JP2002241491A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method which enables synthesis of a polymer having a high modulus at 100% elongation by a coupling reaction utilizing a hydroxy group of a polyoxyalkylene polymer containing in one molecule a crosslinkable silicon group and a hydroxy group. SOLUTION: The production method of the crosslinkable silicon group- containing polyoxyalkylene polymer comprises subjecting a polyoxyalkylene polymer, which contains at least 85% of a polyoxyalkylene polymer having a number-average molecular weight of at least 3,000 and bears an unsaturated group and a hydroxy group in one molecule, to a hydrosilylation reaction with a compound, which contains in one molecule a hydrogen-silicon bond and a crosslinkable silicon group, with a hydrosilylation yield based on the unsaturated group of at least 75%, and effecting a coupling reaction utilizing a hydroxy group of the resultant polyoxyalkylene polymer containing a crosslinkable silicon group and a hydroxy group in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyoxyalkylene polymer containing a crosslinkable silicon group. Specifically, a polyoxyalkylene polymer containing a double metal cyanide complex and having an unsaturated group and a hydroxyl group in one molecule in which the ratio of the polyoxyalkylene polymer is 85% or more, and hydrogen- A compound having a silicon bond and a compound having a crosslinkable silicon group is subjected to a hydrosilylation reaction, and the resulting compound is coupled using a hydroxyl group of a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. The present invention relates to a method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer, which comprises performing a reaction.

[0002]

2. Description of the Related Art A polyoxyalkylene polymer having a crosslinkable silicon group is widely used as a raw material polymer for building or industrial sealing materials, adhesives, coating materials and the like. The main manufacturing method is disclosed in
As exemplified in JP-A-156599, JP-A-52-73998 and JP-A-3-72527, the terminal hydroxyl group of the polyoxyalkylene polymer mainly has a terminal hydroxyl group such as an allyl group or a methallyl group. It is through a step of introducing a saturated group. On the other hand, as another production method, a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule in a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, a hydrosilylation catalyst A production method is also known in which a hydrosilylation reaction is performed in the presence of a compound, and a coupling reaction is performed using a hydroxyl group.

[0003]

SUMMARY OF THE INVENTION A compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule in a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is converted into a hydrosilylation catalyst. The production method in which a hydrosilylation reaction is performed in the presence and a coupling reaction is performed using a hydroxyl group has a high content of a polyoxyalkylene polymer having no unsaturated group in one molecule contained in the polyoxyalkylene polymer. In addition, there is a problem that physical properties required for industrial sealing materials and the like cannot be exhibited. In other words, a polyoxyalkylene polymer having no unsaturated group in one molecule,
Since the hydrosilylation reaction is not performed in the presence of the hydrosilylation catalyst, even if the coupling reaction is carried out using the hydroxyl group contained in the polyoxyalkylene polymer having no unsaturated group in one molecule, A crosslinkable silicon group-containing polyoxyalkylene polymer cannot be obtained. Thus, the polyoxyalkylene polymer having no unsaturated group in one molecule contained in the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule has crosslinkable silicon introduced. Therefore, there was a problem that the crosslinking density was low and only a polymer having a low modulus could be obtained. This is particularly problematic when obtaining physical properties that balance elongation and strength at elongation necessary for industrial sealing materials and the like. In other words, the larger the molecular weight of the polymer, the higher the content of the polyoxyalkylene polymer having no unsaturated group in one molecule in the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, In addition, there is a problem that only a crosslinkable silicon-group-containing polyoxyalkylene polymer having a lower crosslink density can be obtained as the polymer has higher elongation properties. Since a polyoxyalkylene polymer having no unsaturated group in one molecule is polymerized using water or the like in a polymerization monomer as an initiator as described later, this problem occurs in the process of polymerizing the polymer. Appears noticeably.

[0004]

Means for Solving the Problems The present inventors have made intensive studies in view of the above circumstances, and as a result, have found that the content of a polyoxyalkylene polymer having no unsaturated group in one molecule is low in one molecule. A polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule is subjected to a hydrosilylation reaction in the presence of a hydrosilylation catalyst. The present inventors have found that a polymer having a high modulus at 100% elongation can be synthesized by performing a coupling reaction using a hydroxyl group of a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. The invention has been reached.

That is, the present invention has a number average molecular weight of 300
A polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in a molecule of 0 or more having a ratio of 85% or more to a polyoxyalkylene polymer having a hydrogen-silicon bond and a crosslinkable silicon group in a molecule; And a hydrosilylation reaction with a hydrosilylation yield of 75% or more based on the unsaturated group, and utilizing the hydroxyl group of a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule obtained. A method for producing a crosslinkable silicon group-containing polyoxyalkylene-based polymer, characterized in that a coupling reaction is carried out.

In a preferred embodiment, a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is coupled with a compound having two or more isocyanate groups in one molecule. A method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of the above.

In a further preferred embodiment, when coupling a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule with a compound having two or more isocyanate groups in one molecule, The present invention relates to the method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of the above, wherein a tin catalyst containing a sulfur atom is used.

[0008] In a further preferred embodiment, an aliphatic polyvalent isocyanate compound is used as the compound having two or more isocyanate groups in one molecule. The present invention relates to a method for producing a polyoxyalkylene-containing polymer.

In a further preferred embodiment, when a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is coupled with a compound having two or more isocyanate groups in one molecule, (A) Excess isocyanate groups are reacted with hydroxyl groups in a polyoxyalkylene polymer, and (b) excess isocyanate groups are coupled with a compound having two or more active hydrogens in one molecule. The present invention also relates to a method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer as described in any of the above items.

[0010] In a further preferred embodiment, the yield of the coupling reaction utilizing a hydroxyl group is 80% or more based on the hydroxyl group before the hydrosilylation reaction. The present invention relates to a method for producing a silicon group-containing polyoxyalkylene polymer.

In a further preferred embodiment, a polyoxyalkylene polymer having a proportion of 85% or more of a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is used as a double metal cyanide complex catalyst. The present invention relates to the method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of the above, which is a polyoxyalkylene polymer produced by using the same.

In a further preferred embodiment, a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule produced by using a double metal cyanide complex catalyst has a ratio of 85% or more. The present invention relates to the method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of the above, wherein the polymer contains a double metal cyanide complex catalyst.

In a further preferred embodiment, the double metal cyanide complex catalyst is a complex containing zinc hexacyanocobaltate, wherein the crosslinkable silicon group-containing polyoxyalkylene-based catalyst is any of the above. The present invention relates to a method for producing a polymer.

In a further preferred embodiment, a metal coordinating compound is added to a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, followed by heat treatment at 50 ° C. or more. A method for producing the crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of the above, which is characterized by the following.

In a further preferred embodiment, the metal coordinating compound is a compound selected from the group consisting of a compound having a carboxyl group, a chelating agent, and a compound having a phenolic hydroxyl group. The present invention relates to a method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of the above.

Here, the ratio in the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule in the polyoxyalkylene polymer is represented by the following formula (2). Here, V: the content (mol / g) of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule of the polymer W: only the hydroxyl group in one molecule of the polymer Content of polyoxyalkylene polymer (mol / g) X: Ratio of polyoxyalkylene polymer having unsaturated group and hydroxyl group in one molecule (mol%) Y: Having only hydroxyl group in one molecule Ratio of polyoxyalkylene polymer (mol%) Y = W / (W + V) (1) Accordingly, the ratio of polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is as follows: X = 100− Y (2) Here, the content (mol / g) W of the polyoxyalkylene polymer having only a hydroxyl group in one molecule in the polymer is represented by the hydroxyl equivalent (mol / g) and the unsaturated group equivalent of the polymer. (Mol /
g), W (mol / g) = (hydroxyl equivalent (mol / g) -unsaturated group equivalent (mol / g) of polymer) / 2. Further, the content of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule of the polymer (mol / mol)
g) V is V (mol / g) = unsaturated group equivalent (mol / g)
g). The unsaturated group equivalent is determined by a method for measuring the total degree of unsaturation of the polyether, iodine value titration, or the like, and the hydroxyl equivalent is determined by, for example, the hydroxyl value titration of the polyether.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The active hydrogen-containing compound which can be used as a polymerization initiator is not particularly limited as long as it has an unsaturated group and a hydroxyl group in one molecule. There is no particular limitation as long as it is an active hydrogen compound that can be used for a double metal cyanide complex catalyst described below. The hydroxyl group is preferably an alcoholic hydroxyl group, a phenolic hydroxyl group, or a carboxyl group, and more preferably an alcoholic hydroxyl group. Examples of the unsaturated group include an allyl group, a methallyl group, a vinyl group, and an isopropenyl group, and an allyl group is preferable. The ratio of the compound having no unsaturated group in one molecule contained in the compound having an unsaturated group and a hydroxyl group in one molecule used as an initiator is 10 mol as the value defined by the above formula (2). % Or less, more preferably 0 mol%. The ratio of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule in the polyoxyalkylene polymer of the present invention is defined by the above formula (2). When polymerizing a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, it is inevitable that a polyoxyalkylene polymer having only a hydroxyl group without having an unsaturated group in one molecule is mixed. This is because polymerization is started by using water contained in the polymerization monomer as an initiator. Further, a compound having no unsaturated group contained in an active hydrogen-containing compound that can be used as a polymerization initiator is also a cause. The proportion of the polyoxyalkylene polymer having no unsaturated group in the polyoxyalkylene polymer appears in the difference between the hydroxyl equivalent and the unsaturated group equivalent. Since a polyoxyalkylene polymer having no unsaturated group, that is, a polyoxyalkylene polymer having only a hydroxyl group, is not introduced with a crosslinkable silicon group, crosslinking of a polyoxyalkylene polymer containing a target crosslinkable silicon group is not performed. Low density,
Modulus decreases. In order to obtain a polymer having a crosslinkable silicon group at both ends, a coupling described below is used, but a polyoxyalkylene polymer having only a hydroxyl group acts as a chain extension of a polymer having a crosslinkable silicon group at both ends. And the rate of formation of a polymer having crosslinkable silicon groups at both ends is significantly reduced. For this reason, in order to obtain a polymer having a crosslinkable silicon group at both ends, the ratio of the unsaturated group and the hydroxyl-containing polyoxyalkylene polymer in one molecule of the usable polyoxyalkylene polymer is determined. Need to be higher. This ratio is at least 85%, preferably 90%.
% Or more.

Further, in order to secure sufficient elongation properties of a desired polymer having a crosslinkable silicon group at both ends, it is necessary to use a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule. The number average molecular weight needs to be 3000 or more, and preferably 4000 or more. Accordingly, a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is subjected to a hydrosilylation reaction with a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule,
The number average molecular weight of the crosslinkable silicon group-containing polyoxyalkylene polymer obtained by performing a coupling reaction using the hydroxyl group of the polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule obtained. Is 6,00
0 or more, more preferably 8000 or more.

In order to reduce the content of the polyoxyalkylene polymer having no unsaturated group in one molecule in the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, the amount of the polymer to be polymerized is reduced. To reduce the water contained in the epoxide, and when the active hydrogen compound containing an unsaturated group is used as a polymerization initiator, the activity not containing the unsaturated group contained in the active hydrogen compound containing the unsaturated group is used. Examples include, but are not limited to, reducing hydrogen compounds.

The compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule used in the present invention is not particularly limited, but a compound represented by the following general formula (3) is preferred. _{^{H- (Si (R 1 2-}} b) (X b) O) m Si (R 2 3-a) X a (3) ( wherein, R ¹ and R ² are the same or different 1 to 20 carbon atoms in the An alkyl group, an aryl group having 6 to 20 carbon atoms,
An aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ S
shows a triorganosiloxy group represented by Io-, R ¹
Or, when two or more R ² are present, they may be the same or different. Here, R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's 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. Also m
For b in number of _{^{-Si (R 1 2-b)}} (X b) O- groups, they may be may be the same or different. m represents an integer of 0 to 19. However, a + Σ
It satisfies b ≧ 1) 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,
Ketoximate group, amino group, amide group, acid amide group,
Examples include 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 crosslinkable group has one to three silicon atoms.
(A + Δb) is preferably 1 to 5. When two or more crosslinkable groups are present,
They may be the same or different.

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

The compound represented by the general formula (3) is preferably a compound represented by the following general formula (4) because it is easily available. _{^{H-Si (R 2 3-}} C) X a (4) ( wherein R ^2, X, a is the same .C represents 1, 2, 3 above) hydrogen in one molecule - the silicon-bonded crosslinkable As the compound (B) having a silicon group, specifically, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane, 1,1,3,3-tetramethyl-1- Halogenated silanes such as bromodisiloxane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, and trimethylsiloxydiethoxysilane; Acetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethyl Acyloxysilanes such as roxymethylacetoxysilane and trimethylsiloxydiacetoxysilane; bis (dimethylketoxime) methylsilane, bis (cyclohexylketoxime) methylsilane, bis (diethylketoxime) trimethylsiloxysilane, bis (methylethylketox) Mate) methyl silane, ketoxime silanes such as tris (acetoxy mate) silane; and alkenyloxy silanes such as methyl isopropenyloxy silane. Among them, methyldimethoxysilane,
Alkoxysilanes such as trimethoxysilane, methyldiethoxysilane, and triethoxysilane; halogenated silanes such as trichlorosilane and methyldichlorosilane are preferred, and methyldimethoxysilane and trimethoxysilane are particularly preferred. The halogen atom of the halogenated silanes is subjected to a hydrosilylation reaction to an unsaturated group, and then reacted with an active hydrogen compound such as a carboxylic acid, an oxime, an amide, or a hydroxyamine or an alkali metal enolate of a ketone by a known method. It may be converted to another hydrolyzable group.

The amount of the compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule is not particularly limited, but the amount added to the unsaturated group in the above-mentioned unsaturated group-containing polyoxyalkylene polymer is not limited. On the other hand, it is usually 0.5 to 3 equivalents,
Preferably 0.5 to 2 equivalents, more preferably 0.6 to
1.5 equivalents. An excess amount of a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule may be removed by devolatilization under reduced pressure after completion of the reaction.

The hydrosilylation catalyst that can be used in the hydrosilylation reaction of the present invention is not particularly limited, but includes platinum, rhodium, cobalt, palladium, and the like.
And a metal complex selected from Group VIII transition metal elements such as nickel. Among them, H ₂ PtCl ₆ · 6H2
O, platinum-vinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh ₃ ) ₃ , RhCl ₃ ,
Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ ,
_{AlCl 3, PdCl 2 · 2H2O,} NiCl 2, TiC
l _{4 and the} like are preferable, and from the viewpoint of hydrosilylation reactivity,
H ₂ PtCl ₆ · 6H2O, platinum - vinylsiloxane complexes, platinum - platinum metal-containing complexes such as olefin complexes are preferred, platinum - vinylsiloxane complex, a platinum - olefin complexes are particularly preferred. The term "platinum-vinylsiloxane complex" as used herein is a generic term for compounds in which a siloxane, polysiloxane, or cyclic siloxane is coordinated with a platinum atom and has a vinyl group in the molecule as a ligand. Specific examples of the ligand include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. Platinum-
Specific examples of the olefin ligand of the olefin complex include 1,5-hexadiene, 1,7-octadiene, 1,9
-Decadiene, 1,11-dodecadiene, 1,5-cyclooctadiene and the like. 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 and the like.

The amount of the hydrosilylation catalyst used is not particularly limited, but is based on 100 parts by weight of a polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule. In general, 0.000001 to 1 part by weight can be used as a metal, preferably 0.1 to 1 part by weight.
0000-0.1 parts by weight, more preferably 0.000
02 to 0.01 parts by weight, more preferably 0.00005
To 0.005 parts by weight, even more preferably 0.0001
~ 0.001. When the amount of the hydrosilylation catalyst is small, the hydrosilylation reaction may not proceed sufficiently. On the other hand, 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 that the polymer is colored.

In the production method of the present invention, the temperature at the time of the hydrosilylation reaction is not particularly limited.
0 ° C is preferable, and 20 ° C to 120 ° C is more preferable. If the temperature is lower than 0 ° C., the reaction rate may be low,
When the temperature exceeds ℃, a side reaction involving a hydroxyl group, a hydrogen-silicon bond or a crosslinkable silicon group may proceed.

In the present invention, when a coupling reaction is carried out using a hydroxyl group of a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group, a functional group capable of reacting with a hydroxyl group may be used as a coupling agent. The compound is not particularly limited as long as it has two or more compounds, and examples thereof include a polyvalent isocyanate compound, a polyvalent carboxylic acid compound, a polyvalent carboxylic anhydride, and a polyvalent carboxylic acid derivative. Even if the compound has only one functional group, a compound capable of reacting with and binding to two or more hydroxyl groups can also be used. Examples of such a compound include, but are not limited to, an aldehyde compound and a carbonate compound.

In the present invention, when a coupling reaction is carried out by utilizing a hydroxyl group of a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group, usable coupling agents include secondary agents such as acid, water and alcohol. Compounds having two or more isocyanate groups in one molecule because they do not produce organisms, do not require the use of a catalyst that may promote the condensation reaction of crosslinkable silicon groups, and are more readily available. It is preferable to use aliphatic polyisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate), and a polyisocyanate compound obtained by reacting trimethylolpropane with hexamethylene diisocyanate in terms of excellent weather resistance. Even better Arbitrariness. The amount of the coupling agent such as a compound having two or more isocyanate groups in one molecule used in the present invention is based on the amount of hydroxyl groups in the polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. On the other hand, it is preferably 0.5 to 3 equivalents, more preferably 0.8 to 2 equivalents, and particularly preferably 0.95 to 1.5 equivalents in terms of functional groups such as isocyanate groups and carboxyl groups. If the amount is less than 0.5 equivalent, the coupling yield is insufficient, so that the physical properties of the obtained crosslinkable silicon group-containing polyoxyalkylene polymer may be insufficient, and if it exceeds 3 equivalents, it is economically disadvantageous. There are cases. The coupling agents that can be used in the present invention may be used alone or in combination of two or more.

In the practice of the present invention, a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule is reacted with a coupling agent such as a compound having two or more isocyanate groups in one molecule. In this case, a catalyst may not be particularly used, but may be used for the purpose of improving the reaction rate or the reaction rate. For example, as a urethanization reaction catalyst that can be used when performing a coupling reaction using a polyvalent isocyanate compound, for example, Polyurethanes: Chemi
try and Technology, Part
I, Table 30, Chapter 4,
Saunders and Frisch, Inte
rscience Publishers, New
Examples include, but are not limited to, the catalysts listed in York, 1963. Examples of urethanization reaction catalysts that can be used in the case of performing a coupling reaction using a polyvalent isocyanate compound include tin octylate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl malate, dibutyl tin dibutyl malate, and dibutyl tin dilaurate. , 1,1,
3,3-tetrabutyl-1,3-dilauryloxycarbonyldistannoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis (o-phenylphenoxide), dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, Tin catalysts such as dibutyltin bisisononyl-3-mercaptopropionate, dibutyltin bisisooctylthioglycolate, dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin diversate are preferred because of their high activity. Further, it is preferable to use a catalyst having a low activity for the crosslinkable silicon group. For example, a tin catalyst containing a sulfur atom such as dibutyltin bisisononyl-3-mercaptopropionate or dibutyltin bisisooctylthioglycolate is particularly preferable. .

The method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer of the present invention comprises the steps of: preparing a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule; When coupling with a compound having an isocyanate group, (a) an excess amount of an isocyanate group is reacted with a hydroxyl group in the polyoxyalkylene-based polymer, and (b) an excess amount of the isocyanate group is added to one molecule. It is preferred to couple with a compound having one or more active hydrogens.

At the time of the above coupling, (a) an excess amount of isocyanate groups is reacted with the hydroxyl groups in the polyoxyalkylene-based polymer, for example, to compensate for the loss of isocyanate groups due to moisture in the air. Is preferred. In addition, the unreacted polyoxyalkylene-based polymer having an isocyanate group introduced at a terminal, which is not coupled with a compound having two or more isocyanate groups in one molecule, reduces the coupling rate. In addition, it is preferable to couple (b) excess isocyanate groups with a compound having two or more active hydrogens in one molecule.

The process for producing a crosslinkable silicon-group-containing polyoxyalkylene polymer of the present invention is characterized in that a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is combined with a hydrogen-silicon bond in one molecule. It is necessary that the hydrosilylation yield when a compound having a compound having a crosslinkable silicon group is subjected to a hydrosilylation reaction be 75% or more based on the unsaturated group. If the hydrosilylation yield is less than 75% based on the unsaturated group, the resulting cross-linkable silicon group-containing polyoxyalkylene polymer has insufficient mechanical properties.

In the method for producing a crosslinkable silicon-containing polyoxyalkylene polymer according to the present invention, the yield of the coupling reaction utilizing a hydroxyl group is preferably 80% or more based on the hydroxyl group before the hydrosilylation reaction. . If the yield of the above coupling reaction is less than 80% based on the hydroxyl group before the hydrosilylation reaction, it may be inconvenient in that the obtained crosslinkable silicon group-containing polyoxyalkylene polymer has insufficient mechanical properties. Because there is.

The polyoxyalkylene polymer containing a double metal cyanide complex catalyst according to the present invention and having an unsaturated group and a hydroxyl group in one molecule is prepared by using an active hydrogen compound having an unsaturated group as a polymerization initiator. By performing ring-opening polymerization of a monoepoxide containing no unsaturated group or a monoepoxide containing no unsaturated group and a monoepoxide containing an unsaturated group using the double metal cyanide complex described above as a catalyst, or Is obtained by, for example, ring-opening polymerization of a monoepoxide containing no unsaturated group and a monoepoxide containing an unsaturated group using the above-mentioned double metal cyanide complex as a catalyst, using an active hydrogen compound containing no as a polymerization initiator. However, the present invention is not limited to these.

As the double metal cyanide complex which can be used in the present invention, a complex containing zinc hexacyanocobaltate is preferable, and a dimethoxyethane coordination complex of zinc hexacyanocobaltate and a t-butanol coordination complex of zinc hexacyanocobaltate are preferable. Complexes, t-butanol and polyoxypropylene triol coordination complexes of zinc hexacyanocobaltate, and t-butanol and polyoxypropylene triol coordination complexes of zinc hexacyanocobaltate are more preferred. Further, at least 70% by weight of a substantially amorphous double metal cyanide complex is preferable, and at least 90% by weight of a substantially amorphous double metal cyanide complex is more preferable.

In the present invention, when a metal coordinating compound is added to a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, the method of addition is not particularly limited. May be added in the form of a solid dissolved in a solvent, or may be added by heating and melting to a temperature equal to or higher than the melting point of the metal coordinating compound. The metal coordinating compound may be dissolved by heating. Also, after adding the metal coordinating compound, before adding a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule, a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule. It may be heated. When heating, the temperature is preferably 50 ° C. or higher,
50-150 degreeC is more preferable, and 70-130 degreeC is still more preferable.

When the heating temperature is lower than 50 ° C., when the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule contains a double metal cyanide complex catalyst, the hydrosilylation reaction using the double metal cyanide complex catalyst is carried out. In some cases, when the temperature exceeds 150 ° C., the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is thermally degraded, which may be inconvenient.

The metal coordinating compound used in the present invention is a compound capable of coordinating with a metal ion or a metal atom, particularly a metal ion or a metal atom contained in a double metal cyanide complex. . As such a metal coordinating compound, a carboxyl group-containing compound, a chelating agent, a hydroxyl group-containing compound, and a compound having a phenolic hydroxyl group are preferable because of their high coordination ability. The carboxyl group-containing compound is not particularly limited as long as it has a carboxyl group or can generate a carboxyl group in the presence of an active hydrogen compound or a hydrogen-silicon group-containing compound. Examples thereof include carboxylic acids such as polycarboxylic acids having two or more, carboxylic anhydrides, and silylated carboxylic acids. Among these, carboxylic acids and carboxylic anhydrides are more preferred.

The amount of the metal coordinating compound added depends on the amount of the double metal cyanide complex catalyst in the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule. Although not limited, based on 100 parts by weight of the unsaturated group-containing polyoxyalkylene polymer containing the double metal cyanide complex catalyst, 0.00001 to
1 part by weight, preferably 0.0001 to 0.1 part by weight, more preferably 0.001 to 0.05 part by weight. If the amount of the metal coordinating compound is too small, the effect is hardly obtained, while if it is too large, the chemical and physical properties of the target polymer may be adversely affected by side reactions and the like.

The polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule produced by the production method of the present invention gives a crosslinked cured product by reacting with moisture or atmospheric moisture. Alternatively, they are useful as raw materials or raw material intermediates for industrial sealing materials, adhesives, coating materials, and the like.

[0043]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. (Comparative Example 1) In a glass reactor, a polyoxypropylene having an allyl group and a hydroxyl group in one molecule of an average molecular weight of 1,500 (Nippon Oil & Fats Co., PKA5014, 0.675 mm
ol-OH / g, 0.588 mmol-Allyl /
g, the proportion of polyoxypropylene having an allyl group and a hydroxyl group in one molecule in the polymer is 93% from the above formula (1).
), A xylene solution of platinum vinyl siloxane complex (5.7 ppm by weight of platinum), and 5.06 g of dimethoxymethylsilane (0.81 equivalent based on allyl groups in polypropylene) were sequentially added. The reaction was carried out at 80 ° C. for 2 hours and devolatilized under reduced pressure to obtain a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. The hydrosilylation yield determined by 1H-NMR was 78% (based on allyl groups), and the GPC measurement showed that the molecular weight distribution hardly changed before and after the hydrosilylation reaction. After cooling the reaction to room temperature under a nitrogen atmosphere, 5.68 g of hexamethylene diisocyanate
(68 mmol of isocyanate group; 0.
98 equivalents) and 20 mg (200 ppm) of dibutyltin bisoctylthioglycolate at room temperature.
For 7 hours. It was confirmed by IR analysis that there was no residual isocyanate group. 5 g of methanol was added.
The mixture was stirred for 5 hours and devolatilized under reduced pressure. The coupling yield by GPC analysis was 95%. Cured with a mixture of 3 parts by weight of tin octylate and 0.5 part by weight of laurylamine based on 100 parts by weight of the polyoxypropylene-based polymer having a crosslinkable silicon group and a urethane bond in one molecule thus obtained. Was. A JIS No. 3 dumbbell was punched out and the mechanical properties were measured. However, elongation required for modulus measurement at 100% elongation could not be obtained, and measurement could not be performed. In this example, the ratio of polyoxypropylene having an allyl group and a hydroxyl group in one molecule in the polymer was 93%.
%, But the number average molecular weight is as low as 1,500,
The extension required for modulus expression could not be obtained. (Production Example 1) Polyoxypropylene having an unsaturated group and a hydroxyl group in one molecule
Manufacture of a len-based polymer In a stainless steel pressure-resistant reactor, polyoxypropylene having an allyl group and a hydroxyl group in one molecule of an average molecular weight of 1,500 (Nippon Oil & Fats Co., PKA5014, 0.675 mmol)
1-OH / g, 0.588 mmol-Allyl / g)
1220.1 g and 0.68 g of zinc hexacyanocobaltate glyme complex (157 pp based on the finished amount after polymerization)
m) was charged and dehydrated by heating with toluene. 125.5 g of propylene oxide for catalyst activation was charged, and 100
The polymerization reaction was performed by heating to ° C. After the induction period, the temperature of the reaction solution rose rapidly, and then dropped. After confirming the drop in the reaction solution temperature, an additional 2983.4 g of propylene oxide was added dropwise over about 5 hours, and the internal temperature was maintained at 100 to 110 ° C. After completion of the dropwise addition, heating was further continued for 1 hour, and then a small amount of unreacted monomer was removed by devolatilization under reduced pressure. As a result, a polyoxypropylene polymer having about 160 ppm of zinc hexacyanocobaltate glyme complex and having an allyl group and a hydroxyl group in one molecule was obtained. The obtained polymer had an unsaturated group equivalent of 0.1683 mmol / g as determined by iodine titration, a hydroxyl group equivalent of 0.2249 mmol / g as determined by hydroxyl value titration, and a number average molecular weight of about 5,000. The proportion of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule in the obtained polymer was 86 mol% from the formula (1). (Comparative Example 2) Polyoxy having a crosslinkable silicon group and a hydroxyl group in one molecule
Production of Propylene Polymer A xylene solution of a platinum vinyl siloxane complex was added to 100 g of a polyoxypropylene polymer containing the zinc hexacyanocobaltate glyme complex obtained in Production Example 1 and containing an allyl group and a hydroxyl group in one molecule. (2.4p in platinum weight
pm) and 1.43 g of dimethoxymethylsilane (0.80 equivalents to allyl groups in polyoxypropylene) were added in order. The reaction was performed at 80 ° C. for 2 hours, and the mixture was devolatilized under reduced pressure to obtain a polyoxypropylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. ¹ H-NMR
Was 66% (based on allyl group). Poly with crosslinkable silicon group and urethane bond in one molecule
Production of oxypropylene-based polymer After the above reaction product was cooled to room temperature under a nitrogen atmosphere, 1.87 g of hexamethylene diisocyanate (22 mmol of isocyanate group; 0.99 equivalent to hydroxyl group), and dibutyltin bisoctyl thioglycolate. 4mg
(224 ppm) was added at room temperature and heated at 100 ° C. for 7 hours. It was confirmed by IR analysis that there was no residual isocyanate group. 5 g of methanol was added, the mixture was stirred for 0.5 hour, and devolatilized under reduced pressure. The coupling yield by GPC analysis was 95%. Cured with a mixture of 3 parts by weight of tin octylate and 0.5 part by weight of laurylamine based on 100 parts by weight of the polyoxypropylene-based polymer having a crosslinkable silicon group and a urethane bond in one molecule thus obtained. Was. A JIS No. 3 dumbbell was punched out and the mechanical properties were measured. Modulus at 100% elongation = 0.013 MPa
Met. In this example, in the production of the polyoxypropylene polymer, the ratio of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule was 95 mol%, but the hydrosilylation yield was 66%. Low, 100
% Elongation resulted in low modulus. (Example 1) Polyoxy having a crosslinkable silicon group and a hydroxyl group in one molecule
Production of Propylene-Based Polymer 101 g of succinic anhydride was added to 100 g of a polyoxypropylene-based polymer containing the zinc hexacyanocobaltate glyme complex obtained in Production Example 1 and containing an allyl group and a hydroxyl group in one molecule. 100 ° C /
After heating and dissolving for 0.5 hour, the mixture was cooled to 80 ° C., and a xylene solution of platinum vinylsiloxane complex (10.
1 ppm), 1.43 g of dimethoxymethylsilane (0.80 equivalent to allyl group in polyoxypropylene)
Were added in order. The reaction was performed at 80 ° C. for 2 hours, and the mixture was devolatilized under reduced pressure to obtain a polyoxypropylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. ¹ H-N
The hydrosilylation yield determined by MR was 77% (based on allyl groups). Poly with crosslinkable silicon group and urethane bond in one molecule
Production of oxypropylene-based polymer After the above reaction product was cooled to room temperature under a nitrogen atmosphere, 1.93 g of hexamethylene diisocyanate (23 mmol of isocyanate group; 1.02 equivalent to hydroxyl group), dibutyltin bisoctylthioglycolate. 0mg
(202 ppm) was added at room temperature and heated at 100 ° C. for 7 hours. It was confirmed by IR analysis that there was no residual isocyanate group. 5 g of methanol was added, the mixture was stirred for 0.5 hour, and devolatilized under reduced pressure. The coupling yield by GPC analysis was 97%. Cured with a mixture of 3 parts by weight of tin octylate and 0.5 part by weight of laurylamine based on 100 parts by weight of the polyoxypropylene-based polymer having a crosslinkable silicon group and a urethane bond in one molecule thus obtained. Was. A JIS No. 3 dumbbell was punched out and the mechanical properties were measured. Modulus at 100% elongation = 0.140 MPa
Met. In this example, in the production of the polyoxypropylene polymer, the proportion of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule was 85 mol% or more, and the hydrosilylation yield was higher than that of Comparative Example 1. High, 7
7 mol%. Due to this effect, a high modulus at 100% elongation was obtained. (Comparative Example 3) Polyoxypropylene having an unsaturated group and a hydroxyl group in one molecule
Manufacture of a len-based polymer In a stainless steel pressure-resistant reactor, polyoxypropylene having an allyl group and a hydroxyl group in one molecule of an average molecular weight of 1,500 (Nippon Oil & Fats Co., PKA5014, 0.706 mmol)
1-OH / g, 0.591 mmol-Allyl / g)
1230.0 g and 0.35 g of zinc hexacyanocobaltate glyme complex (80 ppm based on the finished amount after polymerization)
And dehydrated by heating with toluene. A polymerization reaction was carried out by charging 120.0 g of propylene oxide for catalyst activation and heating to 100 ° C. After the induction period, the temperature of the reaction solution rose rapidly, and then dropped. After confirming a drop in the reaction solution temperature, an additional 3010 g of propylene oxide was added dropwise over about 5 hours, and the internal temperature was adjusted to 100 to 1
It was kept at 10 ° C. After dropping, continue heating for another hour,
Subsequently, a trace amount of unreacted monomer was removed by devolatilization under reduced pressure. As a result, a polyoxypropylene polymer having about 80 ppm of zinc hexacyanocobaltate glyme complex and having an allyl group and a hydroxyl group in one molecule was obtained. The obtained polymer had an unsaturated group equivalent of 0.1695 mmol / g as determined by iodine titration, a hydroxyl group equivalent of 0.2412 mmol / g as determined by hydroxyl value titration, and a number average molecular weight of about 5,000. The ratio of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule in the obtained polymer was 83 mol% from the formula (1). Polyoxy with crosslinkable silicon and hydroxyl groups in one molecule
Production of propylene-based polymer 100 g of polyoxypropylene-based polymer containing the zinc hexacyanocobaltate glyme complex obtained above and containing an allyl group and a hydroxyl group in one molecule was added with 100 ppm of succinic anhydride, and nitrogen was added. 100 ° C / 0.5 in atmosphere
After heating and dissolving for an hour, the mixture was cooled to 80 ° C., and a xylene solution of platinum vinyl siloxane complex (10.0 pp by weight of platinum)
m) and 1.48 g of dimethoxymethylsilane (0.80 equivalents based on the allyl group in polyoxypropylene) were sequentially added. The reaction was performed at 80 ° C. for 2 hours, and the mixture was devolatilized under reduced pressure to obtain a polyoxypropylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. ^The hydrosilylation yield determined from ¹ H-NMR is 76% (based on allyl group).
In the GPC measurement, the molecular weight distribution hardly changed before and after the hydrosilylation reaction. Poly with crosslinkable silicon group and urethane bond in one molecule
Production of oxypropylene-based polymer After the above reaction product was cooled to room temperature in a nitrogen atmosphere, 2.09 g of hexamethylene diisocyanate (25 mmol of isocyanate group; 1.03 equivalent to hydroxyl group), and dibutyltin bisoctylthioglycolate 20. 1mg
(201 ppm) was added at room temperature and heated at 100 ° C. for 7 hours. It was confirmed by IR analysis that there was no residual isocyanate group. 5 g of methanol was added, the mixture was stirred for 0.5 hour, and devolatilized under reduced pressure. The coupling reaction yield by GPC analysis was 96%. Cured with a mixture of 3 parts by weight of tin octylate and 0.5 part by weight of laurylamine based on 100 parts by weight of the polyoxypropylene-based polymer having a crosslinkable silicon group and a urethane bond in one molecule thus obtained. Was. A JIS No. 3 dumbbell was punched out and the mechanical properties were measured. Modulus at 100% elongation = 0.064M
Pa. In this comparative example, the hydrosilylation yield was 7
6% and 75% or more, but sufficient 100% elongation because the ratio of the polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is 83 mol% in the production of the polyoxypropylene polymer. No polymer with a time modulus was obtained. (Example 2) Polyoxypropylene having an unsaturated group and a hydroxyl group in one molecule
Manufacture of a len-based polymer In a stainless steel pressure-resistant reactor, a polyoxypropylene having an allyl group and a hydroxyl group in one molecule of an average molecular weight of 1,500 (Nippon Oil & Fats Co., Ltd.
1-OH / g, 0.591 mmol-Allyl / g)
1564 g and 0.4 g of zinc hexacyanocobaltate glyme complex (80 ppm based on the finished amount after polymerization) were charged, and the mixture was dehydrated by heating with toluene. The propylene oxide to be used was charged into a stainless steel sealed container filled with nitrogen without opening the reagent bottle, and 192 g of propylene oxide for catalyst activation was charged from the sealed container into a stainless steel pressure-resistant reactor. The polymerization reaction was performed by heating to 100 ° C. After the induction period, the temperature of the reaction solution rose rapidly, and then dropped. After confirming a drop in the reaction solution temperature, an additional 3243 g of propylene oxide was dropped from the above-mentioned closed vessel over about 5 hours, and the internal temperature was lowered to 100 to 1 hour.
It was kept at 10 ° C. After dropping, continue heating for another hour,
Subsequently, a trace amount of unreacted monomer was removed by devolatilization under reduced pressure. As a result, a polyoxypropylene polymer having about 80 ppm of zinc hexacyanocobaltate glyme complex and having an allyl group and a hydroxyl group in one molecule was obtained. The obtained polymer had an unsaturated group equivalent of 0.192 mmol / g as determined by iodine titration, a hydroxyl equivalent of 0.230 mmol / g as determined by hydroxyl value titration, and a number average molecular weight of about 5,000. According to the formula (1), the proportion of the polyoxypropylene-based polymer having an allyl group and a hydroxyl group in one molecule in the polymer was 91 mol%. By charging propylene oxide to the reactor without opening it, the production of a polyalkylene polymer having hydroxyl groups at both terminals using water as an initiator due to moisture absorption is suppressed, and the polyalkylene polymer of Production Example 1 and Comparative Example 2 is suppressed. The proportion of the polyoxypropylene polymer having an allyl group and a hydroxyl group in one molecule of the polymer is higher than that of the polymer. Polyoxy with crosslinkable silicon and hydroxyl groups in one molecule
Manufacture of propylene-based polymer 100 g of polyoxypropylene-based polymer containing the zinc hexacyanocobaltate glyme complex obtained above and containing an allyl group and a hydroxyl group in one molecule was added with 104 ppm of succinic anhydride, and nitrogen was added. 100 ° C / 0.5 in atmosphere
After heating and dissolving for a period of time, the mixture was cooled to 80 ° C., and a xylene solution of platinum vinyl siloxane complex (10 pp by weight of platinum)
m) and 1.70 g of dimethoxymethylsilane (0.83 equivalents to allyl groups in polyoxypropylene) were added in order. The reaction was performed at 80 ° C. for 2 hours, and the mixture was devolatilized under reduced pressure to obtain a polyoxypropylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. ^The hydrosilylation yield determined from ¹ H-NMR is 77% (based on allyl group).
In the GPC measurement, the molecular weight distribution hardly changed before and after the hydrosilylation reaction. Poly with crosslinkable silicon group and urethane bond in one molecule
Production of Oxypropylene Polymer After cooling the above reaction product to room temperature in a nitrogen atmosphere, 1.86 g of hexamethylene diisocyanate (22 mmol of isocyanate group; 0.96 equivalent to hydroxyl group), and dibutyltin bisoctylthioglycolate. 0mg
(100 ppm) was added at room temperature and heated at 100 ° C. for 6 hours. It was confirmed by IR analysis that there was no remaining isocyanate group. The coupling yield was 97% by GPC analysis. 5 g of methanol was added, the mixture was stirred for 0.5 hour, and devolatilized under reduced pressure. Cured with a mixture of 3 parts by weight of tin octylate and 0.5 part by weight of laurylamine based on 100 parts by weight of the polyoxypropylene-based polymer having a crosslinkable silicon group and a urethane bond in one molecule thus obtained. Was. A JIS No. 3 dumbbell was punched out and the mechanical properties were measured. Modulus at 100% elongation = 0.184M
Pa, tensile strength at break was 0.290 MPa, and elongation at break was 109%. In this example, a polyoxyalkylene polymer in which the proportion of a polyoxypropylene polymer having an unsaturated group and a hydroxyl group in one molecule of the polymer was 91 mol% was used. Due to this effect, a polymer having a modulus at 100% elongation = 0.184 MPa was obtained.

[0044]

According to the present invention, a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule is subjected to a coupling reaction utilizing a hydroxyl group,
A method for producing a polymer having a high modulus at 100% elongation can be provided.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazumi Harada 5-1-1 Torigai Nishi, Settsu-shi, Osaka Kanagawa Electric Chemical Industry Co., Ltd. 1-8 Kanebuchi Kagaku Kogyo Kogyo Kogyo Kogyo Kogyo Co., Ltd. F-term (reference) 4J005 AA04 BB02 BD08 4J034 BA08 CA01 CA04 CB02 CB03 DA01 DB03 DM08 DM09 DM13 FA01 FB01 FE07 GA51 GA72 GA75 HA01 HA06 HA07 HC01 HC02 HC03 HC11 HC22 HC46 HC52 HC61 HC63 HC64 HC66 HC67 HC71 HC73 JA42 KA01 KC17 KD21 KE02 QA02 QA05 QB15 RA08 RA10

Claims (11)

[Claims] 1. A polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in a molecule having a number average molecular weight of 3,000 or more and a polyoxyalkylene polymer having a ratio of 85% or more in one molecule. A compound having a hydrogen-silicon bond and a crosslinkable silicon group is subjected to a hydrosilylation reaction with a hydrosilylation yield of 75% or more based on the unsaturated group, and the resulting polyoxysiloxane having a crosslinkable silicon group and a hydroxyl group in one molecule. A method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer, wherein the coupling reaction is carried out using a hydroxyl group of the alkylene polymer. 2. A polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is coupled with a compound having two or more isocyanate groups in one molecule. 2. The method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to 1. 3. When a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is coupled with a compound having two or more isocyanate groups in one molecule, a sulfur atom is contained. The method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to claim 2, wherein a tin catalyst is used. 4. The crosslinkable silicon group-containing polyoxyalkylene compound according to claim 2, wherein an aliphatic polyvalent isocyanate compound is used as the compound having two or more isocyanate groups in one molecule. A method for producing a polymer. 5. A method of coupling a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule with a compound having two or more isocyanate groups in one molecule, wherein (a) Reacting an excess amount of isocyanate groups with respect to the hydroxyl groups in the alkylene polymer,
5. The crosslinkable silicon-group-containing polyoxyalkylene polymer according to claim 2, wherein (b) excess isocyanate groups are coupled with a compound having two or more active hydrogens in one molecule. Manufacturing method of coalescence. 6. The crosslinkable silicon group-containing compound according to claim 1, wherein the yield of the coupling reaction using a hydroxyl group is 80% or more based on the hydroxyl group before the hydrosilylation reaction. A method for producing a polyoxyalkylene polymer. 7. A polyoxyalkylene polymer having a proportion of 85% or more of a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is produced using a double metal cyanide complex catalyst. The method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of claims 1 to 6, which is a polyoxyalkylene polymer. 8. A polyoxyalkylene polymer having a ratio of a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule of not less than 85% in one molecule produced by using a double metal cyanide complex catalyst, The method for producing a crosslinkable silicon-group-containing polyoxyalkylene polymer according to any one of claims 1 to 7, which comprises a double metal cyanide complex catalyst. 9. The crosslinkable silicon-group-containing polyoxyalkylene polymer according to claim 1, wherein the double metal cyanide complex catalyst is a complex containing zinc hexacyanocobaltate. Production method. 10. A polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule, a metal coordinating compound is added, and then a heat treatment at 50 ° C. or more is performed. Item 10. The method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to any one of Items 1 to 9. 11. The method according to claim 1, wherein the metal coordinating compound is a compound selected from the group consisting of a compound having a carboxyl group, a chelating agent, and a compound having a phenolic hydroxyl group. The method for producing a crosslinkable silicon group-containing polyoxyalkylene polymer according to the above.