JPH0693022A - Reactive silicon group-containing isobutylene-based polymer and its production - Google Patents

Abstract

PURPOSE:To obtain an isobutylene-based polymer useful as a raw material for a cross-linked cured material, readily producible by introducing a reactive silicon group, comprising a unit containing a specific reactive silicon group in a molecular chain. CONSTITUTION:An isobutylene-based polymer containing a unit of the formula (R1 is H, methyl or ethyl; R2 is 1-20C bifunctional organic group; Y is reactive silicon group). A polymer consists essentially of an isobutylene monomer unit, has 500-500,000 number-average molecular weight and contains >1 unit of the formula in one molecule on the average. The polymer substantially contains no unsaturated bond and is obtained by reacting an isobutylene-based polymer with an epoxy group-containing reactive organic silicon compound.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art An isobutylene polymer having an average of more than one functional group per molecule is used as it is or by further carrying out various functional group conversion reactions to form a rubber-like cured product by crosslinking curing. You can Further, this polymer can be made into a moisture-curable polymer by introducing a crosslinkable silicon group as disclosed in USP 4,904,732 and JP-A-63-6041. Isobutylene-based polymers having an average of more than one functional group per molecule are disclosed in USP 3,644,315 and USP 4,524,187. This polymer is obtained by copolymerizing isobutylene and a compound having a conjugated double bond. The polymer obtained is a polymer having a double bond in the main chain and inferior in weather resistance, chemical resistance and reactivity.

USP 4,316,973, USP 4,758,6
31 and JP-A-63-105005 disclose a polymer having a functional group at the terminal of the molecular chain. USP
The polymer disclosed in 4,316,973 and the like is 1,4-bis (α-chloroisopropyl) benzene (hereinafter referred to as “p-DC
C)) as an initiator and chain transfer agent, and BC13
It is obtained by further reacting a polymer having a chlorine atom at the terminal, which is obtained by the inifer method in which isobutylene is cationically polymerized using as a catalyst. JP-A-63-10500
The polymer disclosed in Japanese Patent Publication No. 5 is a polymer having an allyl group at both ends by reacting an isobutylene polymer having chlorine atoms at both ends immediately after polymerization or after purification obtained by the Inifer method with allyltrimethylsilane. Obtained as. However, the polymers disclosed in USP 4,316,973 and JP-A-63-105005 required expensive raw materials.

[0004]

An object of the present invention is to provide a novel isobutylene polymer having a reactive silicon group in its molecular chain, and a method for easily producing the isobutylene polymer. is there.

[0005]

Means for Solving the Problems That is, the present invention provides (1) an average of more than 1.0 general formula (1) per molecule:

[0006]

[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 Y represents a reactive silicon group. ] The isobutylene type polymer which has a unit represented by these, and which has a reactive silicon group. (2) An average of more than 1.0 formula (2) per molecule:

[0008]

[Chemical 6]

[In the formula, R ₃ 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):

[0010]

[Chemical 7]

[In the formula, R ₄ represents a divalent organic group having 1 to 20 carbon atoms, and Y'represents a reactive silicon group. ] The method for producing an isobutylene-based polymer having a reactive silicon group according to (1) above, which comprises reacting with an epoxy group-containing reactive silicon compound represented by

In the general formula (1), R ₁ is preferably a hydrogen atom, a methyl group or an ethyl group. R ₂ has 1 carbon
A known structure may be used as long as it is a divalent organic group of up to 20.
It may also have an unknown structure. As a specific example

[0013]

[Chemical 8]

[0014]

[Chemical 9]

[0015]

[Chemical 10]

[0016]

[Chemical 11]

[0017]

[Chemical 12]

[0018] In addition to R, hydrogen, oxygen, nitrogen, silicon and the like may be present in R ₂ as constituent elements.

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

The following may be mentioned. The reactive silicon group represented by Y is not particularly limited, but representative ones include, for example, the general formula (4):

[0023]

[Chemical 16]

[Wherein R ^{5 and} R ⁶ are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ S
iO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R'may be the same or different) and represents a triorganosiloxy group, R ⁵
Alternatively, when two or more R ⁶ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, they may be the same or different. a is 0,
1, 2 or 3 is shown, and b is 0, 1 or 2. Also m

[0025]

[Chemical 17]

B in does not have to be the same. m represents 0 or an integer of 1 to 19. However, a + (sum of b)
It is assumed that ≧ 1 is satisfied. ] The group represented by these is mentioned. The hydrolyzable group represented by X is not particularly limited, and includes conventionally known hydrolyzable groups, specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group. Group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. Particularly preferred. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and the sum of (a + b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group may be one,
It may be two or more, but may be up to about 20 in the case of silicon atoms connected by a siloxane bond or the like. In particular, general formula (5):

[0027]

[Chemical 18]

A reactive silicon group represented by the formula [wherein R ⁶ , X and a are the same as defined above] is preferable from the viewpoint of easy availability.
Specific examples of R ⁵ and R ⁶ in the general formula (4) include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. A group or R'is a methyl group, a phenyl group, etc. (R ') ₃
Examples thereof include a triorganosiloxy group represented by SiO-. Of these, a methyl group is particularly preferable. Specific examples of the unit represented by the general formula (1) include

[0029]

[Chemical 19]

And the like. Among the

[0031]

[Chemical 20]

Is preferred. The isobutylene-based polymer having a reactive silicon group of the present invention is a polymer characterized by having at least a unit represented by the general formula (1), and has a number average molecular weight mainly composed of isobutylene monomer units. Usually 500 to 500,000, preferably 1,
000-50,000 polymers, with more than one on average per molecule. It preferably has 1.05 or more, more preferably 1.1 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. When the number average molecular weight is less than 500, the content of the isobutylene unit is small, and the properties as an isobutylene polymer cannot be exhibited. When it exceeds 500,000, the polymer becomes a resin and 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 and the like.

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 consisting of isobutylene alone, but may be 50% of isobutylene.
It means a monomer in which a weight percent (hereinafter simply referred to as “%”) or less is replaced with a cationically polymerizable monomer capable of copolymerizing with isobutylene. Examples of the cationically polymerizable monomer that can be copolymerized 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 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, vinyltrimetolsilane, 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.

An average of 1.0 per molecule used in the present invention
More than general formula (2):

[0036]

[Chemical 21]

[In the formula, R ₃ 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 ₄ in the formula can be widely used in a known structure as long as it is a divalent organic group having 1 to 20 carbon atoms.

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

And the like. In addition to R, hydrogen, oxygen, nitrogen, silicon and the like may be present in R ₄ as constituent elements.

[0045]

[Chemical 27]

[0046]

[Chemical 28]

[0047]

[Chemical 29]

And the like. The reactive silicon group represented by Y ′ is not particularly limited, but representative ones include, for example, the general formula (4):

[0049]

[Chemical 30]

[In the formula, R ⁵ , R ⁶ , X, a and b are the same as defined above. ) The group represented by is mentioned. The hydrolyzable group represented by X above is not particularly limited and includes conventionally known hydrolyzable groups, specifically, for example, a hydrogen atom,
Examples thereof include a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. Particularly preferred. The hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and the sum of (a + b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon compound may be one or two or more, but in the case of silicon atoms connected by a siloxane bond or the like, it may be up to about 20. In particular, general formula (5):

[0051]

[Chemical 31]

A reactive silicon compound represented by the formula [wherein R ⁶ , X and a are the same as defined above] is preferable from the viewpoint of easy availability. Specific examples of R ⁵ and R ⁶ in the general formula (4) include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. And a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferable. Specific examples of the epoxy group-containing reactive silicon compound represented by the general formula (3) include:

[0053]

[Chemical 32]

And the like. Among these

[0055]

[Chemical 33]

Is preferred.

In the reaction of the phenol group-containing isobutylene polymer with the epoxy group-containing reactive silicon 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 condensation reaction catalyst of phenolic hydroxyl group and epoxy group can be widely used. Further, a catalyst which is currently unknown may be used.

Examples of the reaction catalyst include imidazoles such as 1,2-dimethylimidazole and 2-methylimidazole, amines such as trimethylamine and triethylamine, tetramethylmethylammonium bromide,
Examples thereof include ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine, and phosphonium salts such as benzyltriphenylphosphonium chloride.

The amount of the catalyst that can be used in the present invention is preferably 0.001 equivalent or more and 100 equivalents or less with respect to the phenol group contained in the isobutylene polymer. Furthermore, 0.1 equivalent or more and 10 equivalents or less are preferable.

In the present invention, a reaction solvent which does not adversely influence the reaction can be appropriately used, and for example, a hydrocarbon solvent such as an aliphatic 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 include heptane, pentane, hexane, and the like, and aromatic hydrocarbons include benzene, toluene, xylene, and the like.
Specific examples of the halogenated hydrocarbon include chloromethane, chloroethane, methylene chloride, 1,1-dichloroethane, chloroform, 1,2-dichloroethane and the like. 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.

When 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 epoxy group-containing reactive silicon compound and the like are sequentially charged in one container,
A continuous method may be used in which a solvent, a phenol group-containing isobutylene polymer, a catalyst, an epoxy group-containing reactive silicon compound, etc., are continuously charged into a certain system to carry out the reaction, and then the reaction is carried out. Further, the solvent and the phenol group-containing isobutylene polymer may be charged separately, but may be a 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 about +180 to -80 ° C, more preferably about 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.
An isobutylene-based polymer having a number of 20,000 polymers and having an average of more than one unit represented by the general formula (1) per molecule is produced.

[0063]

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 container was dried by heating at 100 ° C. for 1 hour while pulling a vacuum in the vacuum line to room temperature. After cooling, 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, 40 ml of methylene chloride, which is the main solvent dried by calcium hydride treatment, was introduced into the autoclave using a syringe. Then 20 mmol of distilled and purified tert-butoxystyrene was added.

Next, 7 g (12 g) of isobutylene dehydrated by passing through a column packed with barium oxide was used.
After connecting the pressure-resistant glass liquefied gas sampling tube with a needle valve containing 5m mol) to the three-way cock,
It was immersed in a dry ice-acetone bath at 70 ° C., and the inside of the polymerization vessel was cooled for 1 hour while stirring. After cooling, the inside of the container was decompressed by a vacuum line, the needle valve was opened, and isobutylene was introduced from the pressure-resistant glass liquefied gas sampling tube into the polymerization container. After that, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, cooling was further continued for 1 hour with stirring, and the inside of the polymerization vessel was heated to -30 ° C.

Next, 3.2 g of TiCl ₄ (17 mmol)
Was added from a three-way cock using a syringe to start the polymerization, and when 60 minutes had passed, 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. Thereafter, unreacted isobutylene, methylene chloride, tert-butoxystyrene, methanol and the like were distilled off, the remaining polymer was dissolved in 100 ml of n-hexane, and 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 by pouring this concentrated solution into 0 ml of acetone.

The polymer thus obtained was 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 analyzed by 1H-NMR (300MH
z) 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 dimethoxymethylsilyl glycidyl ether and 0.
01 g of trimethylamine was added and reacted at 80 ° C. for 3 hours. After completion of the reaction, the polymer was obtained by devolatilization under reduced pressure and concentration. The structure of the obtained polymer is analyzed by 1H-NMR.
(300 MHz) method. As a result, a reactive silicon-containing isobutylene polymer having 3.4 dimethoxymethylsilyl groups per molecule was obtained.

[0069]

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

Claims (4)

[Claims] 1. A general formula (1) having an average 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 Y represents a reactive silicon group. ] The isobutylene type polymer which has a unit represented by these, and which has a reactive silicon group. 2. A polymer having a number average molecular weight of 500 to 500,000, which is mainly composed of an isobutylene monomer unit and has an average of more than 1 per molecule of the general formula (1): [In the formula, R ₁ , R ₂ and Y are the same as defined above. ] The isobutylene-based polymer according to claim 1, which has a unit represented by the following formula in the 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 number of more than 1.0 per molecule: [In the formula, R ₃ 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 ₄ represents a divalent organic group having 1 to 20 carbon atoms, and Y ′ represents a reactive silicon group. ] It reacts with the epoxy group containing reactive silicon compound represented by these, The manufacturing method of the isobutylene type polymer which has a reactive silicon group of Claim 1 characterized by the above-mentioned.