JP2001294659A - Method for producing crosslinkable silicon group- containing polyoxyalkylene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyoxyalkylene-based polymer having crosslinkable silicon groups and hydroxyl groups in one molecule from a polyoxyalkylene- based polymer containing a composite metal cyanide complex catalyst and having unsaturated groups and hydroxyl groups in one molecule without removing the composite metal cyanide complex catalyst. SOLUTION: A carboxylic acid compound is added to the polyoxyalkylene- based polymer containing the composite metal cyanide complex catalyst and having the unsaturated groups and hydroxyl groups in one molecule and then subjected to a hydrosilylating reaction with a compound having hydrogen-silicon bonds and crosslinkable silicon groups in one molecule in the presence of a hydrosilylating catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a crosslinkable silicon-containing polyoxyalkylene polymer. Specifically, a polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule is added to one molecule without removing the double metal cyanide complex catalyst. The present invention relates to a method for producing a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule by subjecting a compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group to a hydrosilylation 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. Such a polyoxyalkylene polymer having a crosslinkable silicon group is disclosed in JP-A-50-15.
As exemplified in JP-A-6599, JP-A-52-73998, JP-A-3-72527, etc., the terminal hydroxyl group of a polyoxyalkylene-based polymer is mainly used to make it impossible to form a (meth) allyl group or the like. After producing a polyoxyalkylene polymer having an unsaturated group at the terminal by introducing a saturated group, the compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule is hydrosilyl-modified. It is manufactured by

[0003]

However, these production methods involve a process for producing a polyoxyalkylene polymer having a hydroxyl group, a process for producing a polyoxyalkylene polymer having an unsaturated group, and a process for producing a crosslinkable silicon group. At least three steps of the production process of the polyoxyalkylene polymer are required, and a purification process for removing by-products or impurities such as salts after the production of the polyoxyalkylene polymer having an unsaturated group. Is often required,
There is a problem that the manufacturing process is long and complicated.

As a method for producing a polyoxyalkylene polymer having a crosslinkable silicon group which can reduce by-products and shorten the production process, for example, ring-opening polymerization of a monoepoxide using a double metal cyanide complex catalyst. In this case, after polymerizing a monoepoxide having no unsaturated group, a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule is produced by introducing a monoepoxide having an unsaturated group, and this unsaturated A method in which a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule per group is subjected to a hydrosilylation reaction is disclosed in, for example, JP-A-3-79627.

According to this production method, by-products such as salts are not generated when the unsaturated group is introduced, but the double metal cyanide complex catalyst used in ring-opening polymerization of the monoepoxide is contained in the polyoxyalkylene polymer. Will remain.

The double metal cyanide complex catalyst used in the production of the polyoxyalkylene polymer is usually purified and removed, and a number of purification methods have been studied as described below.

[0007] This double metal cyanide complex catalyst is used for reacting an unsaturated group in a polyoxyalkylene polymer (A) having an unsaturated group and a hydroxyl group in one molecule with hydrogen-in one molecule.
Inhibits the hydrosilylation reaction of the compound (B) having a silicon bond and a crosslinkable silicon group. For this reason, the hydrosilylation reaction is carried out without removing the double metal cyanide complex catalyst from the polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule. However, there is a problem that the introduction rate of the crosslinkable silicon group is not improved or the viscosity is increased as compared with the amount of the compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule.

However, this publication does not disclose any problem or solution when introducing a crosslinkable silicon group without removing the double metal cyanide complex catalyst from the polyoxyalkylene polymer. In the examples, only those from which the double metal cyanide complex catalyst is removed are disclosed.

Further, a polyoxyalkylene polymer (A) having an unsaturated group and a hydroxyl group in one molecule produced by using a double metal cyanide complex catalyst, and a hydrogen-silicon bond and a crosslinkable silicon group in one molecule A method for producing a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule by reacting a compound (B) having
No. -125176. However, since this publication also does not disclose actively removing the double metal cyanide complex catalyst, it contains a double metal cyanide complex catalyst and has a polyoxyalkylene having an unsaturated group and a hydroxyl group in one molecule. A polymer (A) is reacted with a compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule to obtain a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule. It does not disclose the manufacture of the union.

As a method for removing the double metal cyanide complex catalyst, methods such as filtration and water washing are known. In the filtration method, a polyoxyalkylene polymer containing a double metal cyanide complex catalyst is heat-treated to deactivate the catalyst, and then a crystallization agent, an inorganic adsorbent, and an additive having an effect of coagulating the metal. After the treatment, if necessary, filtration is performed to remove the inactivated double metal cyanide complex catalyst. For example, a method in which a double metal cyanide complex catalyst is deactivated with an alkali metal or an alkali metal alcoholate, and then treated with an acid pyrophosphate in the presence of water to remove a catalyst component and a treating agent component (Japanese Unexamined Patent Publication No. No. 88823), a method of adding a mineral acid, and then adding an acid adsorbent to adsorb excess mineral acid, followed by filtration (JP-A-56-45923). There is also known a method of removing a residual metal by bringing it into contact with an ion exchange resin (JP-A-6-179747).

On the other hand, in the water washing method, a polyoxyalkylene polymer containing a double metal cyanide complex catalyst is subjected to heat treatment, acid or alkali treatment to deactivate the catalyst, and then a solvent is added to reduce the viscosity of the system. After lowering, water is added and vigorously stirred to remove the double metal cyanide complex catalyst by transferring it from the organic phase to the aqueous phase.

[0012] However, the filtration method requires a step of regenerating the used inorganic adsorbent, and the adsorbent having reduced adsorption capacity must be discarded as industrial waste. Also,
Since the double metal cyanide complex catalyst remaining in the polyoxyalkylene polymer is not sufficiently removed only by filtration or contact with an ion exchange resin, it is necessary to add various treating agents. If this additive is water soluble, after filtration,
It needs to be dehydrated. If the polymer has a high viscosity, the ability of filtration, ion exchange treatment and the like is reduced, so that it may be necessary to add a solvent. On the other hand, in the water washing method, a large amount of wastewater containing the double metal cyanide complex catalyst is generated, and since a solvent is used to lower the viscosity, the polymer after the double metal cyanide complex catalyst is removed from the polymer. The solvent needs to be removed. In addition, when the emulsifying component in the polymer is large, an emulsifying phase is formed between the organic phase and the aqueous phase, and the separability between the organic phase containing the polymer and the aqueous phase to which the metal has been transferred is significantly reduced. And other problems.
In any case, the step of removing the double metal cyanide complex catalyst from the polyoxyalkylene polymer requires complicated treatment, and has problems such as generation of wastewater and waste.

The process of removing the double metal cyanide complex catalyst from the polyoxyalkylene polymer as described above involves a complicated process and has a problem that waste and waste water are generated. Therefore, from a polyoxyalkylene polymer having an unsaturated group containing a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a crosslinkable silicon group is produced without removing the double metal cyanide complex catalyst. The development of a method was desired.

[0014]

Means for Solving the Problems As a result of intensive studies, the present inventors have obtained a polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule. By adding the carboxylic acid compound, the compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule can be subjected to a hydrosilylation reaction in the presence of a hydrosilylation catalyst. They have found that a polyoxyalkylene polymer having a hydroxyl group and a hydroxyl group can be produced, and have completed the present invention.

That is, the present invention relates to a polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule, after adding a carboxylic acid compound, A compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in a molecule is subjected to a hydrosilylation reaction in the presence of a hydrosilylation catalyst, wherein the polyoxy group has a crosslinkable silicon group and a hydroxyl group in one molecule. The present invention relates to a method for producing an alkylene polymer.

A preferred embodiment relates to the above-mentioned production method, wherein the carboxylic acid compound is at least one selected from the group consisting of carboxylic acids and carboxylic anhydrides.

In a further preferred embodiment, a carboxylic acid compound is added to a polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule. The method according to any one of the above, wherein a heat treatment at 50 ° C. or higher is performed.

As a further preferred embodiment, the present invention relates to any one of the above-mentioned production methods, wherein the double metal cyanide complex is a complex containing zinc hexacyanocobaltate.

[0019] In a further preferred embodiment, the present invention relates to the above-mentioned production method, wherein the hydrosilylation catalyst is a platinum metal-containing complex.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Compound metal usable in the present invention
Genus cyanide complexes are disclosed in U.S. Pat. No. 3,278,457;
U.S. Pat. No. 3,278,458, U.S. Pat.
No. 9, U.S. Pat. No. 3,427,256, U.S. Pat.
No. 427334, U.S. Pat. No. 3,427,335,
U.S. Pat. No. 3,829,505, U.S. Pat.
No. 9, U.S. Pat. No. 3,941,849, U.S. Pat.
355188, U.S. Pat. No. 4,472,560,
U.S. Pat. No. 4,721,818, U.S. Pat.
4, U.S. Pat. No. 5,158,922,
No. 145123, JP-A-7-196778,
JP-A-8-31171, JP-A-8-10474
No. 1, JP-A-9-59373, WO9740
No. 086, WO9723544, Macro
Molecular Synthesis, Vol. 5, page 9, 1
974 and is represented by the following general formula (1).
You. M_p｛M ’[(CN)_q(Y)_r]_s｝_t・ Y (R) ・ z (H_TwoO) (1) (where M is Zn (II), Fe (II), Fe (II)
I), Co (II), Ni (II), Al (III),
Sr (II), Mn (II), Cr (II), Cu (I
I), Sn (II), Pb (II), Mo (IV), M
a group consisting of o (VI), W (IV) and W (VI)
M ′ is Fe (II), Fe (I)
II), Co (II), Co (III), Cr (I
I), Cr (III), Mn (II), Mn (II
I), Ni (II), V (IV) and V (V).
Y is Cl, Br, I, O
H, NO, C _TwoO_Four , SO_Four, CNS, CNO, NCO,
Selected from the group consisting of NCS, where R is keto
, Ethers, polyethers, aldehydes, esters,
Organic selected from the group consisting of alcohol or amide
Is a ligand. M, M ', Y and R are one kind
Or two or more types. p, q, r, s
And t are positive numbers depending on the valence and coordination number of the metal
And y and z vary depending on the coordination number of the metal or drying conditions.
Is a positive number. M in the general formula (1) is preferably Zn (II),
M 'is Fe (II), Fe (III), Co (II),
Co (III) is preferred. Ate as an organic ligand
, Polyether and alcohol are preferred, and dimethoxy is preferred.
Ethane, diethylene glycol dimethyl ether, poly
Oxypropylene diol, polyoxypropylene tri
All, tertiary hydroxyl-containing polyoxypropylene
Riol, t-butanol, isopropyl alcohol
Particularly preferred.

As the double metal cyanide complex, a complex containing zinc hexacyanocobaltate is preferable, a dimethoxyethane coordination complex of zinc hexacyanocobaltate, a t-butanol coordination complex of zinc hexacyanocobaltate,
More preferred are t-butanol and polyoxypropylene diol coordination complexes of zinc hexacyanocobaltate and t-butanol and polyoxypropylene triol coordination complexes of zinc hexacyanocobaltate. 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.

The polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule according to the present invention initiates polymerization of an active hydrogen compound containing an unsaturated group. As an agent, a 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 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 unsaturated group as a polymerization initiator. Etc., but is not limited thereto.

The molecular weight of the polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst which can be used in the present invention and having an unsaturated group and a hydroxyl group in one molecule is not particularly limited. In view of the feature of the double metal cyanide complex catalyst that a polyoxyalkylene polymer having a molecular weight can be produced, 4,000 to 50,000 is preferable, and 4,000 to 20,000 is more preferable.

The smaller the amount of the double metal cyanide complex catalyst contained in the polyoxyalkylene polymer (A) having an unsaturated group and a hydroxyl group in one molecule, the smaller the amount of the carboxylic acid compound added. Although it is preferable because it is possible, it depends on the catalytic activity of a double metal cyanide complex necessary for producing a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one molecule. The amount of the polyoxyalkylene polymer generally has an unsaturated group and a hydroxyl group in one molecule.
The amount is 0.00001 to 15 parts by weight, preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.1 part by weight, and even more preferably 0.01 part by weight with respect to 0 part by weight.
02 to 0.05 parts by weight.

The active hydrogen-containing compound that can be used as the polymerization initiator is not particularly limited as long as it is an active hydrogen compound that can be used for a double metal cyanide complex catalyst, but is not limited to alcoholic hydroxyl groups, phenolic hydroxyl groups, and carboxylic acid groups. Is preferable, and a compound containing an alcoholic hydroxyl group is more preferable. The compound having an alcoholic hydroxyl group is not particularly limited, but includes allyl alcohol, methallyl alcohol, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, and ethylene oxide and / or propylene thereof. A compound having an unsaturated group and an alcoholic hydroxyl group in one molecule such as an oxide adduct is preferable. The molecular weight of these adducts of ethylene oxide and / or propylene oxide is not particularly limited as long as the molecular weight is lower than that of a polyoxyalkylene polymer having an unsaturated group and a hydroxyl group in one target molecule. Allyl alcohol, propylene oxide adducts of allyl alcohol, methallyl alcohol and propylene oxide adducts of methallyl allyl alcohol are more preferred, and allyl alcohol and propylene oxide adducts of allyl alcohol are even more preferred.

Examples of the polyhydric alcohol having no unsaturated group include propylene glycol, dipropylene glycol,
Low molecular weight polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol; adducts of these low molecular weight polyhydric alcohols with propylene oxide; polyoxypropylene glycols, polyoxypropylene triols and polyoxypropylene tetraols; Polyether polyols having a lower molecular weight than oxyalkylene polymers; hydroxyl-terminated hydrocarbon compounds such as hydroxyl-terminated polybutadiene, hydrogen-terminated hydrogenated polybutadiene; alcoholic hydroxyl-terminated silicone compounds such as alcoholic hydroxyl-terminated polydimethylsiloxane; And water is also classified as a polyhydric alcohol, but these can also be used.

The monoepoxide to be subjected to ring-opening polymerization using a double metal cyanide complex catalyst is not particularly limited, and is unsaturated such as propylene oxide, 1,2-butene oxide, 2,3-butene oxide, epichlorohydrin, and styrene oxide. Monoepoxide having no group, (meth) allyl glycidyl ether, glycidyl (meth) acrylate,
Monoepoxides having an unsaturated group such as butadiene monoxide and cyclopentadiene monoepoxide are exemplified. It is preferred that 90 mol% or more of the total monoepoxide is propylene oxide.

The carboxylic acid compound that can be used in the present invention 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 compound containing a hydrogen-silicon bond. , Monocarboxylic acid and carboxyl group
Carboxylic acids such as polycarboxylic acids having at least one carboxylic acid, carboxylic acid anhydrides, carboxylic acid silylated products, and the like. Among these, carboxylic acids and carboxylic anhydrides are more preferred. Examples of the monocarboxylic acid include 2-ethylhexanoic acid, salicylic acid, stearic acid, glycolic acid, lactic acid, gallic acid, cinnamic acid, glycine, lactic acid, tiglic acid, asparagine, etc., and monomethyl succinate, monoethyl succinate, and maleic acid. Examples thereof include partial esters of polycarboxylic acids described below, such as monomethyl acid and monoethyl maleate. Polycarboxylic acids include succinic acid, phthalic acid, malonic acid, malic acid, glutamic acid, itaconic acid, maleic acid, adipic acid, aspartic acid, citric acid, tartaric acid, sebacic acid, thiodipropionic acid, thiomalic acid, iminodiacetic acid Dicarboxylic acid having two carboxyl groups such as isophthalic acid, 2-carboxyphenylacetic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, oxalic acid, glutaric acid, benzenetricarboxylic acid, ethylenediamine Examples thereof include carboxylic acids having three or more carboxyl groups such as acetic acid. Examples of the carboxylic anhydride include succinic anhydride, phthalic anhydride, itaconic anhydride, maleic anhydride, and glutaric anhydride.

The amount of the carboxylic acid 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 of (A). Although not particularly limited, 0.00100 parts by weight of the unsaturated group-containing polyoxyalkylene polymer containing the double metal cyanide complex catalyst,
001 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 carboxylic acid 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 method of adding the carboxylic acid compound to the polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule is not particularly limited. If it is a solid, it may be added by dissolving it in a solvent, or may be added by heating and melting to a temperature higher than the melting point of the carboxylic acid compound. The union may be heated to dissolve the carboxylic acid compound. Further, after adding the carboxylic acid compound, before adding the compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule,
The polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule may be heated. 50 to 15 for heating
0 ° C is preferred, and 70 to 130 ° C is more preferred.

If the heating temperature is lower than 50 ° C., the inhibition of the hydrosilylation reaction by the double metal cyanide complex catalyst may not be sufficiently suppressed. If the heating temperature is higher than 150 ° C., the unsaturated group and the hydroxyl group in one molecule may not be obtained. In some cases, the polyoxyalkylene-based polymer (A) having a thermal degradation may be inconvenient.

The compound (B) 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 formula (2) is preferred. _{^{H- (Si (R 1 2-}} b) (X b) O) m Si (R 2 3-a) X a (2) ( 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.
It may be about individual.

The compound represented by the general formula (2) is preferably a compound represented by the following general formula (3) because it is easily available. _{^{H-Si (R 2 3-}} a) X a (3) ( wherein R2, X, a are as defined above.) Hydrogen in one molecule - Specific examples of the compound having silicon-bonded and a crosslinkable silicon group (B) Specifically, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane, and 1,1,3,3-tetramethyl-1-bromodisiloxane; Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, trimethylsiloxydiethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxy Silane, trimethylsiloxymethylaceto Acyloxysilanes such as silane and trimethylsiloxydiacetoxysilane; bis (dimethylketoxime) methylsilane, bis (cyclohexylketoxime) methylsilane, bis (diethylketoxime) trimethylsiloxysilane, bis (methylethylketoxime) methylsilane And alkenyloxysilanes such as methylisopropenyloxysilane, and the like. 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 which can be used in the present invention is not particularly limited, but may be selected from VI, such as platinum, rhodium, cobalt, palladium and nickel.
A metal complex selected from Group II transition metal elements and the like can be used. Among them, H ₂ PtCl ₆ · 6H2O, platinum - vinylsiloxane complex, a platinum - olefin complexes, Pt metal, Rh
Cl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , Ru
Cl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂
· 2H2O, NiCl _2, TiCl ₄ and the like are preferable, from the viewpoint of reactivity of the hydrosilylation, H ₂ PtCl ₆ · 6H2
Platinum metal-containing complexes such as O, platinum-vinylsiloxane complex, and platinum-olefin complex are preferred, and platinum-vinylsiloxane complex and platinum-olefin complex 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 ligands include:
Examples thereof include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. Specific examples of the olefin ligand of the platinum-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, it is essentially unnecessary to use a solvent, but a solvent is used for the purpose of dissolving the substrate and for controlling the temperature of the reaction system and facilitating the addition of the catalyst component. Can be. Suitable solvents for this purpose include, for example, saturated or unsaturated hydrocarbon compounds such as hexane, cyclohexane, heptane, octane, dodecane, benzene, toluene, xylene, dodecylbenzene; chloroform, methylene chloride, chlorobenzene, Halogenated hydrocarbon compounds such as ortho-dichlorobenzene; ethers such as ethyl ether, tetrahydrofuran, and ethylene glycol dimethyl ether; Further, those which can be used as a plasticizer of a polyoxyalkylene polymer such as phthalic acid esters and polyethers can also be used as a reaction solvent.

According to the present invention, a polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule is added to a carboxylic acid compound, and then added to one molecule. A compound (B) having a hydrogen-silicon bond and a crosslinkable silicon group is subjected to a hydrosilylation reaction in the presence of a hydrosilylation catalyst, and a polyoxyalkylene-based polymer containing a crosslinkable silicon group and a hydroxyl group in one molecule. This is a method for producing a coalesced product, and the crosslinkable silicon group-containing polyoxyalkylene polymer produced by the above production method may be subjected to filtration or the like as it is or after treatment with an additive.

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. Reference Example 1 In an autoclave, 0.56 g of a zinc hexacyanocobaltate glyme complex as an epoxide polymerization catalyst, and a polyoxypropylene-based polymer having an unsaturated group and a hydroxyl group in one molecule of an average molecular weight of 1500 as a polymerization initiator (NOF Corporation) Unisafe PKA-5014 0.676m
(mol-OH / g) 2016 g and propylene oxide 210 g for catalyst activation were charged and heated to 100 ° C. to carry out a polymerization reaction. After the induction period,
The reaction temperature rose rapidly and then fell. After confirming the drop in the reaction solution temperature, additional propylene oxide 476 was added.
0 g was dropped over about 5 hours, and the internal temperature was 100-110 ° C.
Kept. After the completion of dropping, polymerization was carried out for 1 hour, and then unreacted monomers were recovered by devolatilization under reduced pressure.
There were few recoveries. This allows about 8 in the polymer.
A polyoxypropylene polymer containing 0 ppm of a double metal cyanide complex catalyst and containing an unsaturated group and a hydroxyl group in one molecule was obtained. The resulting polymer had an unsaturated group equivalent of 0.183 mmol / g as determined by iodine titration and a hydroxyl group equivalent of 0.225 mmol / g as determined by hydroxyl value titration. Examples 1 to 11, Comparative Example 1 100 g of a polyoxypropylene polymer containing about 80 ppm of a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule (unsaturated) produced in Reference Example 1 Base 1
8.3 mmol) in a nitrogen-sealed glass reactor without purification, and the carboxylic acid compound shown in Table 1 was added in a predetermined amount and in a predetermined addition method. After the addition, a predetermined treatment was performed for 30 minutes. Xylene solution of divinyltetramethyldisiloxane (metal content 3% by weight) 9.5μ
1, 18.5 mmol of methyldimethoxysilane at 60 ° C.
And reacted for 2 hours. After cooling, the rate of hydrosilylation and the rate of residual allyl groups of the reaction product were analyzed by ¹ H-NMR. Table 1 shows the results.

[0044]

[Table 1]

Reference Example 2 Amount of polymerization initiator and propyleneoxy for catalyst activation
In the same manner as in Reference Example 1 except that the amount of
Contains about 160 ppm of double metal cyanide complex catalyst
A polyoxy group containing unsaturated groups and hydroxyl groups in one molecule
A propylene polymer was obtained. Iodine value of the obtained polymer
The unsaturated group equivalent determined by titration is 0.081 mmol / g,
The hydroxyl equivalent determined by hydroxyl value titration is 0.109 mm
ol / g. Example 12 About 160 ppm of a double metal cyanide prepared in Reference Example 2
Containing complex catalysts and having unsaturated groups and hydroxyl groups in one molecule
100 g of unsaturated polyoxypropylene polymer (unsaturated group
8.1 mmol) was sealed under nitrogen without purification
In a glass reactor, add 10 mg of succinic anhydride
Was. Heat to 130 ° C to ensure complete dissolution of succinic anhydride.
After cooling, cool to 60 ° C
Xylene solution of siloxane (metal content 3% by weight) 9.5
μl, 8.1 mmol of methyldimethoxysilane at 60 ° C.
And reacted for 5 hours. After cooling, reactant hydro
The silylation rate and allyl group remaining rate¹H-NMR analysis
Was. The hydrosilylation rate is 74%, and the allyl group remaining rate is 9%.
Met. Comparative Example 2 About 160 ppm of a double metal cyanide prepared in Reference Example 2
Containing complex catalysts and having unsaturated groups and hydroxyl groups in one molecule
100 g of unsaturated polyoxypropylene polymer (unsaturated group
8.1 mmol) was sealed under nitrogen without purification
In a glass reactor, platinum divinyl tetramethyl
Loxane xylene solution (metal content 3% by weight) 9.5μ
1, methyldimethoxysilane (8.1 mmol) in 60
C. and reacted for 5 hours. After cooling, the reactants
Losylation rate and residual allyl group rate ¹H-NMR analysis
Was. The hydrosilylation ratio is 20%, and the allyl group remaining ratio is 72%.
%Met. Example 13 About 80 ppm of a double metal cyanide produced in Reference Example 1
Contains complex catalyst and has unsaturated group and hydroxyl group in one molecule
60 g of polyoxypropylene polymer (unsaturated group 1
1.0 mmol) was sealed under nitrogen without purification.
In a glass reactor, 6.6 mg of succinic anhydride (TH
F5% solution) was added. Platinum divinyl tetrame
Xylene solution of tildisiloxane (metal content 0.6 weight
%) 18 mg, methyldimethoxysilane 7.7 mmol
Was added and reacted at 80 ° C. for 4 hours. After cooling, reactants
The hydrosilylation rate and the allyl group remaining rate of¹By H-NMR
analyzed. Hydrosilylation rate is 42%, allyl group remaining rate
Was 44%. Example 14 About 80 ppm of a double metal cyanide produced in Reference Example 1
Contains complex catalyst and has unsaturated group and hydroxyl group in one molecule
60 g of polyoxypropylene polymer (unsaturated group 1
1.0 mmol) was sealed under nitrogen without purification.
In a glass reactor, 6.6 mg of succinic anhydride (TH
F5% solution) and heat stirring at 100 ° C. for 1 hour.
Stirred. After cooling to 60 ° C, platinum divinyltetramethyl
Xylene solution of disiloxane (metal content 0.6% by weight)
18 mg, 7.7 mmol of methyldimethoxysilane
And reacted at 80 ° C. for 4 hours. After cooling, the reactants
Drosilylation rate and residual allyl group rate¹Analyze by H-NMR
did. The hydrosilylation rate is 57% and the allyl group remaining rate is 2
3%.

[0046]

According to the production method of the present invention, a double metal cyanide complex catalyst is converted from a polyoxyalkylene polymer containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule. Without removal, a polyoxyalkylene polymer having a crosslinkable silicon group and a hydroxyl group in one molecule can be obtained. As a result, the manufacturing process can be greatly simplified.

Continuing on the front page (72) Inventor Ryotaro Tsuji 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Kanebuchi Chemical Industry Co., Ltd. 2-80 Kanebuchi Chemical Industry Co., Ltd. Kobe Research Laboratories (72) Inventor Hiroshi Iwakiri 1-8 Miyamae-cho, Takasago-cho, Takasago-shi, Hyogo F-term (reference) 4K005 AA12 BD08

Claims (5)

[Claims] 1. A polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule, after adding a carboxylic acid compound,
A compound (B) 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, wherein the compound (B) has a crosslinkable silicon group and a hydroxyl group in one molecule. A method for producing an oxyalkylene polymer. 2. The method according to claim 1, wherein the carboxylic acid compound is at least one selected from the group consisting of carboxylic acids and carboxylic anhydrides. 3. A polyoxyalkylene polymer (A) containing a double metal cyanide complex catalyst and having an unsaturated group and a hydroxyl group in one molecule, after adding a carboxylic acid compound,
The method according to claim 1, wherein the heat treatment is performed at 50 ° C. or higher. 4. The production method according to claim 1, wherein the double metal cyanide complex is a complex containing zinc hexacyanocobaltate. 5. The method according to claim 1, wherein the hydrosilylation catalyst is a platinum metal-containing complex.