JP2002194075A - Production method for polyalkylene oxide based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple and low-cost preparation method for a polyalkylene oxide-based polymer having an aryloxy group or a substituted aryloxy group, very low in content of a catalyst, by-product and impurities required for purifying and removing, therefore capable of simplifying or abbrevi ating an after-treating process, and also excellent in thermostability and hydroly sis resistance. SOLUTION: This polyalkylene oxide-based polymer having the aryloxy group or the substituted aryloxy group, is obtained by reacting a polyalkylene oxide-based polymer having one or more hydroxy groups in the molecule, with an aryl ester compound in the presence of a cyanide complex having plural metals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an allyloxy group,
Or a method for producing a polyalkylene oxide polymer having a substituted allyloxy group.

[0002]

2. Description of the Related Art Polyalkylene oxide-based polymers having an allyloxy group or a substituted allyloxy group can be used, for example, by subjecting a silicon compound having a hydrogen-silicon bond to a hydrosilylation reaction to produce an architectural or industrial sealing material, adhesive, or the like. It is widely used as a raw material polymer for coating materials and the like. Such polyalkylene oxide-based polymers having an allyloxy group or a substituted allyloxy group are disclosed in JP-A-50-156599, JP-A-52-73998, and JP-A-3-725.
As exemplified in JP-A-27-27, etc., it is mainly produced by introducing an allyl group or a methallyl group by a Williamson method utilizing a terminal hydroxyl group of a polyalkylene oxide-based polymer.

However, these production methods generally require three steps: a production step of a polyalkylene oxide polymer having a hydroxyl group, an introduction step of an allyl group or a methallyl group, and a purification step. There was a problem that it was complicated. Furthermore, in the step of introducing an allyl group or a methallyl group, since by-products such as salts and impurities are generated, there is a problem that a large amount of waste and wastewater are generated in the purification step.

[0004] As a production method in which by-products such as salts are not generated, a method of introducing an allyloxy group by reacting a carbonate compound with a compound having a hydroxyl group is known as Tetrah.
edron Lett. 1989, Vol. 30, No. 35, 46
69, Synth. Commun. 1990 Vol. 20, No. 10, p. 1551, Bull. Chem. S
oc. Jpn. 1992, 65: 1665, S
ynlett. This is exemplified on page 725 of 1992. These are all methods of reacting a compound having a hydroxyl group with allyl ethyl carbonate to synthesize an allyl ether compound with decarboxylation, using a palladium compound as a catalyst. However, palladium compounds are expensive and therefore impractical from an industrial point of view. Further, when a polyalkylene oxide-based polymer having an allyloxy group is produced by the method described in these documents, the palladium compound remaining in the system is inconvenient in using the polyalkylene oxide-based polymer having an allyloxy group. May be. For example, when performing a hydrosilylation reaction with an allyl group of a polyalkylene oxide-based polymer having an allyloxy group using a silicon compound having a hydrogen-silicon bond, the palladium compound may inhibit the hydrosilylation reaction. This problem is particularly remarkable when a palladium compound having a phosphine ligand is present. In such a case, the palladium compound must be removed from the polyalkylene oxide-based polymer before the hydrosilylation reaction, but a purification step is required, which complicates the production process, increases equipment costs and decreases productivity. There was such a problem.

As a method for introducing an unsaturated bond into the terminal of a polyalkylene oxide using an allyl carbonate compound, for example, a reaction between a polyalkylene oxide and diallyl carbonate is disclosed in JP-A-56-133246.
And Japanese Patent Publication No. 5-26812. These are methods for producing a polyalkylene oxide-α, ω-bisallyl carbonate by reacting a polyalkylene oxide with diallyl carbonate in the presence of a transesterification catalyst. However, the polyalkylene oxide-α, ω-bisallyl carbonate obtained by the method has an allyl carbonate structure at the terminal instead of an allyloxy group, and further has a heat-resistance and a hydrolysis-resistance because a transesterification catalyst remains. There was a problem that was bad. In addition, when an attempt is made to introduce a silicon functional group by a hydrosilylation reaction using a terminal allyl group, a transesterification catalyst often hinders the hydrosilylation reaction. If an attempt is made to remove or deactivate the transesterification catalyst in order to solve these problems, the process becomes complicated, and there are problems such as an increase in equipment costs and a decrease in productivity.

Furthermore, these allyl carbonate compounds also have a problem that they are generally expensive.

[0007]

Because of the above problems, there is no need to newly add a transesterification catalyst or the like, and allyloxy groups having high heat resistance and hydrolysis resistance as unsaturated groups, Alternatively, a method for easily and inexpensively producing a polyalkylene oxide polymer having a substituted allyloxy group has been desired.

[0008] The problem to be solved by the present invention is that the content of catalysts, by-products and impurities that need to be purified and removed is extremely small, so that the post-treatment step can be simplified or omitted.
Moreover, it is an object of the present invention to provide a simple and inexpensive method for producing a polyalkylene oxide polymer having an allyloxy group or a substituted allyloxy group, which is excellent in heat resistance and hydrolysis resistance.

[0009]

Means for Solving the Problems The present inventors have made it possible to react an allyl ester compound with a polyalkylene oxide polymer having one or more hydroxyl groups in one molecule in the presence of a double metal cyanide complex. , An allyloxy group,
Alternatively, they have found that a polyalkylene oxide polymer having a substituted allyloxy group can be produced, and have completed the present invention.

That is, the present invention provides a polyalkylene oxide polymer having one or more hydroxyl groups in one molecule,
General formula (1):

[0011]

Embedded image (Wherein, R ¹ is a hydrogen atom, a halogen atom, or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
A hydrocarbon group selected from an allyl group, a substituted allyl group, an aralkyl group, and a substituted aralkyl group. R ² is a hydrogen atom,
Or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, a substituted allyl group, an aralkyl group,
Shows a hydrocarbon group selected from substituted aralkyl groups. R ¹
And R ² may be the same or different. )
And a method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group, characterized by reacting an allyl ester compound represented by the formula (1) in the presence of a double metal cyanide complex.

In a preferred embodiment, the polyalkylene oxide polymer having one or more hydroxyl groups in one molecule is polymerized using a double metal cyanide complex as a catalyst. The present invention relates to a method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group.

In a further preferred embodiment, the polyalkylene oxide polymer having one or more hydroxyl groups in one molecule has a number average molecular weight of 3,000 or more. And a method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group.

In a further preferred embodiment, the polyalkylene oxide polymer having one or more hydroxyl groups in one molecule has one or more unsaturated groups in one molecule. The present invention relates to a method for producing a polyalkylene oxide polymer having an allyloxy group or a substituted allyloxy group according to any one of the above.

In a further preferred embodiment, the allyl ester compound is allyl formate, allyl acetate, allyl chloroformate, allyl chloroacetate, allyl methoxyacetate, allyl trifluoroacetate, allyl acrylate, allyl methacrylate, diallyl oxalate, Diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl succinate, characterized by being a compound selected from the group consisting of triallyl trimaryl, allyloxy group according to any one of the above, Or a method for producing a polyalkylene oxide polymer having a substituted allyloxy group.

In a further preferred embodiment, the double metal cyanide complex is a complex containing zinc hexacyanocobaltate, wherein the complex has an allyloxy group or a substituted allyloxy group. The present invention relates to a method for producing a polyalkylene oxide polymer.

In a further preferred embodiment, the present invention relates to the method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group according to any one of the above, wherein an acid scavenger is present.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The polyalkylene oxide polymer having one or more hydroxyl groups in one molecule used in the present invention is not particularly limited. For example, an active hydrogen compound may be used as a polymerization initiator, It can be obtained by ring-opening polymerization of an epoxide.

Here, examples of the active hydrogen compound as a polymerization initiator include a hydroxyl group-containing compound, a carboxyl group-containing compound, and water, but are not limited thereto. Such active hydrogen compounds include:
For example, 3-methyl-1-butyn-3-ol, 3,6-
Dimethyl-4-octyne-3,6-diol, 2,5-
Dimethyl-3-hexyne-2,5-diol, N, N-
Diethylethanolamine, N-methyldiethanolamine, 3-amino-1-propanol, allyl alcohol, isoamyl alcohol, isodecyl alcohol, isotridecyl alcohol, isoprene glycol, isopropyl alcohol, monoethanolamine, diethanolamine, triethanolamine, ethyl alcohol , 2-ethyl-1-hexanol, ethylene glycol, diethylene glycol, triethylene glycol,
Ethylene glycol monobutyl ether, ethylene chlorohydrin, ethylene cyanohydrin, choline chloride, octanol, octanediol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol, glycerol α-monochlorohydrin, 2- (2-chloroethoxy) ethanol, 3-chloro-1-propanol, cyclohexanol, 1,4-cyclohexanediol, cyclopentanol, 1,3-dihydroxyacetone, diisopropyl tartrate, diacetone alcohol, 1-thioglycerol, thio Diglycol, trimethylolethane, trimethylolpropane, trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether,
Ethyl lactate, butyl lactate, methyl lactate, neopentyl glycol, nonyl alcohol, α-hydroxyisobutyric acid methyl ester, 2-hydroxyethylaminopropylamine, hydroxydicyclopentadiene, 4-hydroxy-2-butanone, n-butanol, iso- Butanol, sec-butanol, t-butanol, butanediol, 2-butyl-2-ethyl-1,3-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene chlorohydrin, 1,6-hexanediol , 1,2,6-hexanetriol, hexylene glycol, heptanol,
Pentaerythritol, pentaerythritol diallyl ether, pentaerythritol monoallyl ether,
1,5-pentanediol, polyethylene glycol,
Polytetramethylene ether glycol, polypropylene glycol, methanol, methallyl alcohol, methyl isobutyl carbinol, methyl cyclohexanol, 3-methyl-1,5-pentanediol, 3-methyl-3-methoxy-1-butanol, 3-methoxy -1
-Butanol, 2-mercaptoethanol, 2-amino-4-chlorophenol, aminophenol, p-ethylphenol, methyl p-oxybenzoate, p-octylphenol, catechol, xylenol, guaiacol, guetol, p- (α-cumyl ) Phenol, cresol, o-cresol-4-sulfonic acid, 2,4-dinitrophenol, 1,4-dihydroxyanthraquinone, 1,4-dihydroxynaphthalene, 2,4-di-t
-Butylphenol, 2,6-di-t-butylphenol, hydrogenated bisphenol A, p-dodecylphenol, diallyl trimellitate, monoallyl trimellitate, 2,4,6-tris (dimethylaminomethyl) phenol, 2,3 , 4-trihydroxybenzophenone,
2,3,5-trimethylhydroquinone, tropicamide, naphthol, nitrophenol, p-nitrobenzyl alcohol, nonylphenol, hydroquinone, bis (2-hydroxyethyl) terephthalate, bis (4
-Hydroxyphenyl) sulfone, bisphenol A,
p-hydroxyphenylacetamide, p-hydroxyphenylacetic acid methyl ester, p-hydroxyphenethyl alcohol, hydroxypropiophenone, hydroxybenzaldehyde, phenylphenol, phenol, p-phenolsulfonic acid, 2-phenoxyethanol, 4-phenoxyphenol, 4- t-butylcatechol, 2-t-butylhydroquinone, pt-butylphenol, phloroglucinol, heptylparaben, benzoin, 2-methyl-6-t-butylphenol, methol, p- (methoxyethyl) phenol, lauryl gallate , Resorcin, leuco-1,4-dihydroxyanthraquinone, amidole, p-aminophenol, attomar, 1,1'-bi-2-naphthol, 2
-Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, kojic acid, spiroglycol, tetrahydrofurfuryl alcohol, tris (2-hydroxyethyl) isocyanurate, tri Benzylphenol, (hydroxyethyl) piperazine, pyridinemethanol, furfuryl alcohol, 4-methyl-5- (2 ′
-Hydroxyethyl) thiazole, 1-methylol-
5,5-dimethylhydantoin, 2-chloro-4-nitrophenol, chlorophenol, 2,3-dibromo-
1-propanol, 2,2,3,3-tetrafluoropropanol, trifluoroethanol, ω-hydrofluoroalcohol, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, hexafluoro-2-
Propanol, 2,6-di-t-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6
t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) -Hydroxybenzyl) benzene, 1,1-bis (4-hydroxyphenyl) -cyclohexane, isostearyl alcohol, glycerin, diglycerin, bisabolol, phytantriol, isoeugenol, isocampylcyclohexanol, ethyl vanillin, eugenol, silica Skin alcohol, geraniol, isoamyl salicylate, benzyl salicylate, methyl salicylate, cis-hexenol, citronellol, dimethylbenzylcarbinol, tetrahydrolinalool, terpineol, vanillin, hydroxycitronellal, β-
Phenylethyl alcohol, benzyl alcohol, borneol, maltol, menthol, linalool, rosinol, isobutyl parahydroxybenzoate, isopropyl paraoxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, erythorbic acid, isopropyl citrate, dibutylhydroxytoluene, α- Tocopherol, nordihydroguaiaretic acid, butylhydroxyanisole, propyl gallate, retinol, riboflavin, ascorbic acid, ergocalciferol,
Cholecalciferol, gluconodelta lactone, erythritol, xylitol, xylose, sorbitol, glucose, glucosamine, fructose, ribose, maltose, chitin, chitosan, sorbit, mannitol, arbutin, adenosine, 6-allyl adenosine, guanine, guanosine, arabi Hydroxyl-containing compounds such as nosylcytosine, inosine, estradiol, ganciclovir, and sanilvudine; acrylic acid, methacrylic acid, adipic acid, azobiscyanovaleric acid, 12-aminododecanoic acid, isononanoic acid, isobutyric acid, itaconic acid, iminodiacetic acid, undecylenic acid , Ethylenediaminetetraacetic acid, 2-ethylhexanoic acid, formic acid, glycylglycine,
Glutaric acid, crotonic acid, 3-chloropropionic acid, acetic acid, cyclohexanecarboxylic acid, citraconic acid, oxalic acid, diparatoluoyltartaric acid, dibenzoyltartaric acid, sebacic acid, thioglycolic acid, 3,3′-thiodipropionic acid, thiomalein Acid, dodecanedioic acid, 1,2-cyclohexanediaminetetraacetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, pyruvic acid, brasilic acid, propionic acid, malonic acid, methoxyacetic acid, β-mercaptopropionic acid, levulinic acid, p- Aminobenzoic acid, benzoic acid, anthranilic acid, isophthalic acid, diphenyl-4-
Carboxylic acid, diphenylacetic acid, thiosalicylic acid, terephthalic acid, toluic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthoic acid, p
-Nitrobenzoic acid, phenylacetic acid, phenoxyacetic acid, p
-T-butylbenzoic acid, o-benzoylbenzoic acid, trimellitic anhydride, p-methoxyphenylacetic acid, isonicotinic acid, 1-cyanoethyl-2-methylimidazole trimellitate, 3-carbamoyl-pyrazinecarboxylic acid, quinaldic acid , 2-chloronicotinic acid, picolinic acid, 2,3-pyrazinedicarboxylic acid, pyrazine monocarboxylic acid, o-chlorobenzoic acid, p-chlorobenzoic acid,
-Amino-4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 4-chloro-3-nitrobenzoic acid, chlorophenylacetic acid, α-bromopropionic acid, α-bromobutyric acid, trifluoroacetic acid, lauric acid, myristic acid, Palmitic acid, behenic acid, stearic acid, isostearic acid,
Cinnamic acid, butyric acid, sorbic acid, folic acid, isoleucine, tryptophan, valine, phenylalanine, methionine, succinic acid, fumaric acid, aspartame, glycine,
Carboxyl group-containing compounds such as glutamic acid, theanine, lipoic acid, aspartic acid, alanine, arginine, glutamine, glutamic acid, cystine, proline, leucine, citrulline, orotic acid, trandolapril and seratrodast; 4-hydroxybutyl acrylate;
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glyoxylic acid, tartaric acid, α-hydroxyisobutyric acid, β-oxynaphthoic acid, salicylic acid, p
-Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, protocatechuic acid, benzylic acid, mandelic acid, keridamic acid, citrazinic acid, threonine, citric acid, gluconic acid, Compounds having both a hydroxyl group and a carboxyl group, such as lactic acid, malic acid, serine, mesalazine, salazosulfapyridine, etc .; water; monoepoxide adducts of the above compounds, for example, propylene oxide adducts, ethylene oxide adducts, etc. However, the present invention is not limited to these. Among these active hydrogen compounds as a polymerization initiator, a compound having an alcoholic hydroxyl group is preferable in that polymerization proceeds smoothly, and a plurality of allyloxy groups or a substituted allyloxy group can be introduced into one molecule of the polymer. Ethylene glycol, propylene glycol, hexanediol, hexanetriol, pentanediol, trimethylolpropane,
Compounds having a plurality of alcoholic hydroxyl groups in one molecule such as pentaerythritol, glycerin, propylene oxide adduct thereof, and ethylene oxide adduct thereof are more preferable, and allyloxy group or allyl used for introducing substituted allyloxy group is preferable. Allyl alcohol, methallyl alcohol, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether,
Compounds having both an unsaturated group and a hydroxyl group in one molecule, such as pentaerythritol monoallyl ether, pentaerythritol diallyl ether, propylene oxide adduct thereof, and ethylene oxide adduct thereof, are particularly preferable. These active hydrogen compounds as a polymerization initiator may be used alone or in combination of two or more.

The monoepoxide to be subjected to ring-opening polymerization with respect to an active hydrogen compound as a polymerization initiator is not particularly limited, but ethylene oxide, propylene oxide, butene oxide, isobutene oxide, epichlorohydrin, styrene oxide, allyl glycidyl ether, Lyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, cyclopentadiene monooxide and the like can be mentioned. Of these, propylene oxide, allyl glycidyl ether and methallyl glycidyl ether are preferred because they are easy to handle. These monoepoxides may be used alone or in combination of two or more.

The molecular weight of the polyalkylene oxide-based polymer having one or more hydroxyl groups in one molecule used in the present invention is not particularly limited.
00 to 50,000 is preferable, and 3000 to 3000 is preferable.
0 is more preferred. If the number average molecular weight is less than 1500, the viscosity is low, and if it exceeds 50,000, the viscosity is high and handling may be difficult. The polyalkylene oxide polymer having one or more hydroxyl groups in one molecule used in the present invention may be used alone or in combination of two or more. Further, in the present invention, when reacting a polyalkylene oxide polymer having one or more hydroxyl groups in one molecule with an allyl ester compound, a double metal cyanide complex is used as an essential component. A polyalkylene oxide polymer polymerized as a catalyst is preferred. Further, as the polyalkylene oxide polymer used in the present invention, it is preferable that 50% by weight or more of the polymer is a propylene oxide unit in view of excellent physical properties such as heat resistance and weather resistance. More preferably, 90% by weight or more are propylene oxide units.

The double metal cyanide complex used in the present invention is disclosed in US Pat. No. 3,278,457 and US Pat.
No. 458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, US Pat. No. 3,427,335, US Pat.
No. 505, US Pat. No. 3,941,849, US Pat. No. 3,941,849, US Pat. No. 4,355,188, US Pat. No. 4,472,560, US Pat.
No. 818, U.S. Pat. No. 4,843,054, U.S. Pat. No. 5,158,922, JP-A-4-145123, JP-A-7-196778, and JP-A-8-311.
No. 171, JP-A-8-104741, JP-A-9-59373, WO9740086, W
O9723544, Macromolecula
r Synthesis 1974, Vol. 5, p. 9 and the like, represented by the following general formula (2). M _p ｛M ′ [(CN) _q (Y) _r ] _s ｝ _t · y (R) · z (H ₂ O) (2) (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
o (VI), W (IV), and W (VI), wherein M ′ is Fe (II), Fe (II)
(III), Co (II), Co (III), Cr (I
I), Cr (III), Mn (II), Mn (II
A metal selected from the group consisting of I), Ni (II), V (IV), and V (V), wherein Y is Cl, Br, I,
OH, NO, C ₂ O ₄ , SO ₄ , CNS, CNO, NC
A group selected from the group consisting of O and NCS;
Is an organic ligand selected from the group consisting of ketones, ethers, polyethers, aldehydes, esters, alcohols, and amides. These M, M ', Y and R
May be the same or different, and a plurality of types may be used in combination. p, q, r, s, and t are positive numbers depending on the valence and coordination number of the metal, and y and z
Is a positive number that varies depending on the coordination number of the metal or the drying conditions. M) In the general formula (2), M is preferably Zn (II) and M ′ is Fe (II), Fe (III), Co
(II), Co (III) is preferred, and R, which is an organic ligand, is preferably an ether, polyether or alcohol, and contains dimethoxyethane, diethylene glycol dimethyl ether, polyoxypropylene diol, polyoxypropylene triol, and a tertiary hydroxyl group. Polyoxypropylene polyol, t-butanol, and isopropyl alcohol are particularly preferred.

As the double metal cyanide complex, a complex containing zinc hexacyanocobaltate is preferable because of its high activity when used as a polymerization catalyst, and a dimethoxyethane coordination complex of zinc hexacyanocobaltate;
More preferred are t-butanol coordination complex of zinc hexacyanocobaltate, t-butanol and polyoxypropylene diol coordination complex of zinc hexacyanocobaltate, and t-butanol and polyoxypropylene triol coordination complex of zinc hexacyanocobaltate. Also, because of its high activity when used as a polymerization catalyst,
Preferred are at least 70% by weight of a substantially amorphous double metal cyanide complex, more preferred at least 90% by weight of a substantially amorphous double metal cyanide complex.

The allyl ester compound used in the present invention has the general formula (1):

[0025]

Embedded image (Wherein, R ¹ is a hydrogen atom, a halogen atom, or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
It represents a hydrocarbon group such as an allyl group, a substituted allyl group, an aralkyl group, and a substituted aralkyl group. R ² represents a hydrogen atom or a hydrocarbon group such as an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, a substituted allyl group, an aralkyl group, and a substituted aralkyl group. R ¹ and R ² may be the same or different. ).

Examples of such allyl ester compounds include allyl acrylate, allyl methacrylate, diallyl adipate, monoallyl adipate, diallyl azobiscyanovalerate, allyl 12-aminododecanoate, allyl isononanoate, allyl isobutyrate, Diallyl itaconate, diallyl iminodiacetate, allyl undecylenate, tetraallyl ethylenediaminetetraacetate, allyl 2-ethylhexanoate, allyl formate, allyl chloroformate, allyl glyoxylate, glycylglycine allyl ester, diallyl glutarate, allyl crotonic acid, 4 -Allyl chloroacetoacetate, allyl 3-chloropropionate, allyl acetate, allyl cyclohexanecarboxylate, diallyl citraconic acid, diallyl oxalate, diallyl diparatoluoyl tartrate, dibenzoi Diallyl tartrate, diallyl sebacate, allyl thioglycolate, diallyl 3,3'-thiodipropionate, diallyl thiomaleate, diallyl dodecane diate, tetraallyl 1,2-cyclohexanediaminetetraacetate, allyl chloroacetate, allyl dichloroacetate, Allyl trichloroacetate, allyl trifluoroacetate,
Allyl pyruvate, diallyl brasilate, allyl propionate, diallyl malonate, allyl methoxyacetate, β-
Allyl mercaptopropionate, allyl levulinate, p
-Allyl aminobenzoate, allyl benzoate, allyl anthranilate, diallyl isophthalate, diphenyl-4-
Allyl carboxylate, allyl diphenylacetate, allyl thiosalicylate, diallyl terephthalate, allyl toluate, diallyl 1,4-naphthalenedicarboxylate, 2,6
-Diallyl naphthalenedicarboxylate, allyl naphthoate, allyl p-nitrobenzoate, allyl phenylacetate,
Allyl phenoxyacetate, allyl pt-butylbenzoate, allyl o-benzoylbenzoate, allyl trimellitate anhydride, triallyl trimellitate, tetraallyl pyromellitic acid, allyl p-methoxyphenylacetate, allyl isonicotinate, 1- Cyanoethyl-2-methylimidazole trimellitate diallyl, 3-carbamoyl-
Diallyl pyrazinecarboxylate, allyl quinaldinate, 2
-Allyl chloronicotinate, allyl picolinate, 2,3
-Diallyl pyrazinedicarboxylate, allyl pyrazine monocarboxylate, allyl o-chlorobenzoate, allyl p-chlorobenzoate, allyl 2-amino-4-chlorobenzoate, allyl 2,4-dichlorobenzoate, 4-chloro-3
-Allyl nitrobenzoate, allyl chlorophenylacetate,
allyl α-bromopropionate, allyl α-bromobutyrate, allyl laurate, allyl myristate, allyl palmitate, allyl behenate, allyl stearate,
Allyl isostearate, allyl cinnamate, allyl butyrate, allyl sorbate, diallyl folate, isoleucine allyl ester, tryptophan allyl ester, valine allyl ester, phenylalanine allyl ester, methionine allyl ester, diallyl succinate, diallyl fumarate, glycine allyl ester , Diallyl glutamate, allyl aspartate, allyl alanine ester, arginine allyl ester, glutamine allyl ester, diallyl glutamate, cystine diallyl, proline allyl ester, leucine allyl ester, citrulline allyl ester, allyl glyoxylate, diallyl tartrate, α-hydroxyisobutyrate Allyl, allyl β-oxynaphthoate, allyl salicylate, allyl p-hydroxybenzoate, 6-hydrido Allyl roxy-2-naphthoate, allyl p-hydroxyphenylacetate, allyl p-hydroxyphenylpropionate, allyl protocatechuate, allyl benzylate, allyl mandelicate, diallyl chelidate, allyl citrazate, allyl threonate, diallyl citrate Allyl gluconate, allyl lactate, diallyl malate, methallyl acrylate, methallyl methacrylate, dimethallyl adipate, monomethallyl adipate, dimethallyl azobiscyanovalerate, methallyl 12-aminododecanoate, methallyl isononanoate, methallyl isobutyrate, itaconic acid Dimethallyl, dimethallyl iminodiacetate, methallyl undecylenate, tetramethallyl ethylenediaminetetraacetate, methallyl 2-ethylhexanoate, methallyl formate, methallyl chloroformate, Hexyl acid methallyl, glycylglycine methallyl esters, dimethallyl glutarate, methallyl crotonic acid, 4-chloroacetoacetate methallyl, 3-chloropropionic acid methallyl,
Methallyl acetate, methallyl cyclohexanecarboxylate, dimethallyl citraconic acid, dimethallyl oxalate, dimethallyl diparatoluoyl tartrate, dimethallyl dibenzoyl tartrate, dimethallyl sebacate, methallyl thioglycolate, dimethallyl 3,3′-thiodipropionate, dimethallyl thiomaleate, Dimethallyl dodecanedioate, 1,2
-Tetramethallyl cyclohexanediaminetetraacetate, methallyl chloroacetate, methallyl dichloroacetate, methallyl trichloroacetate, methallyl trifluoroacetate, methallyl pyruvate, dimethallyl brasilate, methallyl propionate, dimethallyl malonate, methallyl methoxyacetate, β-
Methallyl mercaptopropionate, methallyl levulinate, methallyl p-aminobenzoate, methallyl benzoate,
Methallyl anthranilate, methallyl isophthalate, methallyl diphenyl-4-carboxylate, methallyl diphenylacetate, methallyl thiosalicylate, methallyl terephthalate, methallyl toluate, 1,4-naphthalenedicarboxylate dimethallyl, 2,6-naphthalenedicarboxylate dimethallyl, Methallyl naphthoate, methallyl p-nitrobenzoate, methallyl phenylacetate, methallyl phenoxyacetate, methallyl pt-butylbenzoate, methallyl o-benzoyl benzoate, methallyl anhydride trimellitate, trimellitate trimellitate, tetramethallyl pyromellitate Methallyl p-methoxyphenylacetate, methallyl isonicotinate, 1-cyanoethyl-2-methylimidazole trimellitate dimethallyl, 3-carbamoyl-pyrazine carboxylate Enough, quinaldine acid methallyl, 2
-Methallyl chloronicotinate, methallyl picolinate,
Dimethallyl 2,3-pyrazinedicarboxylate, methallyl pyrazine monocarboxylate, methallyl o-chlorobenzoate,
methallyl p-chlorobenzoate, methallyl 2-amino-4-chlorobenzoate, methallyl 2,4-dichlorobenzoate, methallyl 4-chloro-3-nitrobenzoate, methallyl chlorophenylacetate, methallyl α-bromopropionate, α- Methallyl bromobutyrate, methallyl laurate, methallyl myristate, methallyl palmitate, methallyl behenate, methallyl stearate, methallyl isostearate, methallyl cinnamate, methallyl butyrate, methallyl sorbate, dimethallyl folate, isoleucine methallyl ester, tryptophan methallyl ester , Valine methallyl ester, Phenylalanine methallyl ester, Methionine methallyl ester, Dimethallyl succinate, Dimethallyl fumarate, Glycine methallyl ester, Dimethallyl glutamate, As Methallyl parapartate, alanine methallyl ester, arginine methallyl ester, glutamine methallyl ester, glutamic acid dimethallyl, cystine dimethallyl, proline methallyl ester, leucine methallyl ester, citrulline methallyl ester, glyoxylate methallyl, dimethallyl tartrate, α-hydroxyisobutyrate methallyl, β -Methallyl oxynaphthoate,
Methallyl salicylate, methallyl p-hydroxybenzoate, methallyl 6-hydroxy-2-naphthoate, methallyl p-hydroxyphenylacetate, methallyl p-hydroxyphenylpropionate, methallyl protocatechuate,
Examples include, but are not limited to, methallyl benzylate, methallyl mandelate, dimethallyl chelidate, methallyl citrazate, threonine methallyl ester, dimethallyl citrate, methallyl gluconate, methallyl lactate, and dimethallyl malate. These may be used alone or in combination of two or more. Of these, in terms of easy availability, allyl formate, allyl acetate, allyl chloroformate, allyl chloroacetate, allyl methoxyacetate, allyl trifluoroacetate, allyl acrylate, allyl methacrylate, diallyl oxalate, diallyl maleate Preferred are diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl succinate and triallyl trimellitate.

In the practice of the present invention, a carboxylic acid compound derived from the allyl ester compound is by-produced. An acid scavenger can be used for the purpose of removing the carboxylic acid compound and assisting the progress of the reaction. Examples of such acid scavengers include alkali metal hydroxides, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal alkoxides, transition metal hydroxides, transition metal alkoxides, Examples include, but are not limited to, amine compounds and basic ion exchange resins.
Of these, 2,6-di-t-butylaniline and 2,6-di-t-t
-Butylpyridine, diphenylamine, triphenylamine, dibutylamine, triethylamine, tributylamine, aniline, anisidine, 2-aminothiazole, aminophenol, 4-aminobenzonitrile, 3
-Isopropoxyaniline, N-ethylaniline, xylidine, xylylenediamine, p-cresidine, dianisidine, 1,4-diaminoanthraquinone, 4,4'-
Diaminobenzanilide, diaminodiphenyl ether, dibenzylamine, 3,3′-dimethyl-4,4 ′
-Diaminodiphenylmethane, N, N-dimethyl-p-
Toluidine, 2,4,5-trichloroaniline, 2,
4,6-tris (dimethylaminomethyl) phenol,
Trizine base, toluidine, m-toluylenediamine, tropicamide, phenylhydrazine, phenylenediamine, phenetidine, phenethylamine, mesidine,
N-methylaniline, N, N-dimethylaniline, N,
N-diethylaniline, N, N-diethylaminotoluidine, paramine, aminopyridine, 1- (2-aminoethyl) piperazine, N- (3-aminopropyl) morpholine, 1-amino-4-methylpiperazine, isoquinoline, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenyl-4-methylimidazole, quinaldine, quinoline, 2-chloropyridine, 2,4,6-collidine, 1,8- Diazabicyclo [5.4.0] undecene-7,2,6-dichloropyridine, 3,6-dichloropyridazine, 4-dimethylaminopyridine, 2,5-
Dimethylpiperazine, cis-2,6-dimethylpiperazine, 2,5-dimethylpyrazine, 3,5-dimethylpyrazole, 1,3-dimethyl-5-pyrazolone, 5-phenyl-1H-tetrazole, 1,2,3 4-tetrahydroquinoline, triethylenediamine, picoline, bis (aminopropyl) piperazine, (hydroxyethyl)
Piperazine, 2-vinylpyridine, 4-vinylpyridine, pipecoline, piperazine, 2- (1-piperazinyl) pyrimidine, 4-piperidinopyridine, piperidine, pyrazine, pyridine, pyridinemethanol, 4-pyrrolidinopyridine, pyrrolidine, o Phenanthroline, phenylpyrazolidone, N-methylpiperazine, 2
-Methylpiperazine, N-methylpiperidine, 2-methylpyrazine, melamine, morpholine, lutidine, N, N
-Diethylethanolamine, N, N-dimethylethanolamine, N- (2-aminoethyl) ethanolamine, N-methyldiethanolamine, N, N-dibutylethanolamine, N-methylethanolamine, allylamine, diallylamine, triallylamine, Isopropylamine, diisopropylamine, 3,3′-iminobis (propylamine), ethylamine, diethylamine, 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino )
Propylamine, di-2-ethylhexylamine, 3-
(Dibutylamino) propylamine, tetramethylethylenediamine, tri-n-octylamine, t-butylamine, sec-butylamine, propylamine, 3-
(Methylamino) propylamine, 3- (dimethylamino) propylamine, N-methyl-3,3′-iminobis (propylamine), 3-methoxypropylamine,
Isopropanolamine, ethanolamine, N-ethylethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-diaminobutane, diaminopropane, diaminomaleonitrile, N, N-diisopropylethylamine, cyclohexyl Amine, N, N-dimethylacetamide, dimethylhydrazine, oleamide, acrylamide, thioacetamide, thiocarbohydrazide, semicarbazide, thiosemicarbazide, carbohydrazide, thiocarbamide, tetramethyl-1,3-diaminopropane,
1,1,3,3-tetramethylurea, N, N, N ',
N'-tetramethyl-1,6-hexamethylenediamine, hexamethylenediamine, hexamethylenetetramine, n-hexylamine, methylamine, N, N'-methylenebis (acrylamide), 3- (lauryloxy) propylamine and the like Amine compound; bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, ADK STAB LA-77 (manufactured by Asahi Denka Co., Ltd.), Sano
l LS-770 (manufactured by Sankyo), Sumithorpe 577 (manufactured by Sumitomo Chemical), Biosoap 04 (manufactured by Kyodo Yakuhin), C
himassorb 944LD (Ciba spec
ialty), Tinuvin 622LD (Ci
ba specialty), BioSoap 03
(Manufactured by Kyodo Yakuhin), Tinuvin 144 (Ciba
specialty), ADK STAB LA-57
(Made by Asahi Denka Co., Ltd.), ADK STAB LA-62 (made by Asahi Denka Co., Ltd.), ADK STAB LA-67 (made by Asahi Denka Co., Ltd.), ADK STAB LA-63 (made by Asahi Denka Co., Ltd.), ADK STAB LA-
68 (made by Asahi Denka), ADK STAB LA-82 (made by Asahi Denka), ADK STAB LA-87 (made by Asahi Denka), Go
odriteUV-3034 (Goodrich)
Hindered amine light stabilizers (HALS) such as 2,6-di-t-butylpyridine, bis (2,2
2,6,6-tetramethyl-4-piperidyl) sebacate, ADK STAB LA-77 (manufactured by Asahi Denka Co., Ltd.), Sano
l LS-770 (manufactured by Sankyo), Sumithorpe 577 (manufactured by Sumitomo Chemical), Biosoap 04 (manufactured by Kyodo Yakuhin), C
himassorb 944LD (Ciba spec
ialty), Tinuvin 622LD (Ci
ba specialty), BioSoap 03
(Manufactured by Kyodo Yakuhin), Tinuvin 144 (Ciba
specialty), ADK STAB LA-57
(Made by Asahi Denka Co., Ltd.), ADK STAB LA-62 (made by Asahi Denka Co., Ltd.), ADK STAB LA-67 (made by Asahi Denka Co., Ltd.), ADK STAB LA-63 (made by Asahi Denka Co., Ltd.), ADK STAB LA-
68 (made by Asahi Denka), ADK STAB LA-82 (made by Asahi Denka), ADK STAB LA-87 (made by Asahi Denka), Go
Odrite UV-3034 (manufactured by Goodrich) is more preferred. The acid scavengers used in the present invention may be used alone or in combination of two or more.

The method for producing the polyalkylene oxide polymer having an allyloxy group or a substituted allyloxy group of the present invention will be described below, but the production method is not limited thereto.

The present invention relates to a polyalkylene oxide polymer having one or more hydroxyl groups in one molecule, represented by the general formula (1):

[0030]

Embedded image (Wherein, R ¹ is a hydrogen atom, a halogen atom, or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
It represents a hydrocarbon group such as an allyl group, a substituted allyl group, an aralkyl group, and a substituted aralkyl group. R ² represents a hydrogen atom or a hydrocarbon group such as an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, a substituted allyl group, an aralkyl group, and a substituted aralkyl group. R ¹ and R ² may be the same or different. The present invention relates to a method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group by reacting an allyl ester compound represented by the formula (1) in the presence of a double metal cyanide complex.

Specifically, the reaction proceeds by mixing a polyalkylene oxide-based polymer having one or more hydroxyl groups in one molecule, the allyl ester compound, and a double metal cyanide complex. The reaction temperature is not particularly limited, but is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of increasing the reaction rate. However, if the temperature is too high, thermal degradation of the polyalkylene oxide-based polymer may proceed, so that the temperature is preferably 300 ° C. or less,
00 ° C or lower is more preferable. As the reaction progresses, a carboxylic acid compound derived from the allyl ester compound is generated.If possible, the reaction proceeds more smoothly by keeping the reaction system under reduced pressure and removing the carboxylic acid compound from the system. I do. In the case where the pressure is reduced while heating, it is preferable to carry out under conditions (temperature and degree of reduced pressure) such that the allyl ester compound is not distilled off and the carboxylic acid compound derived from the allyl ester compound is distilled off. . In order to remove the carboxylic acid compound derived from the allyl ester compound, an acid scavenger can also be used.The amount of the acid scavenger is not particularly limited, but from the balance between the acid scavenging effect and the cost, the carboxylic acid compound is by-produced. Is preferably from 0.2 to 100 equivalents, more preferably from 0.5 to 10 equivalents.

In the present invention, there is no particular need to use a solvent, and the reaction can be carried out without a solvent. However, for the purpose of uniformly dissolving the substrate, the temperature control of the reaction system and the addition of the substrate are easily performed. A solvent can be used for the purpose. As the solvent to be used, for example, hexane, cyclohexane, ethylcyclohexane, heptane, octane,
Dodecane, benzene, toluene, xylene, dodecylbenzene, chloroform, methylene chloride, chlorobenzene, o-dichlorobenzene, 1,2-dichloroethane,
Examples thereof include, but are not limited to, butyl chloride, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane, acetone, and methyl ethyl ketone. Further, those that can be used as a plasticizer for the polyalkylene oxide polymer, such as polyethers, can also be used as the solvent.

The timing of adding each component such as a reaction substrate and a catalyst is not particularly limited. When adding, they may be added all at once, or may be added slowly as the reaction proceeds.
Also, they may be added alone or together with other components or solvents.

In the present invention, in order to prevent the polyalkylene oxide polymer from being oxidized and degraded, it is preferable to carry out the reaction under a condition where the oxygen concentration is low. For example, nitrogen,
The reaction is preferably performed in an atmosphere of an inert gas such as argon or helium.

In the present invention, a transesterification catalyst typified by an acid, a base, a titanium compound, an aluminum compound or the like is not particularly required, and it is rather preferable not to add it. A small amount of transesterification catalyst may be used to partially introduce a carboxy group for the purpose of improving the compatibility with the resin or adjusting the polarity and refractive index of the polyalkylene oxide polymer. However, since the presence of the transesterification catalyst causes a decrease in heat resistance, a decrease in weather resistance, a decrease in hydrolysis resistance, and the like, it is preferable that the amount of the transesterification catalyst used is kept to the minimum necessary.

In the present invention, one of the features is that the purification step before and after the reaction is not particularly required and can be omitted, but it is not excluded that the purification of the polyalkylene oxide polymer is excluded for a special reason. Absent. For example, a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group produced by the present invention may be subjected to filtration and purification, treatment with an adsorption column, or treatment with water and solvent extraction. .

In the production method of the present invention, since a purification step is not particularly required, the production of a polyalkylene oxide polymer having one or more hydroxyl groups in one molecule is continuously carried out in a single reaction vessel. , An allyloxy group or a substituted allyloxy group can be produced.

The polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group produced according to the present invention can be used, for example, to convert a compound having a hydrogen-silicon bond and a crosslinkable silicon group in one molecule into a hydrosilylation catalyst. By conducting a hydrosilylation reaction in the presence, it can be converted to a polyalkylene oxide polymer having a crosslinkable silicon group. The polyalkylene oxide-based polymer having a crosslinkable silicon group produced in this way gives a crosslinked cured product by reacting with water or moisture in the atmosphere, for architectural or industrial sealing materials, adhesives Raw materials such as agents and coating materials,
Alternatively, it is useful as a raw material intermediate. Further, an allyloxy group produced by the present invention, or a polyalkylene oxide polymer having a substituted allyloxy group,
A crosslinked cured product can also be obtained by a hydrosilylation reaction using a compound having two or more hydrogen-silicon bonds in one molecule, and a raw material such as a sealing material, an adhesive, a coating material, or a raw material intermediate Useful as

[0039]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. (Production Example 1) In a autoclave, 0.80 g of a zinc hexacyanocobaltate glyme complex as a polymerization catalyst, and a polypropylene oxide having an allyl group and a hydroxyl group in one molecule of a number average molecular weight of 1500 as a polymerization initiator (Unisafe, manufactured by NOF Corporation) 602.5 g of PKA-5014, hydroxyl equivalent (0.676 mmol / g) and 81.8 g of propylene oxide were charged, and the temperature was gradually raised to 100 ° C. to carry out a polymerization reaction. Subsequently, 4321.4 g of propylene oxide was added dropwise over about 7.5 hours, and the internal temperature was maintained at 100 to 110 ° C. After the completion of the dropwise addition, the mixture was further heated for 0.5 hour, and then a small amount of unreacted monomer was removed by devolatilization under reduced pressure. This allows about 16 in the polymer.
Polypropylene oxide (number average molecular weight: about 16000) containing 0 ppm of zinc hexacyanocobaltate glyme complex and having an allyl group and a hydroxyl group in one molecule was obtained. The unsaturated group equivalent determined by iodine titration is 0.081.
The hydroxyl equivalent obtained by hydroxyl / titration titration was 0.109 mmol / g. (Examples 1 to 13) 160 ppm produced in Production Example 1
Containing a zinc hexacyanocobaltate glyme complex of
100 g (10.9 mmol of hydroxyl group) of polypropylene oxide having an allyl group and a hydroxyl group is weighed into a glass reactor, a predetermined amount of an allyl ester compound is added in a nitrogen atmosphere, and the mixture is heated at a temperature of 80 to 150 ° C. for 1 to 18 hours. Stirred. Thereafter, the mixture was devolatilized under reduced pressure at 130 ° C. for 2 hours to obtain a polypropylene oxide having an allyloxy group or a substituted allyloxy group. Table 1 shows the allyl ester compound used for the reaction, the reaction conditions, and the reaction yield.

[0040]

[Table 1] Example 14 Polypropylene oxide 10 containing 160 ppm of zinc hexacyanocobaltate glyme complex and having an allyl group and a hydroxyl group produced in Production Example 1
0 g (10.9 mmol of hydroxyl group) was weighed into a glass reactor, and 3.27 g (32.7 m
mol) and 3.14 g of 2,6-di-t-butylpyridine
(16.4 mmol), and the mixture was heated and stirred at 100 ° C. for 8 hours. Thereafter, devolatilization under reduced pressure was performed at 130 ° C. for 2 hours to obtain a polypropylene oxide having an allyloxy group.
The allyloxylation yield was 81% based on the hydroxyl groups in the polypropylene oxide. (Example 15) Polypropylene oxide 10 containing 160 ppm of zinc hexacyanocobaltate glyme complex produced in Production Example 1 and having an allyl group and a hydroxyl group.
0 g (10.9 mmol of hydroxyl group) was weighed into a glass reactor, and 5.51 g (4.
9.1 mmol) and 4.17 g (21.8 mmol) of 2,6-di-t-butylpyridine,
For 10 hours. Thereafter, devolatilization under reduced pressure was performed at 130 ° C. for 2 hours to obtain a polypropylene oxide having an allyloxy group. The allyloxylation yield was 94% based on the hydroxyl groups in the polypropylene oxide.

[0041]

The polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group obtained by the production method of the present invention contains almost any carbonate bond or ester bond having problems in heat resistance and hydrolysis resistance. And it contains almost no transesterification catalyst, so that it has excellent heat resistance and hydrolysis resistance. Furthermore, there are almost no by-products that need to be removed or purified, so that the purification process can be simplified or omitted, equipment costs can be reduced, and productivity can be improved. is there.

Claims (7)

[Claims] 1. A polyalkylene oxide polymer having one or more hydroxyl groups in one molecule is represented by a general formula (1): (Wherein, R ¹ is a hydrogen atom, a halogen atom, or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
A hydrocarbon group selected from an allyl group, a substituted allyl group, an aralkyl group, and a substituted aralkyl group. R ² is a hydrogen atom,
Or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, a substituted allyl group, an aralkyl group,
Shows a hydrocarbon group selected from substituted aralkyl groups. R ¹
And R ² may be the same or different. )
A method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group, comprising reacting an allyl ester compound represented by the formula (1) in the presence of a double metal cyanide complex. 2. The method according to claim 1, wherein the polyalkylene oxide-based polymer having one or more hydroxyl groups in one molecule is polymerized by using a double metal cyanide complex as a catalyst. For producing a polyalkylene oxide-based polymer having an alkyloxy group or an allyloxy group or a substituted allyloxy group. 3. The polyalkylene oxide polymer having one or more hydroxyl groups in one molecule has a number average molecular weight of 3
000 or more.
The method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group according to any one of the above. 4. The polyalkylene oxide polymer having one or more hydroxyl groups in one molecule has one or more unsaturated groups in one molecule. Or a method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group. 5. The method according to claim 5, wherein the allyl ester compound is allyl formate,
Allyl acetate, allyl chloroformate, allyl chloroacetate, allyl methoxyacetate, allyl trifluoroacetate, allyl acrylate, allyl methacrylate, diallyl oxalate, diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, succinic acid The production of a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group according to any one of claims 1 to 4, which is a compound selected from the group consisting of diallyl and triallyl trimellitate. Method. 6. The polymetal having an allyloxy group or a substituted allyloxy group according to claim 1, wherein the double metal cyanide complex is a complex containing zinc hexacyanocobaltate. A method for producing an alkylene oxide polymer. 7. The method for producing a polyalkylene oxide-based polymer having an allyloxy group or a substituted allyloxy group according to claim 1, wherein an acid scavenger is present.