JP2000336165A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition having good workability by including a specific reactive silicon group-contg. polyether oligomer and a silanol condensation catalyst so as to indirectly lower the reactivity of the reactive silicon group in the oligomer and thereby control the initial curing rate for the composition. SOLUTION: This curable composition is obtained by including (A) a reactive silicon group-contg. polyether oligomer having a structural moiety of the formula O-R1-CH(CH3)-CH2-[Si(R22-b)(Xb)O]mSi(R33-a)Xa (R1 is H or a 1-20C bivalent organic group containing at least one constitutive atom such as O; R2 and R3 are each a 1-20C alkyl or the like; X is OH or the like; (a) is 0-3; b is 0-2; m is 0-19; wherein a+Σb>=1) and (B) a silanol condensation catalyst such as dibutyltin diacetylacetonate. By the way, the component A is prepared, for example, by introducing an unsaturated group linkage into a hydroxyl-terminated polyether opligomer followed by carrying out a reaction with a reactive silicon group-contg. compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition containing a reactive silicon group-containing polyether oligomer and a silanol condensation catalyst.

[0002]

2. Description of the Related Art Hitherto, room temperature curable compositions containing a reactive silicon group-containing polyether oligomer and a specific silanol condensation catalyst have been known and have been used for sealants, adhesives and the like.

[0003] WO91 / 13928 discloses a curable oxypropylene polymer containing a reactive silicon group, a divalent tin organic carboxylic acid and an organic amine compound for the purpose of improving the resilience of a cured product. A composition is disclosed.

Japanese Patent Application Laid-Open No. 5-125272 discloses that
Oxypropylene polymer containing a reactive silicon group, 4
Disclosed is a curable composition comprising an organic tin compound having a valency, which aims to improve the curing speed.

[0005] Since a room temperature curable composition is cured by moisture in the air, if the curing is too fast, the curing proceeds during the work, which causes a deterioration in workability. Therefore, it is important to adjust the curing speed to improve the workability, and until now, the curing speed has been adjusted by changing the type of catalyst, increasing or decreasing the amount of the catalyst, or changing the terminal reactive silicon group.

However, when the curing speed is reduced by using these methods for the purpose of improving workability, if the speed is excessively reduced, curing problems such as poor curing and deterioration in physical properties occur. Therefore, it is difficult to improve both the workability and the curability with the curable compositions so far, and the curing speed has been merely adjusted while considering the balance between the two.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to indirectly reduce the reactivity of a reactive silicon group in an oligomer by introducing a methyl group near the reactive silicon group in the oligomer. Accordingly, it is to obtain a curable composition having good workability in which the initial curing rate is adjusted.

[0008]

The first aspect of the present invention is as follows.
(A) the general formula shown below in the molecule ^{(1): -O-R 1} -CH (CH 3) -CH 2 - (Si (R 2 2-b) (X b) O) m Si (R 3 _{3- a} ) _Xa (1) (wherein, R ¹ is a divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of hydrogen, oxygen, and nitrogen as a constituent atom. , R ² and R ³ are the same or different and are 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 triorgano represented by (R ′) ₃ SiO—. A siloxy group, when two or more R ² or R ³ are present, they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; And 3
R ′ may be the same or different.
X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. The m-number of _{^{(Si (R 2 2-b}} ) (X
_b ) For b in the group O), they may be the same or different. m represents an integer of 0 to 19. However, the present invention relates to a curable composition containing a reactive silicon group-containing polyether oligomer having a structural portion represented by (a + ａb ≧ 1) and (B) a silanol condensation catalyst.

In a preferred embodiment, R ^{1 of} (A)
Is CH ₂ .

In a further preferred embodiment, the present invention relates to the above curable composition, wherein (A) is a reactive silicon group-containing polyether oligomer having a structural portion represented by the following formula in the molecule. —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (CH ₃ )
(OCH ₃ ) _{2 In} another preferred embodiment, (A) has the general formula (2): —O—R ¹ —C (CH ₃ ) = CH ₂ (2) (R ¹ is the same as the above) a polyether oligomer obtained by introducing an unsaturated bond represented by the general formula (3): H- (Si ( R 2 2-b) (X b) O) m Si (R 3 3-a) X a (3 (R ² , R ³ , a, b, m, and X are the same as defined above) and a compound having a reactive silicon group in an atmosphere containing oxygen, in a system in which a catalyst and a sulfur compound are present. The present invention relates to the above curable composition, which is a reactive silicon group-containing polyether oligomer having a reactive silicon group obtained by the reaction.

In another more preferred embodiment,
(A) is a compound H-Si (CH ₃ ) having a reactive silicon group with a polyether oligomer -O-CH ₂ -C (CH ₃ ) = CH ₂ into which an unsaturated bond represented by the following formula is introduced. OCH ₃ ) ₂ is a reactive silicon group-containing polyether oligomer having a structure shown below, which is obtained by reacting with OCH ₃ ) _{2 in} a system in which a catalyst and a sulfur compound are present in an atmosphere containing oxygen. The present invention relates to the curable composition. —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (CH ₃ )
(OCH ₃ ) ₂ Another more preferred embodiment relates to the curable composition, wherein 85% or more of the terminals of the reactive silicon group-containing polyether oligomer are reactive silicon groups.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The reactive silicon group-containing polyether oligomer which is the component (A) used in the present invention has the general formula (1): -OR ¹ -CH _{(CH 3) -CH 2 - (} Si (R 2 2-b) (X b) O) m Si (R 3 3- a) X a (1) ( wherein R ¹ is hydrogen, oxygen, and nitrogen A divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of R ¹ and R ² , wherein R ² and R ³ are the same or different alkyl groups having 1 to 20 carbon atoms, An aryl group having 6 to 20; an aralkyl group having 7 to 20 carbon atoms; or a triorganosiloxy group represented by (R ′) ₃ SiO—, and when two or more R ² or R ³ are present, they are the same. Wherein R ′ is a monovalent monovalent having 1 to 20 carbon atoms. 3 be a hydrocarbon group
R ′ may be the same or different.
X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. The m-number of _{^{(Si (R 2 2-b}} ) (X
_b ) For b in the group O), they may be the same or different. m represents an integer of 0 to 19. Provided that at least one structure represented by the formula: a + Δb ≧ 1) is contained in the side chain or at the terminal,
Any polyether-based oligomer whose main chain is composed of polyether may be used.

The reactive silyl group-containing olefins conventionally used
Rigomer is, for example, -O-CH_Two-CH_Two-CH_Two-Structure
Reactive via a linear alkyleneoxy group such as
Having a silicon group bonded to the oligomer backbone
In some cases, the curing speed was too high and workability was poor.
In the present invention, -OR having a branched methyl group
¹-CH (CH_Three) -CH_Two-Through the structure, the reactive silicon
In which an elementary group is bonded to an oligomer. like this
By adjusting the curing speed by branching the methyl group to
A cured composition having good workability can be obtained.

R¹From hydrogen, oxygen, and nitrogen.
Contains at least one member selected from the group consisting of
A divalent organic group having 1 to 20 carbon atoms, such as -CH
_Two-, -C_TwoH_Four-, -C_ThreeH₆-, -C_FourH₈-, -C_FiveH_Ten
-, -C₆H_Four-, -C₆H₁₂-, -C₇H₁₄-, -C₈H
₁₆-, -C₉H₁₈-, -C_TenH₂₀-, -CH (CH_Three)
-, -CH_Two-CH (CH_Three)-, -CH_Two-CH (C
H_Three) -CH_Two-, -C_TwoH_Four-CH (CH_Three)-, -CH_Two
-C₆H_Four-, -CH_Two-C₆H_Four-CH_Two-, -C_TwoH_Four-C
₆H_Four-, -C (O)-, -C (O) -CH_Two-, -C
(O) -C₆H_Four-, -C (O) -NH-, -C (O)-
NH-CH_Two-, -C (O) -NH-C₆H_Four-, -C
(O) -O-, -C (O) -O-CH_Two-, -C (O)
-OC₆H_FourAnd the like. Easy to synthesize
-CH at the point_Two-, -C_TwoH_Four-, -CH_Two-CH (CH_Three)
-, -C (O)-, -C (O) -NH- are preferred,
Furthermore, from the availability of raw materials, -CH_Two− Is particularly preferred
No.

Specific examples of R ² and R ³ include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, and R ′ Is a methyl group or a phenyl group, and a triorganosiloxy group represented by (R ′) ₃ SiO—. As R ² , R ³ and R ′, a methyl group is particularly preferred.

[0016] Formula (1) reactive silicon group contained in the reactive silicon group-containing polyether oligomer represented by the general formula (4): - (Si ( R 2 2-b) (X b) O ) _m Si (groups represented by ^{_{R 3 3-a) X a}} (4) can be mentioned. (Wherein R ² and R ³ are the same or different and are represented by 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 SiO—). A triorganosiloxy group, when two or more R ² or R ³ are present, they may be the same or different, wherein R ′ is a monovalent carbon atom having 1 to 20 carbon atoms; X is a hydrogen group, and three R's may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same. A is 0, 1, 2 or 3, b is 0,
1 or 2 is shown, respectively. In addition, m (Si (R ²
_{For b in the 2-b} ) (X _b ) O) group, they may be the same or different. m is 0 to 19
Indicates an integer. However, it is assumed that a + Σb ≧ 1 is satisfied. In the present invention, the reactive silicon group is a group capable of forming a siloxane bond by a condensation reaction between the two and crosslinkable.

The hydrolyzable group in X is not particularly limited, and may be any conventionally known hydrolyzable group. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
Examples thereof include an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group is preferable in terms of gentle hydrolysis and easy handling.

The hydroxyl group and the hydrolyzable group can be bonded to one to three silicon atoms, and (a + Δb) is 1
To 5 is preferred. When two or more hydroxyl groups or hydrolyzable groups are present in the reactive silicon group, they may be the same or different.

The number of silicon atoms in the reactive silicon group may be one or two or more. In the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like, 20 is used.
The number may be about one.

A reactive silicon group represented by the following general formula (5) is preferred because it is easily available. —Si (R ³ _3-a ) X _a (5) (wherein R ³ , X and a are the same as described above.) The reactive silicon group is at least on average with respect to each molecular chain terminal of the polyether oligomer. It is preferred that there be 0.1, and from the viewpoint of curability, it is preferable that 0.5 to 5 be present. More preferably, there are 0.8 to 2 of them. From the viewpoint that a cured product exhibiting good rubber elasticity behavior can be obtained, it is particularly preferred that 0.9 to 1 be present.

Specifically, it is preferable that (A) is a reactive silicon group-containing polyether oligomer having a structural portion represented by the following formula in the molecule. —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (CH ₃ )
(0CH ₃ ) ₂ The molecular weight of the polyether oligomer of the component (A) of the present invention is not particularly limited, but the number average molecular weight is preferably from 1,000 to 100,000. If the number average molecular weight is less than 1,000, the resulting cured product of the reactive silicon group-containing polyether oligomer becomes brittle, and
If it exceeds, the concentration of the functional group becomes too low and the curing rate is lowered, and the viscosity of the oligomer becomes too high, which makes the handling difficult, which is not preferable. Further, the number average molecular weight is particularly preferably from 5,000 to 50,000 from the viewpoint of the viscosity of the obtained reactive silicon group-containing polyether oligomer.

Here, the number average molecular weight of the polyether oligomer is determined by directly measuring the terminal group concentration by a titration analysis based on the principle of the method for measuring the hydroxyl value according to JIS K1557 and the method for measuring the element number such as JIS K0070. And
It is defined as the number average molecular weight determined in consideration of the structure of the polyether oligomer. As a relative measurement method of the number average molecular weight, a calibration curve of the molecular weight in terms of polystyrene obtained by general GPC measurement and the above-mentioned end group molecular weight was prepared, and GP
It is also possible to convert the C molecular weight into a terminal group molecular weight.

The main chain structure of the polyether oligomer of the component (A) may be any polymer having a structure represented by —RO— as a repeating unit, where R is hydrogen, oxygen, And a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of nitrogen and nitrogen as a constituent atom. Further, a homopolymer in which all of the repeating units are the same, or a copolymer containing two or more types of repeating units may be used. Further, the main chain may have a branched structure. As the component (A) of the present invention, for example, a hydroxy group-containing polyether obtainable by the following various methods can be used.

In order to obtain the component (A) of the present invention, alkylene oxides, specifically, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α- Methyl styrene oxide and alkyl or allyl or aryl glycidyl ethers, specifically, methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, etc.
Using a substituted or unsubstituted epoxy having 1 to 12 carbon atoms, ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol Glycol, polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol and other dihydric alcohols or polyhydric alcohols, and various oligomers having hydroxyl groups as initiators And polyethers obtained by ring-opening polymerization in the presence of various catalysts can be used. KOH, NaOH
Known catalysts such as an alkali catalyst such as trifluoroborane-etherate, a double metal cyanide complex catalyst such as an aluminoporphyrin metal complex and a cobalt zinc cyanide-glyme complex catalyst are used. In particular, it is preferable to use a double metal cyanide complex catalyst having few side reactions, but other catalysts may be used.

As a method for producing the component (A) from such a polyether oligomer having a hydroxyl group, a known method may be used, for example, after introducing an unsaturated bond into the polyether oligomer having a hydroxyl group. And a method of reacting a compound having a reactive silicon group.

Examples of a method for introducing an unsaturated bond into a polyether oligomer having a hydroxyl group include a method for forming a bond by an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like. For example, when an unsaturated group is introduced by an ether bond, -OM (M is N
After generating the a or K), the general formula _{(6): H 2 C =} C (CH 3) -R 1 -Y (6) ( wherein R ¹ is selected from the group consisting of hydrogen, oxygen, and nitrogen And a method of producing a polyether having an unsaturated group by reacting with a divalent organic group having 1 to 20 carbon atoms containing at least one kind as a constituent atom and Y being a halogen). .

As a method for reacting a compound having a reactive silicon group with a polyether oligomer into which an unsaturated bond has been introduced, a hydrosilylation reaction carried out in the presence of a catalyst can be mentioned. In the hydrosilylation reaction, in order to accelerate the reaction, it is preferable to perform the reaction in an atmosphere containing oxygen and to add an additive such as a sulfur compound.

The compound having a reactive silicon group used in the hydrosilylation reaction includes one or more silicon groups bonded to the above-mentioned hydroxyl group or hydrolyzable group in the molecule, and one or more silicon-hydrogen groups. Any compound having a group in the molecule may be used. Typical examples include a compound represented by the following general formula (3). Formula (3): H- (Si ( R 2 2-b) (X b) O) m Si (R 3 3-a) X a (3) (R 2, R 3, a, b, m, X is the same as the group described in the general formula (1). Specifically, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane,
Trimethylsiloxymethylchlorosilane, 1,1,3,
Halogenated silanes such as 3-tetramethyl-1-bromodisiloxane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, trimethylsiloxydiethoxysilane Alkoxysilanes, such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane, and trimethylsiloxydiacetoxysilane; bis (dimethylketoxime) methylsilane, bis (cyclohexylke) Toximate) methylsilane, bis (diethylketoxime) trimethylsiloxysilane, bis (methylethylketoxime) methylsilane, tris ( Setokishimeto) such keto carboxylate formate silanes silane; and such alkenyloxy silanes methyl isopropenyloxy silane.
Among these, alkoxysilanes are particularly preferred, and among the alkoxy groups, a methoxy group is particularly preferred.

A reactive silicon group represented by the following general formula (7) is preferred because it is easily available. _{^{H-Si (R 3 3-}} a) X a (7) ( wherein R ^3, X, a the same. The) also the general formula (3) and R ² in the general formula (7),
And specific examples of R ³ include, for example an alkyl group such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl, aralkyl groups such as benzyl group, R 'is a methyl group or a phenyl group And a triorganosiloxy group represented by (R ′) ₃ SiO—. As R ² , R ³ and R ′, a methyl group is particularly preferred.

Specific examples of the above hydrosilylation reaction include an unsaturated compound represented by the following general formula (2): —O—R ¹ —C (CH ₃ ) = CH ₂ (R ¹ is the same as described above) a polyether oligomer obtained by introducing a binding general formula (3): H- (Si ( R 2 2-b) (X b) O) m Si (R 3 3-a) X a (3) (R 2, R ³ , a, b, m, and X are the same as the groups described in the above general formula (1)) and a compound having a reactive silicon group represented by the formula: A reactive silicon group-containing polyether oligomer having a reactive silicon group obtained by reacting in a system in which a sulfur compound is present is preferable, and further a polyether oligomer having an unsaturated bond represented by the following formula -O-CH ₂ -C (CH ₃₎ = compound having CH ₂ with a reactive silicon group H-Si (CH ₃₎ OCH ₃₎ in an atmosphere having a _second oxygen, the catalyst, and a reactive silicon group-containing polyether oligomer -O-CH ₂ -CH having the structure shown below obtained by reacting in situ sulfur compound is present _{(CH 3) -CH 2 -Si (} CH 3)
(OCH ₃ ) ₂ is more preferred.

Further, in the present invention, the hydrolyzable group X in the obtained silyl group can be converted to another hydrolyzable group. In particular, when the X group is a halogen, the compound is preferably converted to another hydrolyzable group since hydrogen halide having a strong pungent odor is generated upon curing with moisture. As the hydrolyzable functional group that can be converted, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group,
Examples include an aminooxy group and a mercapto group.
There are various methods for converting a halogen functional group into these hydrolyzable functional groups. For example, as a method for converting to an alkoxy group, methanol, ethanol, 2-methoxyethanol, sec-butanol, t
alcohols and phenols such as er-butanol and phenol; alkoxides of alcohols and phenols such as sodium, potassium and lithium; orthoformates such as methyl orthoformate and ethyl orthoformate; ethylene oxide; propylene oxide; A specific example is a method of reacting an epoxy compound such as allyl glycidyl ether with a halogen functional group. Particularly, the reaction can be easily carried out by using a reaction system consisting of alcohols and phenols and epoxy compounds in combination with alcohols and phenols and orthoformate esters combined with and. And obtains favorable results. Similarly, as a method for converting into an acyloxy group, a method of reacting a carboxylic acid such as acetic acid and propionic acid, an acid anhydride such as acetic anhydride, a sodium salt, a potassium salt and a lithium salt of a carboxylic acid; Is specifically exemplified. Similarly, methods for converting to an aminooxy group include hydroxylamines such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-methylphenylhydroxylamine and N-hydroxylpyrrolidine; Sodium salts,
Specific examples include a method of reacting a potassium salt and a lithium salt with a halogen functional group. Similarly, as a method of converting to an amide group, N, N-dimethylamine,
A method of reacting primary and secondary amines such as N, N-diethylamine, N-methylphenylamine and pyrrolidine, sodium salts, potassium salts and lithium salts of primary and secondary amines with a halogen functional group. Specific examples are given below. Similarly, as a method of converting to an acid amide,
Specific examples include a method of reacting an acid amide having at least one hydrogen atom on a nitrogen atom such as acetamide, formamide and propionamide, a sodium salt, a potassium salt and a lithium salt of the acid amide with a halogen functional group. It is listed. Ketoximes such as acetoxime and methyl ethyl ketoxime; and the use of a reaction system in which a mercaptan such as N-octyl mercaptan and t-butyl mercaptan is combined with an orthoformate or an epoxy compound, the ketoximate group and the mercapto group, respectively. Some can be converted and the other can be converted to alkoxyl groups derived from orthoformate or epoxy compounds. As described above, it is also possible to convert various hydrolyzable functional groups to other hydrolyzable functional groups and use them instead of converting to other hydrolyzable functional groups only in the case of halogen functional groups.

The hydrosilylation reaction in the production method of the present invention is usually performed at 10 to 200 ° C., preferably at 20 to 150 ° C.
° C, more preferably in the range of 40 to 120 ° C. If necessary, such as adjustment of the reaction temperature and adjustment of the viscosity of the reaction system, benzene, toluene, xylene, tetrahydrofuran, methylene chloride, pentane, Hexane,
Solvents such as heptane can be used.

The catalyst used in the reaction between the polyether oligomer having an unsaturated bond introduced therein and the compound having a reactive silicon group is selected from the group VIII transition metal elements such as platinum, rhodium, cobalt, palladium and nickel. A metal complex catalyst or the like is effectively used. For example,
_{H 2 PtCl 6 · 6H 2 O} , platinum - vinylsiloxane complex, a platinum - olefin complexes, Pt metal, RhCl (P
Ph ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , I
_{rCl 3, FeCl 3, AlCl 3} , PdCl 2 · 2H
Compounds such as ₂ O, NiCl ₂ , TiCl _{4 and} the like can be used, but from the viewpoint of hydrosilylation reactivity, it is particularly preferable to be either a platinum-vinylsiloxane complex or a platinum-olefin complex. The term "platinum-vinylsiloxane complex" as used herein is a generic term for a compound in which a siloxane, a polysiloxane, or a cyclic siloxane is coordinated with a platinum atom having a vinyl group in the molecule as a ligand. Specific examples of the child include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and the like. Is mentioned. Specific examples of the olefin ligand of the platinum-olefin complex include 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene,
11-dodecadienes, 1,5-cyclooctadienes and the like can be mentioned. Among the above ligands, 1,9-decadiene is particularly preferred.

The platinum-vinylsiloxane complex, platinum-
The olefin complex is disclosed in JP-B-8-9006.

The amount of the catalyst used is not particularly limited, but it is usually preferable to use 10 ^-1 to 10 ^-8 mol of a platinum catalyst per mol of the alkenyl group, more preferably ¹ to 10 ^-8 mol.
It can be used in the range of 0 ^-3 to 10 ^-6 mol. If the amount of the catalyst is small, the hydrosilylation reaction may not proceed sufficiently. Further, if the amount of the catalyst is too large, there is a problem that the cost burden due to the consumption of the catalyst increases and the amount of the catalyst remaining in the product increases.

In terms of accelerating the hydrosilylation reaction, reactivation of the catalyst by use of oxygen (Japanese Patent Laid-Open No. 8-28)
It is preferable to add 3339) or a sulfur compound. The addition of the sulfur compound contributes to a reduction in the production time, a reduction in the production cost, and an increase in the productivity without causing a problem such as an increase in the cost of the expensive platinum catalyst or a problem of removing the residual catalyst. Examples of the sulfur compound include simple sulfur, thiol, sulfide, sulfoxide, sulfone, thioketone, and the like. Sulfur is particularly preferred, but is not limited thereto. In order to add the sulfur compound to the liquid phase reaction system, for example, the sulfur compound can be dissolved and mixed in advance in a part of the reaction solution or the solvent and then uniformly dispersed throughout. For example, the compound can be added after dissolving a sulfur compound in an organic solvent such as toluene, hexane, or xylene.

For the amount of the sulfur compound added, for example,
Is 0.1 to 10 times the amount based on the number of moles of the metal catalyst,
Or 10 based on the number of moles of the alkenyl group.^-3From
10 ^-6Double the amount or 0.1% based on the total weight of the reaction solution.
001 to 10 ppm
it can. If the amount is small, the effect of the present invention is sufficiently achieved.
May not be possible. If the amount of sulfur compounds is too high
Problems that reduce the catalytic activity or hinder the reaction
In some cases, it is preferable to select the appropriate amount.
New

The hydrosilylation reaction in the production method of the present invention can be carried out without a solvent or in the presence of a solvent. As the solvent for the hydrosilylation reaction, generally, hydrocarbons, halogenated hydrocarbons, ethers, and esters can be used, but hexane, toluene, xylene,
It is preferable to use methylene chloride, tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether. In particular, when performing hydrosilylation of a polymer compound, a method using a solvent is preferable for liquefaction or viscosity reduction. Further, a plasticizer added in the step of commercializing the polymer compound may be used as the reaction solvent.

In the hydrosilylation reaction in the production method of the present invention, the gas phase of the reactor used for the hydrosilylation reaction may consist solely of an inert gas such as nitrogen or helium, or may contain oxygen or the like. Is also good. When performing a hydrosilylation reaction, the reactor gas phase may be carried out in the presence of an inert gas such as nitrogen or helium from the viewpoint of safety in handling combustible substances. However, when the reactor gas phase is carried out in the presence of an inert gas such as nitrogen or helium, the reaction rate may decrease depending on the reaction system conditions for hydrosilylation.

In the hydrosilylation reaction in the production method of the present invention, the oxygen concentration in the gas phase of the reactor is set to a value that avoids the explosive mixed composition, thereby promoting the hydrosilylation reaction safely in the presence of oxygen. Can be. The oxygen concentration in the gas phase of the reactor can be, for example, 0.5 to 10%.

Further, in order to suppress the oxidation of the polyether oligomer, the reaction solvent, and the plasticizer in the system by oxygen in the hydrosilylation reaction, the hydrosilylation reaction can be carried out in the presence of an antioxidant. As the antioxidant, a phenolic antioxidant having a function of a radical chain inhibitor, for example, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl -6-tert-butylphenol, 2,2'-methylenebis (4-methyl-6
-Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert)
-Butylphenol), tetrakis methylene-3
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate @ methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and the like can be used. As similar radical chain inhibitors, amine antioxidants such as phenyl-β-naphthylamine, α-naphthylamine,
N, N'-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N'-diphenyl-p-phenylenediamine and the like can also be used, but are not limited thereto.

According to the production method of the present invention, a reactive silicon group-containing polyether oligomer characterized in that the number of reactive silicon-containing groups is at least 85% of the number of terminals of the polyether oligomer on average. It is possible. By using a material having a silyl group introduction rate of 85% or more, a material having sufficient properties (e.g., breaking strength, elongation at break, etc.) as a sealing material and an adhesive and having excellent adhesive strength can be obtained.

Various methods can be considered for measuring the silylation rate. At present, an accurate value can be obtained by an NMR measurement method. By calculating the ratio of the terminal into which the reactive silicon-containing group has been introduced to the terminal not having been introduced by NMR, the silyl group introduction ratio can be determined. The reactive silicon group-containing polyether oligomer used for the component (A) may be used alone or in combination of two or more.

As the silanol condensation catalyst (B) of the present invention, titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxy such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; Acid salts; reaction products of dibutyltin oxide and phthalic acid esters; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate Chelates such as titanium, titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine Dibutylamine, monoethanolamine, diethanolamine, triethanolamine,
Diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,
Diethylaminopropylamine, xylylenediamine,
Triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) Amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction of excess polyamines with epoxy compounds Silanol condensation catalysts such as products; silane coupling agents having an amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; and other acidic catalysts and basic Known silanol condensation catalysts such as catalysts You. These catalysts may be used alone or in combination of two or more. Particularly preferred are tin octylate, a reaction product of dibutyltin oxide and a phthalate, and dibutyltin diacetylacetonate.

The amount of these silanol condensation catalysts used is
0.1 to 100 parts by weight of the oxyalkylene polymer
It is preferably about 20 parts by weight, more preferably about 1 to 10 parts by weight. If the amount of the silanol condensation catalyst used is too small relative to the oxypropylene polymer, the curing rate becomes slow, and the curing reaction does not easily proceed sufficiently. On the other hand, if the amount of the silanol condensation catalyst used is too large relative to the oxyalkylene polymer, local heat generation or foaming occurs during curing, and it is difficult to obtain a good cured product, which is not preferable.

The mixture of the reactive silicon group-containing polyether oligomer of the present invention and a silanol condensation catalyst is cured at room temperature by atmospheric moisture to give a coating film having good adhesion to metals, glass, etc. It is useful as a coating composition for automobiles, sealing compositions, coating compositions, and adhesive compositions.

The curable composition of the present invention can contain various plasticizers, fillers, solvents, adhesion-imparting agents, dehydrating agents, and other additives as necessary.

Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate, dioctyl adipate, and dioctyl. Non-aromatic dibasic acid esters such as sebacate, and phosphate esters such as tricresyl phosphate and tributyl phosphate, and the like. As a relatively high molecular weight type plasticizer, for example, dibasic acid and dihydric alcohol And polyethers such as polypropylene glycol and derivatives thereof, and polystyrenes such as poly-α-methylstyrene and polystyrene.

In particular, it is preferable to use polyethers in order to prevent the storage stability of the composition and the curing rate after storage from lowering.

These plasticizers can be used alone or as a mixture. These plasticizers are used in an amount of about 20 to 400 parts by weight based on 100 parts by weight of the reactive silicon group-containing polyether oligomer.

Specific examples of the filler include, for example, wood powder, walnut shell powder, rice husk powder, pulp, cotton chip, mica, graphite, diatomaceous earth, terra alba, kaolin, clay, talc, silicic anhydride, Inorganic fillers such as quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber, glass beads, magnesium carbonate, titanium oxide, alumina, glass balloon, shirasu balloon, silica balloon, calcium oxide, magnesium oxide, and silicon oxide Examples of the organic filler include powdered rubber, recycled rubber, fine powder of thermoplastic or thermosetting resin, and hollow bodies such as polyethylene. These fillers may be used alone or in combination of two or more.

From the viewpoint of workability, the filler is used in an amount of 3 to 100 parts by weight of the polyether oligomer (A).
About 300 parts are preferable, and about 10 to 150 parts is more preferable.

Specific examples of the solvent include hydrocarbons such as toluene, xylene, n-hexane and cyclohexane, acetates such as ethyl acetate and butyl acetate, and alcohols such as methanol, ethanol, isopropanol and n-butanol. And non-reactive solvents such as ethers such as ethyl cellosolve, butyl cellosolve, and cellosolve acetate; methyl ethyl ketone, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone, acetone, cyclohexanone, and cyclooctanone. There is no particular limitation as long as such a solvent is used.

Specific examples of the adhesiveness-imparting agent include:
Amino-containing alkoxysilanes or amino-substituted alkoxysilane derivative compounds are preferred.

Specific examples of the amino group-containing alkoxysilane or amino group-substituted alkoxysilane derivative include:
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- γ-aminopropyltriethoxysilane, N
Amino-substituted alkoxysilanes such as-(β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane, and
The above amino-substituted alkoxysilane and γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy A reaction product with an epoxysilane compound such as silane or a methacryloxysilane compound such as methacryloxypropyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane The reactants are: The reaction between the amino-substituted alkoxysilane and the epoxy silane compound or the acryloylsilane compound is performed by mixing 0.2 to 5 mol of the silane compound with respect to 1 mol of the amino-substituted alkoxysilane, and mixing at room temperature to 1 mol.
It can be easily obtained by stirring at 80 ° C. for 1 to 8 hours.

The amino-substituted alkoxysilane or the amino-substituted alkoxysilane derivative compound is used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polyether polymer having a crosslinkable hydrolyzable silyl functional group at the terminal. Preferably. If the amount is less than 0.01 part by weight, the expected adhesiveness is hardly exhibited, and if it exceeds 20 parts by weight, the physical properties of the cured rubber are adversely affected.

Specific examples of the dehydrating agent include (A)
A component having a hydrolyzable group bonded to a silicon atom which reacts more easily with H ₂ O than a silicon group in the reactive silicon group-containing polyether oligomer as a component is preferable, and usually a compound having a molecular weight of 300 or less is preferable.

The hydrolyzable functional groups include alkoxy
Group, acyloxy group, ketoxmate group, amino group,
Nooxy group, amide group, alkenyloxy group and the like are examples.
Wear. Epoxy-containing and amino-containing substituents
Group, acryl-containing group, mercapto-containing group, etc.
You. Specific examples of such compounds include Si (O
C _TwoH_Five)_Four, CH_Two= CHSi (OC_TwoH_Five)_Three, CH_Two= C
HSi (OCH_Three)_Three, CH _Two= CHSi (OAc)_Three, C
H_Three-Si [ON = C (CH_Three) (C_TwoH_Five)]_Three, CH_ThreeS
i [N (CH_Three)_Two]_Three, CH_ThreeSi [N (CH_Three) (C_TwoH
_Five)]_Three, CH_ThreeSi [N (CH_Three) Ac]_Three, CH_ThreeSi
[OC (C_TwoH_Five) = CH_Two]_Three, CH_Two(O) CHCH_TwoO
(CH_Two)_ThreeSi (OCH_Three)_Three, CH_Two(O) CHCH_Two
O (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three, CH_ThreeCH_TwoSi
(OCH_Three)_Three, CH_ThreeCH_TwoSi (OCH_TwoCH_Three)_Three, C
H_Two= C (CH_Three) COO (CH_Two)_ThreeSi (OCH_Three)_Three,
CH_Two= C (CH_Three) COO (CH_Two)_ThreeSi (OCH_TwoC
H_Three)_Three, HS (CH_Two)_ThreeSi (OCH_Three)_Three, HS (CH
_Two)_ThreeSi (OCH_TwoCH_Three)_ThreeAnd the like. These
The liquid medicines can be used alone or in combination. These dehydration
The agent is a reactive silicon group-containing polyether oligomer 100
About 0.01 to 20 parts by weight
Good. Examples of the other additives include hydrogenated castor
Oil, organic bentonite, calcium stearate, etc.
Aging of anti-sagging agents, coloring agents, UV absorbers, light stabilizers, etc.
And the like.

The method for producing the curable composition of the present invention containing the component (A) and the component (B) is not particularly limited. For example, the component (A) and the component (B) are blended, and a mixer, a roll or a kneader is used. A conventional method such as kneading using a solvent or the like, or dissolving and mixing each component using a solvent can be employed. The composition may be a one-pack or two-pack composition.

[0060]

EXAMPLES In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited to these examples. Synthesis Example 1 Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene oxide having a molecular weight of about 2,000 as an initiator, and the number average molecular weight was about 1
Polypropylene oxide having a molecular weight of 000 (terminal molecular weight calculated by measuring the concentration of the terminal group) was obtained. Subsequently, the hydroxyl group of the hydroxyl group-terminated polyether oligomer was adjusted to 1.
A methanol solution of twice equivalent amount of NaOMe is added to distill off methanol, and 3-chloro-2-methyl-1-propene is added to convert the terminal hydroxyl group to a methallyl group, and both ends are methallyl groups. Number average molecular weight of about 10,000
A functional polypropylene oxide (a1) was obtained. Synthesis Example 2 Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene oxide having a molecular weight of about 2,000 as an initiator, and the number average molecular weight was about 1
Polypropylene oxide having a molecular weight of 000 (terminal molecular weight calculated by measuring the concentration of the terminal group) was obtained. Subsequently, the hydroxyl group of the hydroxyl group-terminated polyether oligomer was adjusted to 1.
A methanol solution of 2 equivalents of NaOMe is added to distill off methanol, and 3-chloro-1-propene is added to convert the terminal hydroxyl group to an allyl group. 10,000 bifunctional polypropylene oxides (b1) were obtained. Synthesis Example 3 (a1) 500 obtained in Synthesis Example 1 in a 1 L autoclave
g, 10 g of hexane and azeotropic dehydration at 90 ° C.
After the hexane was distilled off under reduced pressure, the inside of the vessel was replaced with 8% O ₂ / N ₂ . To this, 25 μl of sulfur (1% by weight in toluene solution) and 56 μl of a platinum divinyldisiloxane complex (3% by weight of xylene solution in terms of platinum) were added, and 24.2 g of dimethoxymethylsilane was added dropwise. After reacting the mixed solution at 90 ° C. for 5 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyether oligomer (a). The obtained reactive silicon group-containing polyether oligomer (a) had a number average molecular weight of about 10,000 (the molecular weight in terms of polystyrene converted by GPC measurement was converted to the molecular weight of the terminal group), and the silyl group introduction rate determined by NMR was 97. %Met. Synthesis Example 4 (b1) 500 obtained in Synthesis Example 2 in a 1 L autoclave
g, 10 g of hexane and azeotropic dehydration at 90 ° C.
Hexane was distilled off under reduced pressure, followed by nitrogen replacement. To this, 30 μl of a platinum divinyldisiloxane complex (a 3 wt% xylene solution in terms of platinum) was added, and then 9.0 g of dimethoxymethylsilane was added dropwise. 90 ℃ of the mixed solution
After reacting for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyether oligomer (b). The number average molecular weight of the obtained reactive silicon group-containing polyether oligomer (b) is about 10.0.
00 (the molecular weight in terms of polystyrene determined by GPC measurement was converted to the molecular weight of the terminal group), and the silyl group introduction rate determined by NMR was 77%. Example 1 Reactive silicon group-containing polyether oligomer (a) 50
0.3 g of H ₂ O and 0.2 g of silanol condensation catalyst dibutyltin diacetylacetonate (product name: Neostan U-220, manufactured by Nitto Kasei Co., Ltd.) were added to the resulting mixture, followed by stirring for 30 seconds and centrifugal defoaming for 1 minute. . Then, the change with time of the viscosity was measured with a BM type viscometer (rotor No. 4, 6 rpm), and the time until the viscosity became 100 Pa · s is shown in Table 1.

In Table 1, the number of parts to be added of the silanol condensation catalyst indicates the amount added to 100 g of the oligomer. Example 2 Reactive silicon group-containing polyether oligomer (a) 50
0.3 g of H ₂ O, silanol condensation catalyst tin octylate (Nitto Kasei Co., Ltd. product name: Neostan U-28)
After adding 3.0 g of laurylamine and 0.5 g, the mixture was stirred for 30 seconds and centrifuged for 1 minute. Thereafter, the change with time of the viscosity was measured with a BM type viscometer (rotor No. 4, 6 rpm), and the time until the viscosity became 100 Pa · s is shown in Table 1. Comparative Example 1 Reactive silicon group-containing polyether oligomer (b) 50
0.3 g of H ₂ O and 0.2 g of a silanol condensation catalyst dibutyltin diacetylacetonate (product name: Neostan U-220, manufactured by Nitto Kasei Co., Ltd.) were added, followed by stirring for 30 seconds and centrifugal defoaming for 1 minute. . Thereafter, the change with time of the viscosity was measured with a BM type viscometer (rotor No. 4, 6 rpm), and the time until the viscosity became 100 Pa · s is shown in Table 1. Comparative Example 2 Reactive silicon group-containing polyether oligomer (b) 50
0.3 g of H ₂ O, silanol condensation catalyst tin octylate (Nitto Kasei Co., Ltd. product name: Neostan U-28)
After adding 3.0 g of laurylamine and 0.5 g, the mixture was stirred for 30 seconds and centrifuged for 1 minute. Thereafter, the change with time of the viscosity was measured with a BM type viscometer (rotor No. 4, 6 rpm), and the time until the viscosity became 100 Pa · s is shown in Table 1.

[0062]

[Table 1] From the above results, it can be seen that in Examples 1 and 2, since a branched methyl group was introduced near the reactive silicon group, the curing time could be adjusted. On the other hand, Comparative Examples 1 and 2 have a structure in which a reactive silicon group is bonded to the oligomer main chain via a linear alkyleneoxy group, and the curing time is short.

[0063]

According to the present invention, by introducing a methyl group in the vicinity of a reactive silicon group in an oligomer, the reactivity of the reactive silicon group is reduced, and a curable composition with good workability in which the curing time is adjusted is obtained. Can be.

Claims (6)

[Claims] 1. A (A) shown below general formula in the molecule ^{(1): -O-R 1} -CH (CH 3) -CH 2 - (Si (R 2 2-b) (X b) O) _m Si (R ³ _{3- a} ) X _a (1) (wherein R ¹ is a divalent having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, oxygen, and nitrogen as a constituent atom. Wherein R ² and R ³ are the same or different and are 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 SiO— And when two or more R ² or R ³ are present, they may be the same or different, wherein R ′ is a group having 1 to 20 carbon atoms. A trivalent hydrocarbon group,
R ′ may be the same or different.
X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. The m-number of _{^{(Si (R 2 2-b}} ) (X
_b ) For b in the group O), they may be the same or different. m represents an integer of 0 to 19. However, a curable composition containing a reactive silicon group-containing polyether oligomer having a structural portion represented by the formula (a + Σb ≧ 1) and (B) a silanol condensation catalyst. 2. The curable composition according to claim ¹ , wherein R ^{1 in} (A) is CH ₂ . 3. The curable composition according to claim 1, wherein (A) is a reactive silicon group-containing polyether oligomer having a structural part represented by the following formula in the molecule. —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (CH ₃ )
(OCH ₃ ) ₂ 4. An unsaturated bond represented by the general formula (2): —O—R ¹ —C (CH ₃ ) = CH ₂ (R ¹ is as defined above) is introduced. a polyether oligomer, the general formula (3): H- (Si ( R 2 2-b) (X b) O) m Si (R 3 3-a) X a (3) (R 2, R 3, a, b, m, and X are the same as defined above), and a compound having a reactive silicon group is reacted in a system containing a catalyst and a sulfur compound in an atmosphere containing oxygen in the presence of oxygen. The curable composition according to claim 1, which is a reactive silicon group-containing polyether oligomer having a silicon group. 5. A compound having a reactive silicon group and a polyether oligomer —O—CH ₂ —C (CH ₃ ) 2CH ₂ having an unsaturated bond represented by the following formula: A reactive silicon group-containing polyether oligomer having the following structural portion obtained by reacting (CH ₃ ) (OCH ₃ ) ₂ with an oxygen-containing atmosphere in a system in which a catalyst and a sulfur compound are present; The curable composition according to claim 1, wherein —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (CH ₃ )
(OCH ₃ ) ₂ 6. The curable composition according to claim 4, wherein 85% or more of the terminals of the reactive silicon group-containing polyether oligomer are reactive silicon groups.