JPH04103606A - Isobutylene polymer having reactive silicon group, its production and curable composition therefrom - Google Patents

Abstract

PURPOSE:To obtain the title polymer capable of giving cured products of high mechanical strength, water resistance, weatherability, etc., by copolymerization of a monomer capable of cationic polymerization including isobutylene with a non-conjugated polyene in the presence of a Lewis acid followed by hydrosilylation of the unsaturated groups in the resulting polymer. CONSTITUTION:A copolymerization is carried out in the presence of a Lewis acid between (A) a monomer capable of cationic polymerization including isobutylene and (B) a polyene of formula I (R<1> and R<2> are each H, methyl or ethyl; R<3> is H, 1-8C alkyl, 6-20C aryl or 7-20C aralkyl; Q is organic group having no unsaturated group other than aromatic ring) (e.g. 1,4-pentadiene) into a unsaturated group-contg. isobutylene-based copolymer with its main chain containing no unsaturated group other than aromatic ring, and this copolymer is then hydrosilylated to obtain the objective copolymer having recurring unit of formula II (R<4> and R<5> are each 1-20C alkyl, 6-20C aryl, etc.; (a) is 0 or 1-3; (b,) is 0, 1 or 2; (l) is 0 or 1-18).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an isobutylene polymer having a reactive silicon group, a method for producing the same, and a curable composition thereof.

[Prior art/problem to be solved by the invention 1 As a rubber-based polymer having a reactive silicon group, a propylene oxide-based polymer having a reactive silicon group at the end of the molecule is known. The composition having the main component has an interesting property of being hardened by moisture even at room temperature and becoming a rubber elastic body (Japanese Patent Application Laid-open No. 73998/1983).
.

However, since the curable composition does not have sufficient properties such as weather resistance, water resistance, and heat resistance, its uses may be limited.

On the other hand, in order to improve these properties, it is known that the main chain skeleton is replaced with a saturated hydrocarbon polymer, but these polymers also have some problems.

That is, an isobutylene polymer having a silyl group introduced at its terminal using the Jeffer method developed by J. P. Kennedy et al.
In this case, the amount of silyl groups is limited by the type (number of functional groups) of the initiator and chain transfer agent used during polymerization, and at most only 2 to 3 silyl groups can be introduced per molecule. Therefore, the strength of the cured product thus obtained is low and has a limit, and further increase in strength is desired. Furthermore, this polymer is an isobutylene-based polymer that is said to have good weather resistance, and the cured product may deteriorate slightly after a long period of time, which may limit its uses.

Additionally, a method of introducing a silyl group into a copolymer of isobutylene and triene (Japanese Unexamined Patent Publication No. 108208/1983) has been reported as a method that is expected to increase strength.
In this case, although an increase in strength can certainly be expected, the unsaturated group generated by the 1,4-addition of the conjugated diene part of the triene or the silyl group remains in the main chain even after the introduction of the silyl group, resulting in poor weather resistance and
This method also poses a major problem since it greatly deteriorates heat resistance and the like.

As described above, the industry is expected to develop polymers that have excellent properties such as weather resistance, water resistance, and heat resistance, and have a high degree of curing due to moisture, and various attempts have been made to develop polymers with such properties. The reality is that no one has yet been found.

The purpose of the present invention is precisely in this point, to provide a polymer that can be expected to have good weather resistance, water resistance, and heat resistance, and which has an arbitrary number of silyl groups introduced not only at the end of the molecule but also within the molecule. The object of the present invention is to provide a polymer that can be cured by moisture with high strength, a method for producing the same, and a curable composition thereof.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the inventors of the present invention co-produced a cationic polymerizable monomer containing isobutylene and a non-conjugated polyene in the presence of a Lewis acid. After polymerizing to obtain an unsaturated group-containing isobutylene copolymer containing no unsaturated groups other than aromatic rings in the main chain, the unsaturated group-containing isobutylene copolymer is then hydrosilylated, We have discovered that it is possible to obtain a saturated hydrocarbon polymer that does not contain any residual unsaturated groups other than aromatic rings in its main chain, and that also has a silyl group introduced therein, and has completed the present invention. It's arrived.

That is, the gist of the present invention is as follows: (1) an isobutylene polymer having at least a repeating unit represented by general formula (I) [wherein R1 and R
2 represents a hydrogen atom, a methyl group, or an ethyl group, Q represents an organic group having no unsaturated group other than an aromatic ring, and R'' represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 6 carbon atoms. -20 aryl group or C7-20 aralkyl group, R4 and R5 each have 1-2 carbon atoms
0 alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group (R', R'' and R
8 are the same or different and represent a monovalent hydrocarbon group having 1 to 20 carbon atoms), X represents a hydroxyl group or a hydrolyzable group, and when two or more X are bonded, they are the same or different. , and a is 0. 1. b represents 0, 1 or 2; l represents 0 or an integer from 1 to 18;

] (2) A cationically polymerizable monomer containing isobutylene and a non-conjugated polyene are copolymerized in the presence of a Lewis acid to produce an unsaturated group-containing isobutylene copolymer containing no unsaturated groups other than aromatic rings in the main chain. A method for producing an isobutylene polymer, which comprises obtaining a polymer, and then hydrosilylating the unsaturated group-containing isobutylene copolymer, and (3) using the isobutylene polymer described in (1) above as an active ingredient. The present invention relates to a curable composition.

Regarding general formula (I), R1 and R2 each represent a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom.

Regarding general formula (I), the organic group having no unsaturated group other than an aromatic ring in Q is a divalent organic group having 1 to 30 carbon atoms, such as hexene.

Regarding general formula (I), the alkyl group having 1 to 8 carbon atoms in R3 may be linear or branched,
Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 5eC-butyl group, and preferably methyl group.

Further, examples of the aryl group having 6 to 20 carbon atoms in R3 include a phenyl group, a naphthalene group, and the like, with a phenyl group being preferred. In addition, the number of carbon atoms in R3 is 7 to 2
Examples of the aralkyl group having 0 include phenyl groups and naphthalene groups in which the aryl group moiety is unsubstituted or substituted with a methyl group, etc., and the alkylene group moiety has 1 carbon number.
-5, preferably a methyl group.

R3 may be a hydrogen atom or any of the alkyl, aryl, and aralkyl groups described above, but is preferably a hydrogen atom or a methyl group.

Regarding general formula (I), the number of carbon atoms in R4 and R5 is 1
The ~2σ alkyl group may be linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 5eC-butyl group, etc., and are preferred. is a methyl group.

Examples of the aryl group having 6 to 2 carbon atoms in R4 and R5 include a phenyl group and a naphthalene group, with a phenyl group being preferred.

In addition, examples of the aralkyl group having 7 to 2 o carbon atoms in R4 and R5 include phenyl groups and naphthalene groups in which the aryl group moiety is unsubstituted or substituted with a methyl group, etc., and the alkylene group moiety has 1 to 2 carbon atoms. -5, preferably a methylene group.

Also, R' and R5i:, R'R7R''S
The triorganosiloxy group represented by iO□ is a monovalent hydrocarbon group having 1 to 20 carbon atoms in which R', R7 and R8 may be the same or different, and specifically Examples of the hydrogen group include a methyl group, an ethyl group, a phenyl group, and the like, with a methyl group being preferred.

R4 and R5 may be any of the aforementioned alkyl groups, aryl groups, aralkyl groups, or triorganosiloxy groups, and are preferably methyl groups.

Regarding the general formula (I), the hydrolyzable group in The following groups are listed. X may be a hydroxyl group or any of the above-mentioned hydrolyzable groups.

be.

Regarding general formula (I), a represents 0, 1.2 or 3, b represents 0, 1 or 2, and l represents 0 or an integer from 1 to 18.

The isobutylene polymer of the present invention has at least the general formula (
The number of repeating units represented by I) is usually 1 to 10, preferably 3 to 10 per molecule.

The molecular weight of the isobutylene polymer of the present invention is 500 to 5.
00,000 or preferably, especially 1,000~
A liquid material with a weight of about 30,000 is preferred because it is easy to handle. The number of reactive silicon groups contained in the molecule is usually 1 to 10, and if it is less than 1, the curability will be insufficient and it will be difficult to obtain a good cured product, so it is not preferable. Exceeding this is not preferable because the cured product also becomes brittle.

The isobutylene-based polymer of the present invention is produced by copolymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated polyene in the presence of a Lewis acid, so that the main chain contains no unsaturated groups other than aromatic rings. It can be produced by obtaining a saturated group-containing isobutylene copolymer and then hydrosilylating the unsaturated group-containing isobutylene copolymer.

Here, the cationic polymerizable monomer containing isobutylene is not limited to a monomer consisting only of isobutylene, but is a cation that can copolymerize up to 50% by weight (hereinafter simply referred to as 1%) of isobutylene with isobutylene. It means a monomer substituted with a polymerizable monomer.

Examples of cationically polymerizable monomers that can be copolymerized with isobutylene include olefins having 3 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, and the like. Among these, olefins having 3 to 12 carbon atoms are preferred from the viewpoint of polymerizability.

Specific examples of cationic polymerizable monomers that can be copolymerized with the isobutylene include propylene, 1-butene,
2-butene, 2-methyl-1-butene, 3-methyl-2
-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, methyl vinyl ether,
Examples include ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, and indene. Among these, propylene, -butene, 2-butene, styrene, etc. are preferred from the viewpoint of polymerizability. These cationically polymerizable monomers that can be copolymerized with isobutylene may be used alone or in combination with isobutylene. Further, as a cationic polymerizable monomer copolymerizable with isobutylene, a small amount of conjugated dienes may be used as long as the object of the present invention is not impaired. Examples of conjugated dienes include butadiene, isoprene, cyclopentadiene, and the like.

The non-military polyene used in the present invention refers to a compound containing a plurality of unsaturated groups that are not conjugated to each other.

Preferably, non-conjugated dienes are mentioned. Specifically, general formula (It) [wherein R', R2, R' and Q have the same meanings as above. ] Compounds represented by the following can be mentioned.

In the present invention, conventionally known nonconjugated polyenes are widely used, such as 1.4-pentadiene, 1.5-hexadiene, 1,6-hebutadiene, 1.7-octadiene, 1.8-nonadiene, 1.9-decadiene, l,
19-dodecadiene, 2-methyl-2,7-octadiene, 2,6-cymethyl-1. 5-pentagene, 1
．． 5. Examples include non-conjugated dienes and trienes such as 9-decatriene. Among these, from the viewpoint of the activity of the functional group of the resulting copolymer, α,ω-diene is selected.

4-Pentadiene, l,5-hexadiene, ■.

6-hebutadiene, 1,7-octadiene, l.

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 catalyst, such as A IICl z , S n Cl 4
, Ti(14, VCl5, FeC1z, BF2, etc., and organic aluminum compounds such as Et2AlCl, EtAIC12, etc., but are not limited to these. Among these Lewis acids, 5nC14, Ti
C1<, Et2AlIC1, EtAβCl2, etc. are preferred.

The amount of the Lewis acid used is preferably 0.1 to 10 times the amount of the nonconjugated polyene to be copolymerized with isobutylene,
More preferably 0. It would be good to increase it by 2 to 5 times.

In the present invention, it is preferable that an initiator is further present in the reaction system. As such an initiator, a proton source such as a small amount of water that normally remains in the system can be used for the growth effect, and for example, an initiator and chain transfer agent can be suitably used.

Examples of the initiator and chain transfer agent that can be used in the present invention include those represented by the general formula (II[) [wherein W is a halogen atom, R''Coo- group, or
2 represents an o- group (R12 represents a monovalent organic group). R" represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R9 and R" are the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. represent.

However, when R'' is a polyvalent aliphatic hydrocarbon group, R9 and R'' are not hydrogen atoms at the same time. ] Examples include organic compounds having a group represented by the following.

Specific examples of such organic compounds include (1) General formula (■): BYn General formula (IV) [wherein B represents a group having 1 to 4 aromatic rings. Y
is the general formula (V) 〒゛.

-C-W General formula (V) In the formula, R'' and Rl 4 are the same or different and represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 2 o carbon atoms.W
has the same meaning as above. ) represents a group bonded to an aromatic ring. n represents an integer from 1 to 6. ], (2) general formula (VI) DZm general formula (V'f) [wherein D represents a hydrocarbon group having 4 to 4 o carbon atoms. Z is a halogen atom bonded to a tertiary carbon atom, R”COO- group or R12
Represents an o-group (R” has the same meaning as above).m
represents an integer from 1 to 4. ], and (3) an oligomer having an α-halostyrene unit, but is not limited thereto.

These compounds may be used alone or in combination of two or more.

1 to 1 in the compound represented by general formula (IV)
B, which is a group having four aromatic rings, may be formed by a condensation reaction or may be a non-condensed group. Specific examples of such a group having an aromatic ring include, for example, 1-
Hexavalent phenyl group, biphenyl group, naphthalene group, anthracene group, phenanthrene group, pyrene group, Ph-(C
H,)j-Ph group (Ph is a phenyl group, j is an integer of 1 to 10), etc., and these aromatic ring-containing groups include linear and/or branched aliphatic groups having 1 to 20 carbon atoms. It may be substituted with a group having a functional group such as a group hydrocarbon group, a hydroxyl group, an ether group, or a vinyl group.

On the other hand, Z in the compound represented by general formula (VI) is F bonded to a tertiary carbon atom, a halogen atom such as (1, Br, ■), R12co〇- group or R'20- group, and D in formula (VI) is a hydrocarbon group having 4 to 40 carbon atoms, preferably an aliphatic hydrocarbon group, and when this carbon number is less than 4, it is a halogen atom, R12Coo
The carbon to which the - group or R''O- group is bonded ceases to be a tertiary carbon atom, and polymerization progresses (becomes unsuitable for use).

Additionally, α can be used as an initiator and chain transfer agent.
- Examples of oligomers containing halostyrene units include oligomers of α-chlorostyrene and oligomers obtained by copolymerizing α-chlorostyrene and monomers copolymerizable therewith.

In the method of the present invention, a halogen atom, R12COO- group, or RI
The use of a compound having two or more 20-groups as an initiator and chain transfer agent is very effective because the degree of functionalization can be increased.

Specific examples of these initiators and chain transfer agents include those shown below.

Shil-1, U H3, (n-C8H+i) (n-Cm F
(+7), CH3CH, C) (.

w-C-CH2CH, -C-CH2CH2-C-W+
1 1CH3W
CH3, [wherein W represents the same meaning as above. [Also,] a halogen atom-containing organic compound such as an oligomer of α-chlorostyrene or R”COO-
Examples include, but are not limited to, group-containing organic compounds. Among these compounds, the following are preferred.

That is, CH, CH.

CII! -C-C-Cz CH, CH,... CH, CH, CH.

Shit'13 Shij! Shit
``-C which is easy to generate stable carbon cations such as i2
(CH3), 0.1 or -C(CHs)-Br, a halogen atom-containing growth compound, C=○ CH.

CH3COO- group-containing organic compounds, such as C
Examples include H, O-group-containing organic compounds.

These compounds are components used as initiators and chain transfer agents, and the molecular weight of the resulting polymer can be controlled by adjusting the amount of these compounds used, the amount of residual water, or the polymerization temperature. In the present invention, the above-mentioned compound is added to a cationically polymerizable monomer containing usually isobutylene at 0.0%. O about 1 to 20%, preferably 0. It is preferable to use it at a ratio of about 1 to IO%.

Examples of the polymerization solvent used in the present invention include hydrocarbon solvents such as aliphatic hydrocarbons and halogenated hydrocarbons. Among these, halogenated hydrocarbons are preferred, and chlorinated hydrocarbons having a chlorine atom are more preferred.

Specific examples of such aliphatic hydrocarbons include pentane, hexane, etc., and specific examples of halogenated hydrocarbons include chloromethane, chloroethane, methylene chloride, 1,1
~Dichloroethane, chloroform, 1,2-dichloroethane, etc. can be exemplified. These may be used alone or in combination of two or more. Furthermore, a small amount of other solvents, such as acetic esters such as ethyl acetate, or organic compounds having a nitro group such as nitroethane, may be used in combination.

When carrying out the production method of the present invention, there are no particular restrictions, and conventional polymerization methods can be widely applied.

For example, a batch method may be used in which the polymerization solvent, monomer, non-conjugated polyene, catalyst, and if necessary an initiator and chain transfer agent are sequentially charged into one container, or the polymerization solvent, monomer, non-conjugated polyene, catalyst, If necessary, a continuous method may be used in which an initiator/chain transfer agent and the like are continuously introduced into a certain system to react and then taken out.

In the production method of the present invention, the polymerization temperature is +lO~
It is preferably about -80°C, more preferably 0 to -40°C.
The temperature is preferably about °C, and the polymerization time is usually 0.5 to 1
It is about 20 minutes, preferably about 1 to 60 minutes. The monomer concentration during polymerization is preferably about 0.1 to 8 mol/l, and 0.1 to 8 mol/l. About 5 to 5 mol/l is more preferable.

Furthermore, in the present invention, the non-conjugated polyene added to the polymerization system before the polymerization reaction of the cationic polymerizable monomer is added in an amount of 0°0f-1 times the mole of the monomer used and stirred to become uniform. It is preferable to do so. In the present invention, it is preferable to stop the polymerization reaction by adding an alcohol such as methanol for ease of later handling, but the present invention is not particularly limited to this, and any conventional commonly used means can be applied. There is no particular need to perform the termination reaction again.

Number average molecular weight mainly composed of cationically polymerizable monomer units containing isobutylene from 5°O to 500.0
00 copolymer, at least 1.0 per molecule
Five general formulas (■) [wherein, R3 represents the same meaning as above]. ] An isobutylene polymer having an unsaturated group represented by the following formula at the end of the side chain or main chain of the copolymer is produced.

This copolymer can be suitably used in a hydrosilylation reaction as described below.

Examples of the reactive silicon group in the present invention include a hydrolyzable silicon group and a silanol group.

Hydrolyzable silicon group means a hydrolyzable group or a group bonded to a silicon atom that can be hydrolyzed by moisture in the presence or absence of a silanol condensation catalyst, and specific examples of hydrolyzable groups are as follows: Examples include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group,
Commonly used groups include an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.

Among these, alkoxy groups are particularly preferred because they are mildly hydrolyzable and easy to handle. One to three hydrolyzable groups can be bonded to one silicon atom, and when two or more are bonded, they may be the same or different.

The number of silicon atoms forming the hydrolyzable silicon group may be one or two or more, but in the case of silicon atoms connected by siloxane bonds or the like, up to 20 silicon atoms are preferable.

The method for introducing reactive silicon groups into the molecules of the isobutylene polymer used in the present invention is to use isobutylene having an unsaturated group represented by the general formula (■) at the end of the side chain or main chain of the copolymer. System polymer and general formula (■) [In the formula, R', R', X, a, b and! has the same meaning as above. ], for example, F(2PtCps-6H20Pt metal,
RhCl! (PPhz)z, Rhcz3, Rh/
A l 20 z , Ru Cl z , IrCj'2,
FeCl2, AlC1x, PdCl! z” 28
20, N1CA'z, TiCA'n, etc. is used as a catalyst to introduce the compound to the end of the molecule through a so-called hydrosilylation reaction.

The hydrosilylation reaction is generally carried out at a temperature range of 0 to 150'C, and n-pentane, n-hexasan, or n-hebutane is added as necessary to adjust the reaction temperature and the viscosity of the reaction system. , benzene, toluene, xylene, and other solvents may be used.

Specific examples of the hydrogenated silicon compound represented by the general formula (■) include chlorosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, methyldimethoxysilane, Phenyldimethoxysilane! , 3. 3. 5.
5. 7. Alkoxysilanes such as 7-hebutamethyl-l,l-dimethoxytetrasiloxane, acyloxysilanes such as methyldiacetoxysilane, trimethylsiloxymethylacetoxysilane: bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate) Ketoximate silanes such as methylsilane, bis(diethylketoximate)trimethylsiloxysilane, dimethylsilane, trimethylsiloxymethylsilane, 1,1°3.3-tetramethyldisiloxane,
1. 3. Hydrosilanes having two or more 5i-H bonds in the molecule such as 5=trimethylcyclotrisiloxane: Examples include, but are not limited to, alkenyloxysilanes such as methyldi(isopropenyloxy)silane. It's not a thing. However, isobutylene polymers having chlorosilyl groups obtained by hydrosilylation reactions using chlorosilanes produce hydrogen chloride gas or hydrochloric acid when condensed and cured, which may cause practical problems. In addition, the generated chlorine ions act as a catalyst for the condensation reaction of reactive silicon groups, adversely affecting the storage stability of polymers containing such groups. Therefore, it is preferable to use the chlorosilyl group after converting the chlorine atom into an alkoxy group, acyloxy group, aminooxy group, alkenyloxy group, hydroxyl group, or the like. Among these, alkoxy groups are particularly preferred since they are mildly hydrolyzable and easy to handle.

Since the cured product of the isobutylene polymer of the present invention contains no or substantially no unsaturated groups other than aromatic rings in the main chain, it does not contain oxypropylene polymers or other unsaturated bonds. It has significantly better weather resistance and heat resistance than cured organic polymers.

Furthermore, since the isobutylene polymer of the present invention is a hydrocarbon polymer, it has good water resistance, and its cured product has extremely low water vapor permeability.

In the curable composition using the polymer of the present invention, hard r
Various silane compounds may be used as physical property modifiers to widely control physical properties such as strength and elongation of the resin.

Specific examples of such compounds include (CH,
) = S 1OH1 (CH, CH2): + S 1OH
1(CH,CH2CH2)2S iOH1(CH=),
S i (OCR,), (CHt CHt)t S
i (OCR,)2, (CHs)2 S i (
OCR2CH3)2, (CH,CHz), S i (
OCR2CH,), (CHz)-S i (OCH
-CH20CH3)2, (CH=CH2)2S
i (OCH,CH,0CHi)2, (CH,)(
CH, CH2) S i (OCR,)2, (x+y=
0 to 18), (CH=), S i NS i (CH=), (C
H3) -S i N (CHl)-, OH I 11 1 (CH3), S i -N -C-N -3i (
Hydrolyzable groups such as CH,)-1 and silanol groups are
Examples include, but are not limited to, silicon compounds containing one or more silicon compounds. Incidentally, V in the formula is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

There are roughly three methods for adding these silicon compounds.

One is a method of simply adding the compound to the isobutylene polymer. Depending on the properties of the compound, it may be uniformly dispersed and dissolved by heating and stirring, if necessary. In this case, it is not necessary to make it completely uniformly transparent;
Even in an opaque state, the purpose can be achieved as long as it is dispersed. Further, if necessary, a dispersibility improver such as a surfactant may be used in combination.

The second method is to add and mix a predetermined amount of the compound when the product is finally used. For example, when used as a two-component sealing material, the compound may be mixed as a third component in addition to the base and curing agent.

The third method is to react the compound with the isobutylene polymer in advance, and if necessary, a tin-based, titanate-based, acid or basic catalyst may be used in combination. In the case of a compound that generates a silanol group-containing compound by moisture, the objective can be achieved by adding the required amount of water and devolatilizing it by heating under reduced pressure.

Specific examples of catalysts that can be used in this case include titanate esters such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylic acids such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate. Salts: lead octylate, nibutylamine, octylamine, dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Ethylenediamine, guanidine, diphenylguanidine, 2,4.6-tris(dimethylaminomethyl)phenol, morpholine, N
-Methylmorpholine, 1,3-diazabicyclo(5,4
゜6) Amine compounds such as undecene-7 (DBU) or their salts such as carboxylic acids: Low molecular weight polyamide resin obtained from excess polyamine and polybasic acid, reaction product between excess polyamine and Epoquine compound thing;
A silane coupling agent having an amino group, such as γ-
Examples include silanol condensation catalysts with aminopropyltrimethoxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane. These catalysts may be used alone or in combination of two or more.

In the curable composition of the present invention, in addition to the isobutylene polymer having a reactive silicon group as an active ingredient, various silane compounds as physical property modifiers as described above may be used as necessary. In addition, various fillers, plasticizers, silanol condensation catalysts commonly used for curing isobutylene polymer components having reactive silicon groups as active ingredients, water, anti-aging agents, ultraviolet absorbers, lubricants,
Pigments, foaming agents, adhesion promoters, etc. may be added as necessary.

Examples of the filler used in the present invention include wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber,
Mica, walnut shell powder, rice flour, graphite, diatomaceous earth, white clay, hume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint You can open powder, zinc dust, etc. These fillers may be used alone or in combination of two or more.

Plasticizers include polybutene, hydrogenated polybutene, α
-methylstyrene oligomer, biphenyl, triphenyl, triaryl dimethane, alkylene triphenyl,
Hydrocarbon compounds such as liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl, and partially hydrogenated terphenyl; chlorinated paraffins, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, butylbenzyl phthalate, butyl phthalate Phthalate esters such as rubutyl glycolate; Non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; esters of polyalkylene gelylcols such as diethylene glycol benzoate and triethylene glycol dibenzoate; tricresyl phosphate and phosphoric acid esters such as tributyl phosphate. These may be used alone or in combination of two or more. These plasticizers may be used in place of a solvent for the purpose of adjusting the reaction temperature, adjusting the viscosity of the reaction system, etc. when introducing reactive silicon groups into the isobutylene polymer.

A silanol condensation catalyst may be used as necessary to cure the isobutylene polymer component having a reactive silicon group, which is an active component of the curable composition of the present invention. Such condensation catalysts include, for example, titanate esters such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; Reactant with phthalate ester Nidibutyltin diacetylacetonate: Organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoquine aluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate Chelate compounds such as lead octylate-nibutylamine, monoethanolamine, triethylenetetramine, guanidine, 2-ethyl-4-methylimidazole, 1,3-diazabicyclo(5,4,6)undecene-7 (DBU), etc. amine compounds or salts thereof such as carboxylic acids; and other acidic catalysts, basic catalysts, and known silanol catalysts.

In addition, in order to promote curing or develop deep hardening,
Water or a hydrate of an inorganic compound may be used as a moisture source.

The curable composition of the present invention may be used in combination with various adhesion promoters for the purpose of further improving adhesiveness.

Specifically, by using one or more types of silane coupling agents such as epoxy resins, phenol resins, aminorane compounds, and epoxysilane compounds, alkyl titanates, and aromatic polyisocyanates, a wide variety of types can be produced. The adhesion to the adherend can be improved.

Moreover, the heat resistance of the curable composition of the present invention can be improved by blending 10 to 50 parts by weight with a thermoplastic resin such as hot melt butyl.

The curable composition of the present invention thus obtained can be suitably used as adhesives, pressure-sensitive adhesives, paints, sealing compositions, waterproofing materials, spraying materials, molding materials, casting rubber materials, etc. sell.

[Effects of the Invention] The isobutylene polymer of the present invention is a polymer that does not contain any unsaturated groups other than aromatic rings in its main chain, and its cured product has excellent tensile properties and weather resistance.

In addition, this cured product is not only a cured product of the polymer using triene (Japanese Patent Application Laid-open No. 58-108208), but also
Cured product of the polymer using the above-mentioned Vinifer method (Japanese Unexamined Patent Publication No. 6
4-038407) is characterized by superior weather resistance.

[Margin below]

[Examples] Next, Examples are given to further clarify the present invention, and the present invention is not limited by the Examples.

Production Example 1 A 100ml pressure-resistant glass autoclave was equipped with a stirring blade, a three-way cock, and a vacuum line, and the polymerization container was heated at 100°C for 1 hour while being evacuated with the vacuum line to dry it, and after cooling to room temperature. The pressure was returned to normal pressure with nitrogen using a three-way cock.

Thereafter, 40 ml of methylene chloride, the main solvent, which had been dried by calcium hydride treatment, was introduced into the autoclave using a syringe while flowing nitrogen through one of the three-way cocks. Then, 20 m of distilled and purified 1,9-decadiene
Add mol and further tricumyl chloride (TCC)
Methylene chloride solution (10 ml) in which 3 mmol of
) was added.

Next, a pressure-resistant glass liquefied gas sampling tube 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, and the container body was placed on dry ice at -70"C. - Immersed in an acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel.After cooling, the inside was depressurized with a vacuum line, 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 by flowing nitrogen through one of the three-way cocks, and cooling was continued for 1 hour while stirring, and the temperature inside the polymerization vessel was raised to -30°C.

Next, 2.3.2 g (10 mmol) of TiCl was added from the three-way cock using a syringe to start polymerization, and 6.
After 0 minutes had elapsed, the reaction was completed by adding methanol that had been previously cooled to below 0°C.

Thereafter, the reaction mixture was taken out into an eggplant-shaped flask, unreacted isobutylene, methylene chloride, l,9-decadiene, and methanol were distilled off, and the remaining polymer was dissolved in 100 mj of n-hexane until it became neutral. Washing of this solution with water was repeated. Then, add 20 m of this n-hexane solution (
! The polymer was precipitated and separated by pouring the concentrated solution into 300% acetone.

The polymer thus obtained was again added to 100 ml of n
- by dissolving in hexane, drying over anhydrous magnesium sulfate, filtering, and removing n-hexane under reduced pressure.
An isobutylene polymer was obtained.

The yield is calculated from the yield of the obtained polymer, and M
n and Mw/Mn were determined by GPC method, and the terminal structure was determined by
It was determined by measuring and comparing the intensities of proton resonance signals belonging to each structure using H-NMR (300 MHz) method. The results are shown in Table 2.

In addition, Figure 1 shows the rR spectrum of the obtained isobutylene polymer, and Figure 2 shows the 'H-NMR spectrum (3
00MHz).

Production Examples 2 to 7 Polymers were produced in the same manner as Production Example 1, except that the initiator/chain transfer agent was not grown, the type and amount of nonconjugated polyene used, and the polymerization catalyst were changed as shown in Table 1. ,evaluated.

The results are also shown in Table 2.

Example 1 1CH obtained in Preparation Example 1 in a 50-4-hole flask
=CH, group-containing isobutylene polymer 5g (0,8
Add 6 mm of n-heptane lomt' and stir.
After uniformly dissolving, the mixture was degassed under reduced pressure at 90°C for 2 hours.

Next, under a nitrogen atmosphere, 10 mj of dry n-hebutane was added.
' was added and stirred to uniformly dissolve again.

There, at 50℃, dimethoxymethylsilane 0.5g (4
, 7 mmol) and 2 μ! of platinum chloride catalyst solution! ! (H,
After adding a solution of 1 g of PtC.6H, OIg dissolved in 9 g of methanol, the mixture was reacted at 90°C for 6 hours.

Thereafter, by degassing under reduced pressure at 90°C for 2 hours, isoCH having two -3i (OCH3) groups in the molecule was obtained.

A butylene polymer was obtained (Table 3).

In addition, Figure 3 shows the IR spectrum of the obtained isobutylene polymer, and Figure 4 shows the 'H-NMR spectrum (3
00MHz).

As is clear from FIG. 4, no unsaturated groups other than aromatic rings remain in the polymer.

Examples 2 to 6 -CH=C obtained in each production example (2, 3, 4, 6, 7)
The H2 group-containing isobutylene polymer was hydrosilylated in the same manner as in Example 1 to form -3i (OCR=)
Isobutylene heavy CH having = group.

Coalescence was obtained (Table 3).

Example 7 5 g (0.94 mmol) of tyrenic polymer and 10 ml of n-hebutane were added and stirred to uniformly dissolve, and then
The mixture was degassed under reduced pressure at °C for 2 hours.

Next, 10 ml of dry n-hebutane was added under a nitrogen atmosphere, stirred, and uniformly dissolved again.

There, at 50°C, 0.0% methyldichlorosilane was added. 7g (6
, 1 mmol) and 5 μl of chloroplatinic acid catalyst solution (
A solution of 82P t Cl g ・68.01 g dissolved in 8 g of 1,2-dimethoxyethane and Ig of ethanol)
was added, and the mixture was reacted at 90″C for 12 hours.

Next, 2 g of methyl orthoformate and 0.7 g of methanol were added, and the mixture was reacted at 70°C for 3 hours. At this point, the pH of the reaction system became approximately 7, which became neutral. After the volatile components were distilled off under reduced pressure, 20 ml of hexane was added to the remaining components and the mixture was homogenized by stirring, and then insoluble components were removed by filtration. Hexane was distilled off from the filtrate, and 100 parts of isobutylene-based polymer containing the following Table 3 Example 8 groups, hydrogenated polybutene (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: Polybutene OH).
1 used as a plasticizer) 50 parts, fatty acid-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo ■, product name: CCR1 used as a filler) 100 parts, Na, SO4/IOH! 5 parts of O (used as a moisture source), hindered phenolic antioxidant (manufactured by Ohmukai Shinko Kagaku ■, trade name: Nicklac NS-6)
) Weigh out 1 part, mix well, and thoroughly knead by passing it through three paint rolls three times, then add a silanol condensation catalyst consisting of 3 parts of tin octylate and 0.75 parts of laurylamine prepared separately. was added and thoroughly kneaded. The composition was poured into a mold with a thickness of about 3 mm, avoiding bubbles as much as possible, and kept at room temperature for 4 days and then for 50 minutes.
After curing at °C for 4 days, a cured product was obtained. A No. 3 dumbbell conforming to JIS K6301 was punched out from the sheet of the cured product and subjected to a tensile test at a tensile speed of 500 mm/min. The strength at break was 20 kg/cnf, and the elongation at break was 400%.

Example 9 100 parts of an isobutylene-based polymer having a group, 0.5 parts of water, and 50 parts of toluene were thoroughly stirred to form a uniform toluene solution. This solution was poured into a mold with a thickness of about 3 mm, and cured at room temperature for 1 day, then at 50°C for 4 days, and then heated at 50°C for 2 to 3 am to completely volatilize the toluene.
It was devolatilized under reduced pressure of Hg for 2 hours.

The resulting cured sheet was exposed to a Sunshine Carbon Arc Weathermeter (120 minute cycle, 18 minute spray) for 2,000 hours to measure its weather resistance.The sheet surface showed no deterioration at all, and the sheet itself showed no signs of deterioration. No resinization or softening occurred at all.

Further, when the initial physical properties of the cured product were subjected to a dumbbell tensile test in the same manner as in Example 8, the strength at break was 15 kg/
cnf, elongation at break was 90%.

[Margin below]

Comparative example 1 The molecular formula is CH3CH3CH3CH.

Ph +C-(CH2-C+T-CH2-CH-CH2
-3l-(OCH3)2]3CH,CH.

The procedure was repeated in the same manner as in Example 9 except that a polymer having a molecular weight of approximately 5,800 and having approximately three silyl groups at the terminal was used, and the initial physical properties (dumbbell tensile test) of the cured product were measured. The strength at break was 7 kg/al, and the elongation at break was 80%. Further, this cured sheet was exposed to a Sunshine Carbon Arc Weathermeter (120 minute cycle, 18 minute spray) for 500 hours to measure weather resistance, and it was found that part of the sheet surface had softened.

Example 10 Using a composition prepared in the same manner as in Example 8, approximately 0.3
A cured thin film having a thickness of mm was prepared.

This is done using the cup method (JIS Z0208 moisture permeability test)
When the moisture permeability was measured by
An extremely low value of g-an/cn[sec·cmHg was obtained.

Example 11 The same procedure as Example 8 was carried out except that the isobutylene polymer obtained in Example 5 was used.

As a result of the dumbbell tensile test, the strength at break was 15 kg/d and the elongation at break was 350%.

Example 12 Heat resistance was measured using the cured sheet prepared in Example 9.

The cured product sheet was placed in a hot air dryer at 150°C, and changes in properties over time were observed.

There was no change at all after 5 hours, and although there was some discoloration even after 24 hours, the surface tack had not increased at all.
No phenomena of resinization or softening were observed.

[Brief explanation of drawings]

FIG. 1 is an IR spectrum diagram of the isobutylene polymer obtained in Production Example 1. FIG. 2 is an 'H-NMR spectrum diagram (300MH2) of the isobutylene polymer obtained in Production Example 1. FIG. 3 is an IR spectrum diagram of the isobutylene polymer obtained in Example 1. FIG. 4 is an 'H-NMR spectrum diagram (300MH2) of the isobutylene polymer obtained in Example 1. Patent applicant Kanebuchi Kagaku Kogyo Co., Ltd. Representative Patent attorney Yoshinori Hosoda Indication of the Haka 1 case 1990 Patent application No. 221969 2 Name of the invention Isobutylene polymer having reactive silicon groups, method for producing the same and its curable composition 3, and its relationship to the case of the person making the amendment Patent applicant address: 3-2-4 Nakanoshima, Kita-ku, Osaka Name:
(094) Representative Director of Kanebuchi Chemical Industry Co., Ltd.
Tate Tsuyoshi 4, Representative Human Occupation/Terrorism 40 Dog Sales Market Nakaba Jizo 2-12 Tenma Hakkenya Hill 4th Floor Hosoda Nemoto In Patent Office 5 Date of Amended Umbrella Ordinance (
November 27, 1990 Drawings subject to amendment 6 Contents of amendment 7 Figures 2 and 4 of the drawings will be amended as shown in the attached sheet. 8 The residence of the agent other than the above is also 4th floor, Tenma Hakkenya Building, 2-12 Nakaken Genjo Higashi, Taisaka City, 40 Hosoda Nemoto M Patent Office Tn 06 (94
9) 0035, Second Duke---=-5

Claims (4)

[Claims] (1) An isobutylene polymer having at least a repeating unit represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼General formula (I) [In the formula, R^1 and R^2 each represent a hydrogen atom, a methyl group, or an ethyl group, and Q represents an unsaturated group other than an aromatic ring. R^3 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R^4 and R
^5 is 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 a triorganosiloxy group (R^) represented by R^6R^7R^8SiO-, respectively. 6, R^7 and R^8 are the same or different and represent a monovalent hydrocarbon group having 1 to 20 carbon atoms)
, X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are bonded, they may be the same or different,
a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and l represents 0 or an integer from 1 to 18. ] (2) The isobutylene polymer according to claim (1), wherein the number of repeating units represented by the general formula (I) is 1 to 10 per molecule. (3) An unsaturated group-containing isobutylene copolymer containing no unsaturated groups other than aromatic rings in the main chain by copolymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated polyene in the presence of a Lewis acid. The method for producing an isobutylene polymer according to claim 1 or 2, characterized in that the unsaturated group-containing isobutylene copolymer is obtained by hydrosilylation. (4) A curable composition containing the isobutylene polymer according to claim (1) or (2) as an active ingredient.