JP2892081B2 - Curable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a curable composition. More specifically, a styrenic monomer unit and / or an alkenyl ether monomer unit are mainly used as a curing agent, and a homosilicate or a copolymer having a hydrosilyl functional group at a terminal is contained. And a curable composition containing a catalyst.

[Problems to be Solved by Conventional Techniques / Inventions] Conventionally, various compositions have been developed as curable liquid compositions that cure to form a rubber-like substance. Among them, a polyorganosiloxane having an average of two or more vinyl groups per molecule at the molecular terminal or in the molecular chain is crosslinked with a polyorganohydrosiloxane having two or more hydrogen atoms bonded to silicon atoms per molecule. The composition to be used is excellent in deep curing properties, and is also excellent in weather resistance, water resistance, and heat resistance, and is therefore used as a sealing agent, a potting agent, and the like. However, the use of this composition is limited because of its high cost, poor adhesiveness, and easy mold generation.

On the other hand, a composition obtained by reacting an organic polymer having an alkenyl group with the polyorganohydrogensiloxane and curing is generally poor in compatibility with the organic polymer of the polyorganohydrogensiloxane. There is a problem that the hydrolysis and dehydrocondensation reaction of hydrogen siloxane are promoted, voids are generated, and a cured product having sufficient mechanical properties cannot be obtained.

[Means for Solving the Problems] In the present invention, as a result of intensive studies in view of the above-mentioned circumstances, the present invention has found that the number-average molecular weight is 600 to 200,000 and that the styrene monomer unit and / or alkenyl ether monomer unit is used alone or A copolymer having at least 1.05 hydrosilyl functional groups per molecule at the end of a molecule, generally having better compatibility with an organic polymer having an alkenyl group than polyorganohydrogensiloxane; Further, if an organic polymer having an alkenyl group and the polymer having a hydrosilyl functional group acting as a curing agent are reacted with each other using a hydrosilylation catalyst, the composition can be rapidly cured and excellent in deep curing. And arrived at the present invention.

That is, the present invention relates to (A) a homo- or copolymer mainly composed of a styrene monomer unit and / or an alkenyl ether monomer unit having a number average molecular weight of 600 to 200,000, wherein at least 1.05 A curable composition comprising (B) an organic polymer having at least one alkenyl group per molecule, and (C) a hydrosilylation catalyst.

[Examples] The composition of the present invention contains a styrene-based monomer unit and / or an alkenyl ether-based monomer unit as a component (A) acting as a curing agent and has a hydrosilyl functional group at its terminal or in combination. A polymer composed of a polymer is used. The term “mainly composed of styrene-based monomer units and / or alkenyl ether-based monomer units” as used in the present specification means that 30% of the polymer is preferable.
(% By weight, the same applies hereinafter), and more preferably 50% or more is composed of styrene monomer units and / or alkenyl ether monomer units. In addition, the homopolymer is a polymer in which the monomer unit constituting the main chain is one kind, and may include a unit derived from an initiator or a terminator.

The monomer unit constituting the main chain of the component (A) does not need to be one kind, but may be composed of several kinds of monomer units at an arbitrary ratio. That is, a polymer having one kind of styrene-based monomer unit or one kind of alkenyl ether-based monomer unit as a main chain may be used, and two or more styrene-based monomer units or two or more alkenyl-ether-based monomer units may be used. It may be a polymer having a main chain,
It may be a polymer having a styrene-based monomer unit and an alkenyl ether-based monomer unit as a main chain, a random copolymer, or a block copolymer.

The component (A) has a number average molecular weight of 600 to 200,000, preferably 600 to 100,000, more preferably 600 to 50,000.
000. If the number average molecular weight exceeds 200,000, the compatibility with the organic polymer having an alkenyl group (component (B)) decreases.

Examples of the styrene-based monomer unit include, for example, general formula (III): (Wherein R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and R ⁹ is a phenyl group or a substituted phenyl group). Can be In the general formula (III), R ⁶ and R ⁷ are preferably a hydrogen atom, and R ⁸ is preferably a hydrogen atom or a methyl group.

Specific examples of such a monomer include, for example, styrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene.
Methyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, 4-butyl styrene, 4-tert-butyl styrene, 4-hexyl styrene, -Octyl styrene, 4
-Decylstyrene, 4-tetradecylstyrene, 4-hexadecylstyrene, 4-methoxystyrene, 4-butoxystyrene, 4-meoxy-α-methylstyrene, 2
-Butoxy-α-methylstyrene, 2-dimethylaminostyrene, 4-dimethylaminostyrene, 4-phenylstyrene, 4- (4-biphenyl) styrene, α-methylstyrene, α-methyl-4-isopropylstyrene and the like. However, the present invention is not limited to these.

Examples of the alkenyl ether-based monomer unit include, for example, a compound represented by the general formula (IV): CHR ¹⁰ CHCH (OR ¹¹ ) (IV) (wherein R ¹⁰ is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, R ¹¹ Represents a monovalent alkyl group having 1 to 24 carbon atoms, and the alkyl group may be branched, straight-chain, or substituted with a group containing a hetero atom. Units are given. General formula (IV)
In the formula, R ¹⁰ is preferably a hydrogen atom or a methyl group.

Specific examples of such a monomer include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-vinyloxyethyl benzoate, 2-acetoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, diethyl [2 -(Vinyloxy) ethyl] malonate, 3-tris (ethoxycarbonyl) propyl vinyl ether, 2-vinyloxyethyl cinnamate, cyclohexyl vinyl ether, n-hexadecyl vinyl ether, 2-chloroethyl vinyl ether, 4-fluorobutyl vinyl ether, 3-bromo Butyl vinyl ether, 4-ethoxybutyl vinyl ether, methyl propenyl ether, ethyl propenyl ether, isopropyl Propenyl ether, n- butyl propenyl ether, isobutyl propenyl ether, cyclohexyl propenyl ether, n- hexadecyl propenyl ether, 2-but such chloroethyl propenyl ether and the like, but is not limited thereto.

The hydrosilyl functional group present at the terminal of the component (A) used in the present invention is a group containing a hydrosilyl group (Si-H), and when the composition of the present invention is heated or the like, the organic weight of the component (B) is reduced. It is a group for reacting with the alkenyl group in the coalescence and crosslinking to cure the composition.

Not particularly limited to the hydrosilyl functional group. For example _{-SiH a (CH 3) 3-} a, -SiH a (C 2 H 5) 3-a -SiH a (C 6 H 5) 3-a (a = _{1~3), - SiH 2 (C} 6 H 13) 1 piece a group having silicon atom, such _{as, -Si (CH 3) 2 Si} (CH 3) 2 H, -Si (CH 3) 2 CH 2 SH 2 _{Si (CH 3) 2 H,} -Si (CH 3) 2 Si (CH 3) H 2, _{-Si (CH 3) 2 NHSi (} CH 3) 2 H, -Si (CH 3) 2 N [Si (CH 3) 2 H] 2, A group having two or more silicon atoms, such as (R = —CH ₃ , —C ₂ H ₅ , —C ₆ H ₅ , —OSi (CH ₃ ) ₃ (however, a plurality of Rs may be the same or different, the same applies hereinafter), a = 0 to 50 ) And the like, and groups derived from various polyvalent hydrogen siloxanes having a chain, branched or cyclic shape.

Among the various hydrosilyl functional groups, the molecular weight of the portion constituting the hydrosilyl functional group is desirably 500 or less from the viewpoint that the compatibility with the organic polymer as the component (B) is less likely to be impaired. Further considering the reactivity of the hydrosilyl functionality, Are preferred.

The number of hydrosilyl functional groups contained in the component (A) may be at least 1.05 per molecule, preferably two, more preferably 2 to 15, and particularly preferably 3 to 12. When the number of the hydrosilyl functional groups is less than 1.05, when the composition of the present invention is cured by a hydrosilylation reaction, the curing is slow and the curing failure easily occurs.
On the other hand, when the number is more than 15, the stability of the component (A) decreases, and a large amount of hydrosilyl functional groups easily remain in the cured product even after curing, which may cause voids and cracks. .

The component (A) having a hydrosilyl functional group as described above has a silyl functional group represented by the general formula (I): (Wherein X represents a hydrosilyl functional group, R ¹ 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). It is preferred to have.

Specific examples of the alkyl group having 1 to 8 carbon atoms, which is one kind of R ^{1 in} the general formula (I), include specific examples of an aryl group having 6 to 20 carbon atoms such as a methyl group and an ethyl group. Specific examples of the aralkyl group having 7 to 20 carbon atoms such as a phenyl group include a benzyl group.

The method for producing the polymer having the hydrosilyl functional group (component (A)) is not particularly limited, and it may be produced by any method. For example, (i) a homo- or copolymer mainly composed of a styrene-based monomer unit and / or an alkenyl ether-based monomer unit and having a Si—Cl group in a molecule, such as LiAlH ₄ , NaBH _4, etc. (Ii) reducing the Si—Cl group in the polymer to the Si—H group, (ii) a styrene monomer unit and / or an alkenyl ether monomer unit, A polymer having a functional group Y ¹ in the molecule,
A method of reacting a compound having a functional group Y ² and hydrosilyl functional group reactive with the functional group Y ¹ in the molecule, either alone or co mainly of (iii) a styrene-based monomer unit and (or) alkenyl ether monomer units A polymer having at least 1.05 alkenyl groups per molecule is reacted with a polyhydrosilane compound having at least two hydrosilyl groups, and the hydrosilyl functional group remains in the polymer molecule even after the reaction. And a method of performing selective hydrosilylation so as to remain in the compound.

Of the above methods, the method (iii) is preferred because the manufacturing process is generally simple. In this case, some polyhydrosilane compounds may react with two or more molecules of the polymer to increase the molecular weight, but such a polymer may be used as the component (A) without any problem.

A method for producing a polymer having at least 1.05 alkenyl groups per molecule, which is a homo- or copolymer mainly composed of a styrene monomer unit or an alkenyl ether monomer unit used in the method (iii), includes: An adduct consisting of a compound having at least two ethylenically unsaturated groups and a protonic acid compound is used as an initiator, and a halogen group present at the terminal of a polymer obtained by living polymerization with the monomer is treated with a polymerization terminator having an alkenyl group. There is a method of end capping.
Specific examples of the terminator include, for example, CH ₂ CHCH—CH ₂ O
H, And the like, but are not limited thereto.

The organic polymer (component (B)) used in the present invention comprises 1
Polymers having at least one alkenyl group per molecule.

The number average molecular weight of the organic polymer is preferably from 500 to 50,000, more preferably from 500 to 20,000, from the viewpoint of the properties of the cured product and the compatibility with the polymer of the component (A). The number average molecular weight per alkenyl group is preferably from 100 to 25,000.

There is no particular limitation on the main chain skeleton of the organic polymer, and polymers having various main chain skeletons can be used.

Specific examples of the main chain skeleton include, for example, polyether polymers such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymer;
Polyester copolymer obtained by condensation of basic acid and glycol or ring-opening polymerization of lactones; ethylene-propylene copolymer; polyisobutylene; copolymer of isobutylene and isoprene; polychloroprene; polyisoprene; isoprene Copolymer of butadiene, acrylonitrile, styrene, etc .; polybutadiene; copolymer of butadiene and styrene, acrylonitrile, etc .; Polyacrylate polymer obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; acrylate ester such as ethyl acrylate and butyl acrylate and vinegar Vinyl, acrylonitrile,
Acrylate copolymers with methyl methacrylate, styrene, etc .; Graft polymers obtained by polymerizing vinyl monomers in the organic polymer; Polysulfide copolymers; Nylon 6 by ring-opening polymerization of α-aminocaprolactam; Nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid; Nylon 610 by condensation polymerization of hexamethylenediamine and sebacic acid; Nylon 11 by condensation polymerization of ε-aminoundecanoic acid; Nylon by ring-opening polymerization of ε-aminolaurolactam 12; a polyamide-based polymer such as a copolymer nylon having two or more components among the above-mentioned nylons; a polycarbonate-based polymer produced by condensation polymerization of bisphenol A and carbonyl chloride; a diallyl phthalate-based polymer; Styrene monomer unit or alkenyl ether Homopolymers or copolymers mainly comprising ether-based monomer unit and the like are exemplified.

Among the organic polymers having various main chain skeletons as described above, a polyether polymer, an acrylate polymer, and a polyester are preferable because of good compatibility with the hydrosilyl functional group-containing polymer of the component (A). Polymer, hydrocarbon polymer, polyvinyl ether polymer,
Polystyrene-based polymers are preferred. Further, a polyvinyl ether-based polymer and a polystyrene-based polymer are preferred because they have particularly good compatibility with the component (A).

The alkenyl group in the component (B) is not particularly limited, but has the general formula (II): _Or R ² —CH ＝ CH ₂ (II) (wherein R ² is —R ³ —, —R ⁴ — ^{O-R 5 -, - R} 4 -O-CO-
And ^{-R 4 -CO- (R 3, R} 4, R 5 is a divalent hydrocarbon group having 1 to 20 carbon atoms) group selected from divalent organic groups represented by, r is 0 or 1)
An alkenyl group represented by is preferred. Among these, an allyl group is preferred from the viewpoints of high reactivity to the hydrosilylation reaction and high substituent introduction rate.

The alkenyl group may be present at any position in the molecule, but when a rubber-like cured product is prepared using the composition of the present invention, the alkenyl group is preferably present at the molecular end in the cured product. Is preferable because the effective mesh chain length of the polymer becomes longer.

The number of alkenyl groups is at least 1 per molecule.
And an average of 2 to 5 is preferred. If the number of alkenyl groups is less than one, it tends to cause poor curing.

Organic polymer having alkenyl group (component (B))
As a method for introducing an alkenyl group into the organic polymer when producing the polymer, various methods can be adopted, but a method of introducing an alkenyl group after polymerization and a method of introducing an alkenyl group during polymerization Can be roughly divided into

As a method of introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group or an alkoxy group at a terminal, a main chain or a side chain may be prepared by adding an active group and an alkenyl group reactive to the functional group. The alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having

Specific examples of the organic compound having an active group and an alkenyl group having reactivity with the functional group include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide having 3 to 20 carbon atoms. unsaturated fatty acids, acid halides, or an acid anhydride, allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , unsaturated fatty acids having 3 to 20 carbon atoms such as allyl bromo formate (CH ₂ = CHCH ₂ OCOBr) substituted Carbonic halide, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) Ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloro Chill) such as benzene, and the like.

As a method of introducing an alkenyl group during the polymerization, for example, when an organic polymer as the component (B) is produced by a radical polymerization method, an alkenyl group having low radical reactivity is added to a molecule such as allyl methacrylate or allyl acrylate. By using a radical chain transfer agent having an alkenyl group having a low radical reactivity such as a vinyl monomer having an alkenyl group or an allyl mercaptan, an alkenyl group can be introduced into the main chain or terminal of the polymer.

The method for introducing an alkenyl group at the terminal of a homo- or copolymer mainly composed of a styrene-based monomer unit or an alkenyl ether-based monomer unit has been described in the method (iii) of the polymer of the component (A). .

There is no particular limitation on the mode of bonding between the alkenyl group and the organic polymer, and when directly bonded by carbon-carbon engagement, via an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, or the like. The alkenyl group is bonded to the main chain skeleton of the organic polymer.

The proportion of the component (A) and the component (B) in the composition of the present invention is such that the ratio of the hydrosilyl functional group in the component (A) to 0.2 to 5.0 per alkenyl group in the component (B). Is preferable, and a ratio of 0.4 to 2.5 is more preferable. When the number of hydrosilyl functional groups is less than 0.2, when the composition of the present invention is cured, the cured product is likely to be insufficiently cured and become a cured product having a sticky and low strength, and 5.0%.
If the number is more than the number, the active hydrosilyl functional group remains in the cured product in a large amount even after the curing, so that cracks and voids are generated and a uniform cured product tends to be unable to be obtained.

The hydrosilylation catalyst which is the component (C) used in the present invention is not particularly limited, and any catalyst can be used.

Specific examples of the hydrosilylation catalyst include, for example, simple substance of platinum, alumina, silica, solid platinum supported on a carrier such as carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone and the like. Complex, platinum-olefin complex (eg, Pt (CH ₂ CHCH ₂ ) _{2
(PPh 3) 2, Pt (} CH 2 = CH 2) 2 Cl 2), platinum - vinylsiloxane complex (e.g. _{Pt a (ViMe 2 SiO SiMe 2} Vi) b, P
t [(MeViSiO) ₄ ] _a ), platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complex (for example, Pt [P (OPh ₃ )] ₄ , Pt [ P (OBu)
₃ ] ₄ ). In the above formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group,
a and b represent integers. Further dicarbonyldichloroplatinum, Ashby US Pat. Nos. 3,159,601 and 31
No. 59662, a platinum-hydrocarbon complex,
The platinum alcoholate catalyst described in US Pat. No. 3,209,972 to Lamoreaux, Mododi
Also useful are the platinum chloride-olefin complexes described in c) U.S. Pat. No. 3,516,926. Examples of the catalyst other than the platinum compound include, for example, RhCl (PPh ₃ )
_{3, RhCl 3, Rh / Al} 2 O 3, RuCl 3, IrCl 2, FeCl 3, AlCl 3, P
dCl ₂ · 2H ₂ O, NiCl ₂ , TiCl ₄ (wherein Ph represents a phenyl group) and the like. These catalysts may be used alone or in combination of two or more.

Among these hydrosilylation catalysts, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity.

The amount of the hydrosilylation catalyst to be used is not particularly limited, but may be 10 ^-1 to 10-1 per ¹ mol of the alkenyl group in the component (B).
^-8 mol, preferably 10 ^-3 to 10 ^-6 mol. If the amount of the catalyst is less than 10 ^-8 mol, the curing tends not to proceed sufficiently, and it is preferable not to use more than 10 ^-1 mol in view of economy and corrosiveness to metals.

The method for preparing the composition of the present invention from the components (A), (B) and (C) is not particularly limited.

Although the curing conditions of the composition of the present invention are not particularly limited, it can be generally cured at 0 to 200 ° C, preferably 30 to 150 ° C, for 10 seconds to 4 hours. Especially at high temperatures of 80-150 ° C.
It can be cured in a short time of about 0 seconds to 1 hour.

Since the composition of the present invention has good compatibility between the polymer having a hydrosilyl functional group (component (A)) and the organic polymer having an alkenyl group (component (B)), it does not involve a phenomenon such as foaming. It can be cured and has excellent deep curability, mechanical properties, etc., and also has excellent weather resistance, water resistance, heat resistance, etc., so it can be used as a sealing agent, potting agent, paint, paint film waterproofing agent, etc. It is useful as a material for blending with a resin. The properties of the obtained cured product depend on the molecular weight of the component (A) used, the main chain skeleton and the molecular weight of the component (B), etc., but are prepared from rubber-like to resin-like (rigid plastic-like) ones. I can do it.

In the composition of the present invention, in addition to the components (A), (B) and (C), a solvent, a weld improver, a physical property modifier, a storage stability improver, and a plasticizer may be used depending on the purpose of use. , Fillers, anti-aging agents, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, amine radical chain inhibitors,
Various additives such as a phosphorus peroxide decomposer, a lubricant, a pigment, and a foaming agent may be appropriately added.

Next, the present invention will be described more specifically based on examples. In the following production example, the reaction was carried out in a glass container equipped with a three-way cock after drying sufficiently, replacing the inside with dry nitrogen, and injecting the reagent under a stream of dry nitrogen using a syringe through the three-way cock. Performed in

Synthesis Example 1 [Synthesis of bifunctional polyisobutyl vinyl ether (IBVE)] Toluene 35 ml, carbon tetrachloride 2.5 ml, compound Z92 mg (0.25
mmol), and then cooled to -78 ° C.
5 ml of an HI solution (n-hexane solution, 100 mM) was charged, left for 2 minutes, and kept at −78 ° C. with isobutyl vinyl ether (IB
VE) (2.5 ml, 19.1 mmol) and a ZnI ₂ solution (diethyl ether solution, 10 M) (5 ml) were added, and the mixture was stirred to be uniform. Thereafter, the entire container was transferred to a thermostat at 0 ° C. and reacted for 10 minutes (95% polymerization rate).

After adding 40 ml of allyl alcohol as a terminator thereto, the mixture was thoroughly stirred.

After purifying the obtained polymer, the molecular weight was determined by GPC method. As a result, n = 7400 and w / n = 1.07. Further, according to ¹ H-NMR method, the polymer has a bisphenol skeleton in the main chain in the main chain, the main chain is a unit from IBVE, and a polymer in which 1.1 aryliether groups are introduced per molecule at the terminal. It could be confirmed.

Synthesis Example 2 [Synthesis of bifunctional poly p-methoxystyrene (pMeOSt)] [Compound Z] _o = 5 mM [HI] _o = 10 mM [pMeOSt] _o = 376 mM [ZnI ₂ ] _o = 5 mM Toluene 35 ml, tetralin 2.5 ml , Compound Z92 mg (0.25
mmol), and then cooled to -78 ° C.
5 ml of an HI solution (n-hexane solution, 100 mM) was charged, and left for 2 minutes. Then, p-methoxystyrene (pMeSO
t) 2.5 ml (18.8 mmol) and 5 ml of a Znl ₂ solution (diethyl ether solution, 50 mM) were added, and the mixture was stirred to make it uniform. Thereafter, the whole container was transferred to a thermostat at 0 ° C. and reacted for 20 minutes (polymerization rate: 92%).

After adding 40 ml of allyl alcohol as a terminator thereto, the mixture was thoroughly stirred.

After the obtained polymer was purified by reprecipitation of methanol, the molecular weight was examined by a GPC method.
0, w / n = 1.09. Further, the bisphenol skeleton of the compound Z was found in the main chain by ¹ H-NMR method, and the main chain was pMeO.
It was a unit from St, and it was confirmed that the polymer was one in which 1.1 allyl ether groups were introduced per molecule at the terminal.

Synthesis Example 3 [Synthesis of bifunctional (pMeOSt-IBVE-pMeOSt)] [Compound Z] _o = 5 mM [HI] _o = 10 mM [IBVE] _o = 190 mM [ZnI ₂ ] _o = 0.1 mM ([pMeOSt] _o = 188 mM [ZnI ₂ ] _o = 5 mM) Toluene 35 ml, tetralin 2.5 ml, compound z92 mg (0.25
mmol), and then cooled to -78 ° C.
5 ml of an HI solution (n-hexane solution, 100 mM) was charged, and after standing for 2 minutes, 1.25 ml of IBVE (9.95 mmol) and ZnI ₂ were kept at −78 ° C.
5 ml of a solution (diethyl ether solution, 1 mM) was added, and the mixture was stirred to be uniform. Then transfer the whole container to a 0 ° C thermostat
The reaction was carried out for 10 minutes (polymerization rate 100%). Then, immediately p
1.25 ml (9.4 mmol) of MeSOt and 5 ml of a Znl ₂ solution (diethyl ether solution, 50 mM) were added and reacted at 0 ° C for 20 minutes (95% polymerization rate).

After adding 40 ml of allyl alcohol as a terminator thereto, the mixture was thoroughly stirred.

After purification, the molecular weight of the obtained polymer was examined by GPC method, whereupon n = 7900 and w / n = 1.08. In addition, according to ¹ H-NMR method, the main chain has a bisphenol skeleton of compound Z in the main chain, the main chain is a block of pMeOSt-IBVE-pMeOSt, and a polymer in which 1.1 allyl ether groups are introduced at one end per molecule. That was confirmed.

In addition, it was also confirmed that by changing the terminator of Synthesis Examples 1 to 3 from allyl alcohol to a sodium salt of allyl alcohol, the introduction rate of the terminal functional group was increased.

Synthesis Example 4 A 50 ml four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. As a cyclic polysiloxane under nitrogen atmosphere in this flask (LS 8600, manufactured by Shin-Etsu Chemical Co., Ltd.) 174 mg (0.72 mmol)
Was charged. 2 g of polyisobutyl vinyl ether (IBVE) having 1.1 allyl ether groups introduced per molecule at the molecular end synthesized in Synthesis Example 1 in a dropping funnel (0.29 mmol of moles of allyl ether group), 23 ml of toluene and a chloroplatinic acid catalyst solution _{(H 2 PtCl 6 · 6H 2} O 1g of ethanol 1 ml, 1,2-dimethoxyethane 99ml solution dissolved in) was charged toluene solution consisting of 30.mu..

The flask was heated to 70 ° C. and the toluene solution was added dropwise over about 15 minutes. Thereafter, the reaction temperature was raised to 80 ° C., and after stirring for about 6 hours, the remaining allyl groups in the reaction solution were quantified by the IR method, and it was confirmed that the carbon-carbon double bond at 1645 cm ⁻¹ had disappeared. Was done.

Further, in order to remove toluene and unreacted excess cyclic polysiloxane in the reaction system, deaeration under reduced pressure at 80 ° C. was performed at 3 ° C.
Over time, about 2.09 g of polyisobutyl vinyl ether with hydrosilyl functionality was obtained as a colorless viscous liquid.

The hydrosilyl functionality in the polyisobutyl vinyl ether was confirmed by IR spectroscopy as a strong absorption at 2150 cm ^-1 . In addition, as a result of measurement by 300 MHz ¹ H-NMR spectrum method, the peak of the allyl group disappeared, and 0.1 to 0.3 pp was newly added.
absorption derived from Si-CH ₃ in the vicinity of m, Si near 4.6~4.8ppm
Absorption from -H appeared. Further 0.1 ppm of Si-CH2
Absorption of triplets derived from -CH ₂ -CH ₂ -O~ was observed, it was confirmed that the new Si-C bonds by hydrosilylation has been generated.

From the above results, the molecular weight of the obtained polymer was increased by the cyclic polysiloxane. It was found to be a polyisobutyl vinyl ether having a molecular terminal represented by

Synthesis Example 5 As cyclic polysiloxane (LS 8990, manufactured by Shin-Etsu Chemical Co., Ltd.) 217 mg (0.72 mmol)
The reaction was carried out in exactly the same manner as in Synthesis Example 4 except that was used, to obtain about 2.11 g of a colorless viscous polyisobutyl vinyl ether having a hydrosilyl functional group.

From the results of analysis by IR spectroscopy and NMR spectroscopy, the obtained polymer had a molecular weight increased by the cyclic hydrogen polysiloxane. It was found to be a polyisobutyl vinyl ether having a molecular terminal represented by

Synthesis Example 6 Allyl ether group at the molecular end synthesized in Synthesis Example 2
1.1 polyp-methoxystyrene introduced per molecule (p
The reaction was carried out in exactly the same manner as in Synthesis Example 4 except that 2.44 g (0.27 mmol) of MeOSt) was used to obtain about 2.53 g of a colorless viscous poly (p-methoxystyrene) having a hydrosilyl functional group.

Synthesis Example 7 One allyl ether group at the molecular end synthesized in Synthesis Example 3
2.11 g of pMeOSt-IBVE-pMeOSt 1.1 introduced per molecule
(0.27 mmol), except that pMeO having a colorless viscous hydrosilyl functional group was reacted in exactly the same manner as in Synthesis Example 4.
2.20 g of St-IBVE-pMeOSt was obtained.

Examples 1 to 8 Compatibility between the allyl ether group-containing polymer produced in Synthesis Examples 1, 2 and 3 and the hydrosilyl functional group-containing polymer (curing agent) produced in Synthesis Examples 4, 5, 6 and 7 is examined. For this purpose, a hydrosilyl functional group-containing polymer was added in a combination as shown in Table 1 so that the number ratio of allyl ether group to hydrosilyl functional group was 1/1 with respect to 1.0 g of the allyl ether group-containing polymer. The mixture was thoroughly mixed, centrifuged, defoamed, and the state of mixing was observed.

As a result, although some of them are slightly cloudy, all combinations are generally transparent and uniform, and the hydrosilyl functional group-containing polymer has good compatibility with the allyl ether group-containing organic polymer. I knew it was there.

Next, in order to examine the curability, a 10-fold diluted solution of the chloroplatinic acid catalyst solution used in Synthesis Example 4 was added to each of the above-mentioned mixtures, and Pt was 1 × with respect to 1 mol of the allyl ether group of each polymer.
It was added to 10 ^-3 mol and mixed well.

A part of the obtained mixture was taken on a gelling tester (manufactured by Nissin Kagaku Co., Ltd.), and the snap-up time (time until showing rubber elasticity) was measured at a predetermined temperature. The results are shown in Table 1.

Table 1 shows that the composition of the present invention is high-temperature fast-curing.

Comparative Examples 1 and 2 Instead of the hydrosilyl functional group-containing polymer synthesized in Synthesis Example 4, the formula: (A unit represented by Si (CH ₃ ) ₂ —O is 60 to 70%) (polymethylhydro-dimethylsiloxane copolymer having an average molecular weight of about 2000 to 2100, PS 1 manufactured by Chisso Corporation)
23) was used in the same manner as in Example 1 or 5, except that the molar ratio between the allyl ether group and the hydrosilyl group of PS 123 in the polymer synthesized in Synthesis Example 1 or 3 was 1/1. An attempt was made to produce a cured product.

As a result, each organic polymer containing an allyl ether group and PS 123 were poorly compatible and became turbid during mixing. Also,
All were separated when left for a long time. Each of the mixtures had a large amount of foaming even after defoaming under reduced pressure, and only a cured product containing a large number of foams was obtained.

[Effects of the Invention] When used in the composition of the present invention, a cured product having a uniform composition that is fast-curing and excellent in deep-part curability can be obtained.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takanao Iwahara 1-1-43-403 Kita-Ochiai, Suma-ku, Kobe-shi, Hyogo (72) Inventor Kazuya Yonezawa 5-12-11, 56, Tsutsujigaoka, Tarumizu-ku, Kobe-shi, Hyogo (56 References JP-A-62-220503 (JP, A) JP-A-3-243603 (JP, A) JP-A-63-35656 (JP, A) JP-A-3-152164 (JP, A) 3-200807 (JP, A) JP-A-3-181565 (JP, A) Patent 2732315 (JP, B2) Patent 2752196 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 1/00-101/14

Claims (14)

(57) [Claims] (A) A homo- or copolymer having a number average molecular weight of 600 to 200,000 and mainly composed of a styrene monomer unit and / or an alkenyl ether monomer unit, wherein at least 1.05 hydrosilyl per molecule. A curable composition comprising: a polymer having a functional group at a terminal; (B) an organic polymer having at least one alkenyl group per molecule; and (C) a hydrolylation catalyst. 2. The composition according to claim 1, wherein the ratio of the component (A) to the component (B) is (B)
2. The ratio of the hydrosilyl functional group in the component (A) to 0.2 to 5.0 per alkenyl group in the component.
A composition as described. (3) The hydrosilyl functional group of the component (A) has a general formula (I): (Wherein, X is a hydrosilyl functional group containing at least one hydrosilyl group, R ¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms.
The composition according to claim 1, which is contained in a form represented by the following formula: 4. X in the general formula (I) is: (Wherein, R is a group selected from the group consisting of a hydrogen atom, -OSi (CH ₃ ) ₃ groups and a hydrocarbon group having 1 to 10 carbon atoms,
A plurality of Rs may be the same or different, m, n, p,
q is an integer of 0 to 50, where m + n ≧ 1, m + n + p + q
= 1 to 50) or the general formula: (Wherein, R is the same as above, i is an integer of 1 to 50, j is 0 to
The composition according to claim 3, which is a group represented by an integer of 49, wherein i + j = 2 to 50). 5. X in the general formula (I) is: 5. The composition according to claim 3, wherein k and l are groups represented by the following formula: 2 ≦ k + 1 ≦ 4. 6. An organic polymer having at least 1.05 alkenyl groups per molecule, wherein the component (A) is a homo- or copolymer mainly composed of styrene monomer units and / or alkenyl ether monomer units. 4. The composition according to claim 1, which is a polymer produced by reacting the coalesced compound with a polyhydrosilane compound in the presence of a hydrosilylation catalyst such that the hydrosilyl functional group remains. (7) The component (A) is a polyhydrosilane compound 1
The composition according to claim 1, 2 or 6, comprising a hydrosilyl functional group-containing polymer whose molecular weight is increased by reaction of two or more molecules of the alkenyl group-containing organic polymer according to claim 6 with respect to the molecule. 8. The number average molecular weight of the organic polymer of component (B) is as follows:
3. The composition according to claim 1, wherein the composition is 500 to 50,000. 9. The organic polymer (B) having a number average molecular weight of 500 to 50,000 and at least one compound represented by the general formula (I)
I): _Or R ² —CH ＝ CH ₂ (II) (wherein R ² is —R ³ —, —R ⁴ —O—R ⁵ —, —R ⁴ —O—CO—
And -R ⁴ -CO- (wherein R ³ , R ⁴ , and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms), and r is 0 or 3. The composition according to claim 1, which is a polymer having a group represented by the following formula: 10. The composition according to claim 1, wherein the alkenyl group in the component (B) is an allyl group. 11. The composition according to claim 1, wherein component (B) is a hydrocarbon polymer. 12. The composition according to claim 1, wherein component (B) is a polyether polymer. 13. The composition according to claim 1, wherein component (B) is an acrylate polymer. 14. The composition according to claim 1, wherein component (B) is a polyester polymer.