be present at the terminal. If the number average molecular weight is less than 500, the content of isobutylene units is small, and the properties as an isobutylene polymer cannot be expressed. If it exceeds 500,000, the polymer becomes a resin,
It becomes difficult to handle. Further, it is preferable that the polymer of the present invention has substantially no unsaturated bond in the main chain from the viewpoint of weather resistance.

In the present specification, the isobutylene polymer means a polymer of a cationically polymerizable monomer containing isobutylene. Here, the cationically polymerizable monomer containing isobutylene is not limited to a monomer composed of only isobutylene, and 50% by weight (hereinafter simply referred to as “%”) or less of isobutylene can be copolymerized with isobutylene. It means a monomer substituted with a cationically 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, vinylsilanes and the like. Of these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferable, but when weather resistance and the like are a problem, olefins other than conjugated dienes are preferable.

Specific examples of the cationically polymerizable monomer copolymerizable with the above isobutylene include propylene and
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, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.
Among these, 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 with two or more kinds.

The average number of molecules used in the present invention is 1.
General formula (2) exceeding 0:

[0025]

[Chemical 12]

[In the formula, R ₄ represents a hydrogen atom, a methyl group or an ethyl group. ] As the isobutylene-based polymer having a phenol group having a unit represented by the following, those produced by a conventionally known production method can be widely used, and those produced by an unknown production method at present. It may be. With respect to the general formula (3), R ₅ in the formula may be a widely known structure as long as it is a divalent organic group having 1 to 20 carbon atoms, and may have an unknown structure.
As a concrete example,

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

And the like. In addition to carbon, hydrogen, oxygen, nitrogen, silicon and the like may be present in R ₅ as constituent elements. As a specific example

[0031]

[Chemical 16]

And the like. 1 carbon in R ₆
Specific examples of the monovalent organic group of 10 to 10 include a methyl group, an ethyl group, a propyl group and the like. Further, R ₆ is most preferably a hydrogen atom. X represents a halogen atom,
A chlorine atom, a bromine atom and an iodine atom are most preferable, and among them, a chlorine atom and a bromine atom are preferable. General formula (3)
Specific examples of the unsaturated group-containing compound represented by

[0033]

[Chemical 17]

And the like. In the reaction of the phenol group-containing isobutylene polymer and the unsaturated group-containing compound in the present invention, various catalysts can be added in order to effectively carry out the reaction. As the catalyst to be used, those known as a catalyst of Friedel-Crafts reaction for phenol can be widely used. Further, a catalyst which is currently unknown may be used.

As the above reaction catalyst, AlCl ₃ , Sn
Examples thereof include Cl ₄ , TiCl ₄ , VCl ₅ , FeCl ₃ , BF _{3 and the} like, and organic aluminum compounds such as Et ₂ AlCl and EtAlCl ₂ . The amount of the catalyst that can be used in the present invention is 0.001 equivalent or more and 100 with respect to the phenol group contained in the isobutylene polymer.
An equivalent amount or less is preferable. Further, it is preferably 0.1 equivalent or more and 10 equivalents or less.

In the present invention, a reaction solvent that does not adversely influence the reaction can be appropriately used, and for example, a hydrocarbon solvent such as a fatty acid hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon or the like is used. Among these, halogenated hydrocarbons are preferable, and chlorinated hydrocarbons having a chlorine atom are more preferable. Specific examples of such aliphatic hydrocarbons are pentane, hexane, etc., aromatic hydrocarbons are benzene, toluene, xylene, etc., and specific examples of halogenated hydrocarbons are chloromethane, chloroethane, methylene chloride. , 1,1-dichloroethane, chloroform, 1,2-dichloroethane and the like can be exemplified. These may be used alone or in combination of two or more. Further, these solvents may be used in combination with a small amount of another solvent, for example, an acetic acid ester such as ethyl acetate or an organic compound having a nitro group such as nitroethane.

In carrying out the production method of the present invention, there is no particular limitation, and conventional reaction methods can be widely applied. For example, a batch method may be used in which a solvent, a phenol group-containing isobutylene-based polymer, a catalyst, an unsaturated group-containing compound, and the like are sequentially charged in one container, or a solvent, a phenol group-containing isobutylene-based polymer, and A continuous method in which a catalyst, an unsaturated group-containing compound and the like are continuously charged in a system to react and then taken out may be used. further,
The solvent and the phenol group-containing isobutylene polymer may be charged separately, but may be the reaction solution after the reaction in the production of the phenol group-containing isobutylene polymer.

In the production method of the present invention, the reaction temperature is preferably +180 to -80 ° C, more preferably 100 to -30 ° C, and the reaction time is usually 0.5 minutes to 24 hours. It is about 1 minute to 15 hours. By such a production method, the number average molecular weight mainly composed of isobutylene monomer units is 500 to 50.
10,000 polymers, 1 on average per molecule
An isobutylene-based polymer having more than one unit represented by the general formula (1) is produced.

[0039]

EXAMPLES Next, the present invention will be further clarified with reference to examples, but the present invention is not limited to the examples. Synthesis Example 1 A 100 ml pressure-resistant glass autoclave was equipped with stirring blades, a three-way cock, and a vacuum line, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while pulling a vacuum on the vacuum line, and then cooled to room temperature on the three sides. The pressure was returned to normal pressure with nitrogen using a cock.

Then, while flowing nitrogen from one of the three-way cocks, methylene chloride 4 which was the main solvent was dried by calcium hydride treatment in an autoclave using a syringe.
0 ml was introduced. Then, 20 mmol of distilled and purified tert-butoxystyrene was added. Then, a pressure-resistant glass liquefied gas sampling tube with a needle valve containing 7 g (125 mmol) of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock, and then the container body was kept at -70 ° C. Dry ice
Immerse in an acetone bath and stir inside the polymerization vessel 1
Cooled for hours. After cooling, after decompressing the inside with a vacuum line, the needle valve was opened and isobutylene was introduced into the polymerization vessel from the pressure-resistant glass liquefied gas sampling tube. Then return the pressure to normal pressure by flowing nitrogen from one of the three-way cocks,
Cooling is continued for 1 hour with stirring, and the inside of the polymerization vessel is -30 ° C.
The temperature was raised to.

Next, 3.2 g of TiCl ₄ (10 mmo
1) was added from a three-way cock using a syringe to start the polymerization, and when 60 minutes had elapsed, methanol precooled to 0 ° C. or lower was added to complete the polymerization. Then, concentrated hydrochloric acid was added to the reaction mixture and the mixture was reacted at 60 ° C. for 5 hours. Then, unreacted isobutylene, methylene chloride, tert-butoxystyrene, methanol and the like were distilled off, and the remaining polymer was dissolved in 100 ml of n-hexane. After that, this solution was repeatedly washed with water until it became neutral.
Then, the n-hexane solution was concentrated to 20 ml,
The polymer was precipitated and separated by pouring the concentrated solution into 300 ml of acetone.

The polymer thus obtained is reconstituted with 1
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 3.6 g of isobutylene polymer.
The structure of the obtained polymer was determined by the ¹ H-NMR (300 MHz) method. As a result, a phenol group-containing isobutylene polymer having 3.8 phenyl groups in one molecule was obtained.

Example 1 3.0 g of the phenol group-containing isobutylene polymer obtained in Synthesis Example 1 was placed in a 100 ml glass 4-neck flask and dissolved in 30 ml of dry toluene. Furthermore, 0.
3 g of allyl chloride and 0.3 g of aluminum chloride were added and reacted at 50 ° C. for 3 hours. After completion of the reaction, neutralization, washing with water,
A polymer was obtained by extraction and concentration. The structure of the obtained polymer was determined by the ¹ H-NMR (300 MHz) method. As a result, an unsaturated group-containing isobutylene polymer having 6.4 allyl groups in one molecule was obtained.

[0044]

The polymer of the present invention is a novel isobutylene polymer having an unsaturated group and can be easily obtained. The polymer thus obtained can be used as it is, or by converting its unsaturation into an alkoxysilyl group, a hydrogensilyl group or the like, as a raw material for a crosslinked cured product. Further, in the method for producing an isobutylene-based polymer of the present invention, it is possible to simply introduce an average of more than one unsaturated group into one molecule.

Claims (4)

[Claims] 1. A general formula (1) having an average number of more than 1.0 per molecule: [In the formula, R ₁ represents a hydrogen atom, a methyl group or an ethyl group. R ₂ represents a divalent organic group having 1 to 20 carbon atoms, and R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.
n represents an integer of 1 to 4. ] The isobutylene type polymer which has a unit represented by these, which has an unsaturated group. 2. A polymer represented by the general formula (1) having a number average molecular weight of 500 to 500,000, which is mainly composed of an isobutylene monomer unit and has an average number of more than 1 per molecule: [In the formula, R ₁ , R ₂ and R ₃ are the same as defined above. ] The isobutylene-type polymer of Claim 1 which has the unit represented by this in a polymer. 3. The polymer according to claim 1, which has substantially no unsaturated bond in the main chain. 4. A general formula (2) having an average of more than 1.0 per molecule: [In the formula, R ₄ represents a hydrogen atom, a methyl group or an ethyl group. ] An isobutylene-based polymer having a phenol group having a unit represented by the following general formula (3): [In the formula, R ₅ is a divalent organic group having 1 to 20 carbon atoms, R _5
6 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. X represents a halogen atom. ] The unsaturated-group-containing compound represented by these is made to react, The manufacturing method of the isobutylene type-polymer which has an unsaturated group of Claim 1 characterized by the above-mentioned.