JPH1160723A - Production of polyalkylene oxide polymer and moisture-curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer that is useful as a raw material for adhesive, coating and the like with excellent productivity in no need of complicated processes by converting the hydroxyl groups in polyol containing a specific amount of polyoxyalkylene polyol prepared by a specific production process to an unsaturated group. SOLUTION: In the presence of catalyst of tetrakis[tris(dimethylamino) phosphoranilydenamino]phosphonium hydroxide, an alkylene oxide as propylene oxide is polyaddition-polymerized to an active hydrogen-bearing compound as dipropylene glycol. Then, the hydroxyl groups on the polyol containing 60-100 wt.% of the resultant polyoxyalkylene polyol are converted to alkali or alkaline earth metal alkoxide and the alkoxides are allowed to react with a compound bearing an unsaturated group to convert it to an unsaturated group whereby the objective polymer useful as a starting material for a sealing material is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyalkylene oxide polymer having excellent productivity and a moisture-curable composition containing the same. Specifically, the present invention provides a method for producing an unsaturated group-terminated polyalkylene oxide polymer,
The present invention relates to a method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer, and a moisture-curable composition containing the hydrolyzable silicon group-containing polyalkylene oxide polymer as a curing component. Moisture-curable compositions containing a hydrolyzable silicon-containing polyalkylene oxide polymer as a curing component are used for industrial parts such as one-part and two-part sealants, paints, flooring materials, adhesives, and rollers. .

[0002]

2. Description of the Related Art In the presence of a curing catalyst, an unsaturated group-terminated polyalkylene oxide polymer undergoes a molecular weight extension reaction and a crosslinking reaction to form a rubber-like elastic material. In addition, a hydrolyzable silicon-containing polyalkylene oxide polymer having a hydrolyzable group introduced into the terminal of an unsaturated group is also a rubber-like elastic material having a siloxane bond because a molecular weight extension reaction and a crosslinking reaction are promoted by moisture and a curing catalyst. Becomes Since these cured products are required to have properties such as flexibility, conformability to modification, and water resistance, polyoxyalkylene polyols containing propylene oxide as a main monomer are widely used as raw materials for the above-mentioned polyalkylene oxide polymers. ing. Polyoxyalkylene polyols are usually produced on an industrial scale by addition polymerization of an alkylene oxide to an active hydrogen compound in the presence of a potassium hydroxide (hereinafter abbreviated as KOH) catalyst. As the molecular weight increases, the side reaction of propylene oxide becomes remarkable, and the main reaction of molecular weight growth reaction is suppressed. Therefore, the maximum molecular weight of a commercially available polyoxypropylene diol having a small amount of propylene oxide by-product is about 3,000, and a cured product of a hydrolyzable silicon-containing polymer using such a polyol as a raw material has flexibility,
It is known that mechanical properties such as elongation are reduced. In order to solve these problems, studies have been made on a method for producing a high molecular weight polyoxyalkylene polyol.

[0003] Japanese Patent No. 2558165 discloses that the main chain is composed of a repeating unit represented by the formula -R ¹ -O- (where -R ¹ -is a divalent alkylene group having 2 to 8 carbon atoms). A polyalkylene oxide having a hydroxyl group at a terminal as a raw material, an alkali metal compound which reacts with an alkali metal and / or water to form an alkali metal hydroxide is added thereto, and the terminal hydroxyl group is converted to an alkali metal alkoxide;
Next, a method of increasing the molecular weight of a polyalkylene oxide by reacting with a polyvalent halogen compound is disclosed. As a result of investigations by the present inventors, in the method, unless an alkoxide agent (alkali metal compound) is used in an amount equivalent to one equivalent of a hydroxyl group in the polyoxyalkylene polyol, a high-molecular-weight polyoxyalkylene is obtained in good yield. Since a polyol cannot be obtained, and a step of alkoxidizing terminal hydroxyl groups and a step of increasing the molecular weight using a polyvalent halogen compound are required, the molecular weight distribution of the resulting polyoxyalkylene polyol is wide, and a high molecular weight polyoxyalkylene polyol is produced. It has been found that a considerable amount of reaction time is required in order to do so.

Japanese Patent Application Laid-Open No. 9-12863 discloses a double metal cyanide complex (Double Metal Cyan).
ide complex; hereinafter, abbreviated as DMC. A) an organic polymer having a hydrolyzable silicon group derived from a hydroxyl group-containing polyoxyalkylene polymer obtained by polymerizing an alkylene oxide with an initiator as a catalyst, and having a total amount of ionic impurities of 50 ppm or less; A room temperature curable composition containing an organotin carboxylic acid and an organic amine compound is exemplified. According to the publication, it is possible to obtain a hydroxyl group-containing polyoxyalkylene polymer having a lower Mw / Mn, a higher molecular weight, and a lower viscosity by using DMC than using a conventional alkali metal catalyst. (Column 4, rows 1-5).
However, US Pat. No. 5,300,535 teaches that high molecular weight polyoxyalkylene polyols catalyzed by DMC have high viscosities, and thus use acrylate or vinyl ether compounds as viscosity reducing agents. 2, 5 to column 4, 12), JP-A-8-1
No. 34203 describes that in polymerization of polyalkylene oxide using DMC, there is a problem that the polymerization condition width is narrow and the polymerization control is not easy (column 2, lines 20 to 23).

[0005] DMC exhibits excellent performance as a polymerization catalyst for propylene oxide. However, when addition polymerization of ethylene oxide as an alkylene oxide is carried out,
Deactivate DMC by reacting with oxygen-containing gas, oxidizing agent such as peroxide and sulfuric acid, separate catalyst residue from polyol, and further use alkali metal hydroxide such as KOH or alkoxide thereof. It is necessary to carry out addition polymerization of ethylene oxide (USP 5,144,093, USP
5,235,114). A method using an alkali metal alkoxide or an alkaline earth metal alkoxide in addition to an oxidizing agent in order to deactivate the DMC catalyst (Japanese Unexamined Patent Publication No.
No. 08833) and a treatment method using a strong base and an ion-exchange resin (US Pat. No. 4,355,188) have been proposed. When remaining in the alkylene polyol, there is a problem that the storage stability of the hydrolyzable silicon group-containing polyalkylene oxide polymer is deteriorated, or the action of the curing catalyst is hindered.

In the case of producing polyethers using DMC as described in JP-A-4-59825, a monoepoxide reaction occurs when the initiator (polymerization initiator) has a low molecular weight. However, there is a problem that the reaction speed is extremely low. In order to solve these problems, Japanese Patent Application Laid-Open No. Hei 4-59825 proposes to use, as a polymerization initiator, polyoxypropylene glycol obtained by addition-polymerizing propylene oxide in advance. In addition, the manufacturing process becomes complicated.

Japanese Patent Publication No. 13604/1994 teaches a method for producing a polyalkylene oxide having an unsaturated group at a molecular terminal and having a narrow molecular weight distribution. According to the publication, it is difficult to produce polyoxypropylene glycol having a molecular weight of 3,000 or more in ordinary anionic polymerization of propylene oxide with a KOH catalyst because a growing terminal causes a chain transfer reaction to a propylene oxide monomer. In addition, in order to have a problem that the molecular weight distribution is widened, and to obtain a polymer having a molecular weight of 3,000 or more, it is necessary to carry out a molecular chain extension reaction by reacting hydroxyl groups of polyoxypropylene glycol. It is described that a complicated reaction step is required, and that it is difficult to obtain a polymer having a narrow molecular weight distribution (column 3, lines 6 to 18). In order to solve these problems, in this publication, a propylene oxide is used in the presence of an active hydrogen-containing compound by using a complex catalyst obtained by reacting an organoaluminum compound with porphyrin (hereinafter abbreviated as aluminum porphyrin complex). A method for producing polypropylene oxide having a high molecular weight and a narrow molecular weight distribution by carrying out the polymerization of
JP-A-134203 describes that there is a problem that a polyalkylene oxide is colored under the influence of a metal porphyrin complex used as a catalyst (column 2,
Lines 12-19). As a result of the present inventors' polymerization of propylene oxide using an aluminum porphyrin complex, as taught in JP-A-8-134203, a polyoxyalkylene polyol synthesized with the catalyst is easily colored, In addition, there is a problem that it is not easy to remove the catalyst from the polyoxyalkylene polyol, and it has been difficult to synthesize a high-molecular-weight polyoxyalkylene polyol expected by the present inventors with high productivity and high yield.

In order to solve the problem of a method for producing a high molecular weight polyoxyalkylene polyol using a KOH catalyst, a molecular weight increasing reaction, a DMC catalyst and an aluminum porphyrin complex catalyst, Japanese Patent Application Laid-Open No. 8-134203 discloses a cesium-based catalyst. By polymerizing the monoepoxide, it is possible to polymerize by a simple operation as in the case of the conventional KOH catalyst, and by introducing a terminal unsaturated group into the polyalkylene oxide thus polymerized, the molecular weight distribution is reduced by a high molecular weight substance. That is, it is described that a highly practical unsaturated group-terminated polyalkylene oxide having an Mw / Mn close to 1 and little coloration can be obtained (column 2, lines 26 to 33). As a result of polymerization of propylene oxide using cesium hydroxide which is a cesium-based catalyst, the present inventors can obtain a relatively high molecular weight polyoxyalkylene polyol without coloring, but produce a polyol having a narrow molecular weight distribution. It has been found that a considerable amount of reaction time is required in order to do so. Furthermore, using a polyoxyalkylene polyol polymerized by each of the above-described methods, an unsaturated group-terminated polyalkylene oxide polymer and a hydrolyzable silicon group-containing polyalkylene oxide polymer were synthesized, and the physical properties of the cured product were examined. However, the mechanical properties expected by the present inventors could not be obtained.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain a high-molecular-weight polyoxyalkylene polyol having excellent productivity, low viscosity and no coloring in the polymerization of alkylene oxide. Method for producing unsaturated group-terminated polyalkylene oxide polymer using the polyoxyalkylene polyol, and hydrolysis excellent in storage stability obtained by reacting a silicon compound having a specific structure with an unsaturated group of the polymer An object of the present invention is to provide a method for producing a water-soluble silicon group-containing polyalkylene oxide polymer and a moisture-curable composition having excellent mechanical properties using the hydrolyzable silicon group-containing polymer as a curing component.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, produced a polyoxyalkylene polyol by subjecting an active hydrogen compound to addition polymerization of an alkylene oxide using a phosphazenium compound as a catalyst. After that, by converting the hydroxyl group in the polyol containing the polyoxyalkylene polyol to an unsaturated group, it is possible to obtain a high productivity, low viscosity and high molecular weight unsaturated group-terminated polyalkylene oxide polymer can be obtained. I found it. Further, they have found that a hydrolyzable silicon-containing polyalkylene oxide polymer having excellent storage stability can be obtained by reacting the unsaturated group-terminated polyalkylene oxide polymer with a silicon compound having a specific structure. . Furthermore, it has been found that a cured composition containing the hydrolyzable silicon group-containing polyalkylene oxide polymer gives a cured product having excellent flexibility, high elongation and good appearance.

That is, a first object of the present invention is obtained in (Step 1) a step of producing a polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound using a phosphazenium compound as a catalyst, and (Step 2) in Step 1. Polyoxyalkylene polyol from 60 to 100
Converting a hydroxyl group in a polyol containing 1% by weight to an unsaturated group.

A second object of the present invention is that the phosphazenium compound used in step 1 of the first object of the present invention is represented by the following chemical formula (3):

[0013]

Embedded image [A, b, c and d in the chemical formula (3) are each 0
And a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;
^r- represents an inorganic anion having a valence of r. In the presence of a salt of a phosphazenium cation and an inorganic anion represented by the formula (I) and an alkali metal or alkaline earth metal salt of an active hydrogen compound, or a compound represented by the chemical formula (4):

[0014]

Embedded image [The a, b, c and d in the chemical formula (4) are integers of 0 to 3, but not all of a, b, c and d are simultaneously 0. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion. ] The first object of the present invention is to produce an unsaturated group-terminated polyalkylene oxide polymer which is a phosphazenium compound represented by the formula:

[0015] A third object of the present invention is to provide an active hydrogen compound 1 in the presence of a phosphazenium compound and an active hydrogen compound.
The phosphazenium compound represented by the chemical formula (3) or (4) is prepared in a range of 5 × 10 ^-5 to 1 mol per mol, the reaction temperature is 15 to 160 ° C., and the maximum reaction pressure is 9 kgf / cm ^2. Production of an unsaturated group-terminated polyalkylene oxide polymer which is a first object of the present invention using a polyol containing 60 to 100% by weight of a polyoxyalkylene polyol obtained by subjecting an alkylene oxide to addition polymerization under a condition of (882 kPa). Method

A fourth object of the present invention is to provide an active hydrogen compound by addition polymerization of an alkylene oxide with a phosphazenium compound as a catalyst to obtain a hydroxyl value of 2 to 100 mg KOH /.
This is a method for producing a polyalkylene oxide polymer having an unsaturated group terminal, which is the first object of the present invention, using the polyoxyalkylene polyol as g.

A fifth object of the present invention is to provide a polyoxyalkylene polyol obtained by addition-polymerizing an active hydrogen compound with an alkylene oxide using a phosphazenium compound as a catalyst. The first object of the present invention is a method for producing a polyalkylene oxide polymer having an unsaturated group end, which is at least one kind of polyol selected from polyethylene adipate, polycarbonate polyol, hydrocarbon polyol and castor oil polyol.

A sixth object of the present invention is to provide (step 3) a step of producing a polyoxyalkylene polyol in which an alkylene oxide is addition-polymerized to an active hydrogen compound using a phosphazenium compound as a catalyst, and (step 4) a polyoxyalkylene polyol obtained in step 3. Converting a hydroxyl group in a polyol containing 60 to 100% by weight of an oxyalkylene polyol into an unsaturated group; (Step 5) converting the unsaturated group-terminated polyalkylene oxide polymer obtained in Step 4 into a compound represented by the chemical formula (1) ]

[0019]

Embedded image [R ¹ in the chemical formula (1) is a substituted or unsubstituted monovalent organic group or halogenated hydrocarbon group having 1 to 20 carbon atoms,
When two R ¹ are present, R ¹ may be different from each other. X is a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, Xs may be different from each other. a
Is an integer of 1 to 3. Or the chemical formula (2)

[0020]

Embedded image [R1 in the chemical formula (2) is a substituted or unsubstituted monovalent organic group or halogenated hydrocarbon group having 1 to 20 carbon atoms,
When two R ¹ are present, R ¹ may be different from each other. X is a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, Xs may be different from each other. a
Is an integer of 1 to 3. R ² is a divalent organic group having 1 to 20 carbon atoms, and W is a mercapto group. Reacting with at least one compound of the silicon compound represented by:
A method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer, comprising:

A seventh object of the present invention is that the alkylene oxide addition polymerization catalyst used in step 3 of the sixth object of the present invention is a phosphazenium compound of the second object of the present invention. This is a method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer.

An eighth object of the present invention is to provide a polyol wherein step 4 of the sixth object of the present invention contains 60 to 100% by weight of the polyoxyalkylene polyol produced by the method according to the third object of the present invention. A method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer according to the sixth object of the present invention using

A ninth object of the present invention is to provide a polyoxyalkylene polyol obtained by addition-polymerizing an active hydrogen compound with an alkylene oxide using the phosphazenium compound as the second object of the present invention as a catalyst and having a hydroxyl value of 2 to 100 mg KO.
A method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer according to the sixth object of the present invention, which is H / g.

A tenth object of the present invention is to provide a polyol which is used in addition to the polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound, using the phosphazenium compound in step 4 of the sixth object of the present invention as a catalyst, A sixth object of the present invention, which is at least one kind of polyol selected from liquid polybutadiene polyol, polytetramethylene glycol, polycaprolactone polyol, polyethylene adipate, polycarbonate polyol, hydrocarbon polyol and castor oil polyol. This is a method for producing a silicon group-containing polyalkylene oxide polymer.

An eleventh object of the present invention is to provide a sixth object of the present invention wherein the phosphorus content derived from the phosphazenium compound used in step 3 of the sixth object of the present invention is 100 ppm or less. This is a method for producing a silicon group-containing polyalkylene oxide polymer.

A twelfth object of the present invention is a moisture-curable composition comprising the hydrolyzable silicon-containing polyalkylene oxide polymer produced for the sixth object of the present invention as a curing component.

[0027]

First, step 1 will be described.
The phosphazenium compound in the present invention is represented by the following chemical formula (3)
Alternatively, the phosphazenium cation in the phosphazenium compound represented by the chemical formula (4) is represented by an extreme structural formula in which the positive charge is localized on a central phosphorus atom. Is drawn, and the positive charge is actually delocalized as a whole.

In the present invention, a in the phosphazenium cation represented by the chemical formula (3) or (4),
b, c and d are each an integer of 0 to 3. Preferably it is an integer of 0 to 2. However, in all cases, all are not simultaneously 0. More preferably, regardless of the order of a, b, c and d, (2,1,1,1), (1,
(1,1,1), (0,1,1,1), (0,0,1,
1) or a number in the combination of (0,0,0,1). More preferably, (1,1,1,1), (0,
1,1,1), (0,0,1,1) or (0,0,
(0, 1).

R in the phosphazenium cation represented by the chemical formula (3) or (4) in the present invention is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms. R is, for example, methyl, ethyl, n
-Propyl, isopropyl, allyl, n-butyl, se
c-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1
-Butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-
Methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-
It is selected from aliphatic or aromatic hydrocarbon groups such as octyl, 2-ethyl-1-hexyl, tert-octyl, nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl. Among these, an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, 1-octyl or tert-octyl is preferable, and a methyl group or ethyl Groups are more preferred.

In the case where two Rs on the same nitrogen atom in the phosphazenium cation combine to form a ring structure, the divalent hydrocarbon group on the nitrogen atom is 4 to 6 A divalent hydrocarbon group having a main chain composed of carbon atoms (the ring is a 5- to 7-membered ring containing a nitrogen atom), preferably, for example, tetramethylene, pentamethylene or hexamethylene; These are those whose main chains are substituted by an alkyl group such as methyl or ethyl. More preferably, it is a tetramethylene or pentamethylene group. Such a ring structure may be employed for all possible nitrogen atoms in the phosphazenium cation, or a part thereof may be employed.

In the present invention, T ^r− in the chemical formula (3) represents an inorganic anion having a valence of r. And r is an integer of 1 to 3. Such inorganic anions include, for example, boric acid, tetrafluoroboric acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, hydrohalic acid such as hydrochloric acid or hydriodic acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid Inorganic anions such as acids, hexafluorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothallic acid and perchloric acid are included. In addition, H as an inorganic anion
SO ₄ ^-, HCO ₃ ^- in some cases. In some cases, these inorganic anions can be exchanged with each other by an ion exchange reaction. Of these inorganic anions, boric acid,
Anions of inorganic acids such as tetrafluoroboric acid, hydrohalic acid, phosphoric acid, hexafluorophosphoric acid and perchloric acid are preferred, and chlorine anions are more preferred.

The synthesis of a salt of a phosphazenium cation represented by the chemical formula (3) and an inorganic anion according to the present invention includes the following method as a general example. (A) One equivalent and three equivalents of a disubstituted amine (HN
R ₂ ) and 1 equivalent of ammonia, followed by treatment with a base to give a compound of the formula (5)

[0033]

Embedded image 2,2,2-tris (disubstituted amino) -2λ represented by
Synthesize ⁵ -phosphazene.

(B) bis (disubstituted amino) obtained by reacting this phosphazene compound [formula (5)] with bis (disubstituted amino) phosphorochloridate {(R ₂ N) ₂ P (O) Cl} ) Tris (disubstituted amino) phosphoranylideneaminophosphine oxide is chlorinated with phosphorus oxychloride, which is then reacted with ammonia, treated with a base, and treated with a chemical formula (6).

[0035]

Embedded image To obtain 2,2,4,4-pentakis (disubstituted amino) -2λ ⁵ , 4λ ⁵ -phosphazene.

(C) This phosphazene compound [Chemical formula (6)] is used in place of the phosphazene compound [Chemical formula (5)] used in (b), and reacted by the same operation as (b) to obtain a compound represented by the chemical formula (C). 7) [Chemical formula 9]

[0037]

Embedded image [In formula, q represents the integer of 0 and 1-3. When q is 0, it is a disubstituted amine, 1 is the compound of formula (5), 2 is the compound of formula (6), and 3 is the oligophosphazene obtained in (c). To obtain an oligophosphazene wherein q is 3.

(D) reacting the compounds of formula (7) of different q and / or R sequentially or simultaneously with the same compounds of formula (7) of the same q and R with 4 equivalents of phosphorus pentachloride, In the chemical formula (3), r = 1, Tr− = Cl
^- salts with the desired phosphazenium cation and chlorine anion is obtained is. When it is desired to obtain a salt of an inorganic anion other than a chloride anion, ion exchange is performed by a usual method, for example, a method of treating with a salt of an alkali metal cation and a desired inorganic anion or a method of using an ion exchange resin. be able to. Thus, a salt of a general phosphazenium cation represented by the chemical formula (3) and an inorganic anion is obtained.

The alkali metal or alkaline earth metal salt of the active hydrogen compound coexisted with the chemical formula (3) is obtained by dissociating the active hydrogen of the active hydrogen compound as a hydrogen ion and replacing it with an alkali metal or alkaline earth metal ion. It is a salt in the form. As the active hydrogen compound giving such a salt, preferred are monohydric unsaturated group-containing alcohols such as allyl alcohol and propenyl alcohol, dihydric or higher alcohols, phenol compounds, polyamines and alkanolamines. For example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , Neopentyl glycol, methylpentadiol, 1,6-hexanediol, dihydric alcohols such as 1,4-cyclohexanediol, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, glycerin, diglycerin, triethanolamine Methylolpropane, pentaerythritol,
Dipentaerythritol, glucose, sorbitol,
Polyhydric alcohols such as sucrose and methylglycoside, phenol compounds such as bisphenol A, bisphenol F, bisphenol S, resorcin and hydroquinone, and aliphatic amines such as ethylenediamine, di (2-aminoethyl) amine and hexanemethylenediamine. No.

Alternatively, polyethylene glycol having a molecular weight of 100 to 1,000 can be used. These active hydrogen compounds can be used in combination of two or more. Further, a compound obtained by addition polymerization of an alkylene oxide to these active hydrogen compounds by a conventionally known method in an amount of about 2 to 8 mol per equivalent of an active hydrogen group can also be used. Preferred among these active hydrogen compounds are compounds having 1 to 4 active hydrogen groups in one molecule.

In order to obtain a salt of an alkali metal or an alkaline earth metal from these active hydrogen compounds, the active hydrogen compound and a metal selected from alkali metals or alkaline earth metals, or a basic alkali metal or A usual method of reacting with a compound of an alkaline earth metal is used. Examples of the metal selected from alkali metals or alkaline earth metals include lithium metal, sodium metal, potassium metal, cesium metal, rubidium metal, magnesium metal, calcium metal, strontium metal, and metal barium, and the like. As the alkali metal or alkaline earth metal compound,
Amides of alkali metals or alkaline earth metals such as sodium amide, potassium amide, magnesium amide or barium amide; n-propyl lithium, n-butyl lithium, vinyl lithium, cyclopentadienyl lithium, ethynyl sodium, n- Butyl sodium, phenyl sodium, cyclopentadienyl sodium, ethyl potassium, cyclopentadienyl potassium, phenyl potassium, benzyl potassium, diethyl magnesium, ethyl isopropyl magnesium,
Organic alkalis such as di-n-butylmagnesium, di-tert-butylmagnesium, vinylmagnesium bromide, phenylmagnesium bromide, dicyclopentadienylmagnesium, dimethylcalcium, potassium acetylide, ethylstrontium bromide, and phenylbarium iodide A metal or alkaline earth metal compound, sodium hydride, potassium hydride, a hydride compound of an alkali metal or alkaline earth metal such as calcium hydride, sodium hydroxide, potassium hydroxide,
Lithium hydroxide, rubidium hydroxide, cesium hydroxide,
Magnesium hydroxide, calcium hydroxide, alkali metal or alkaline earth metal hydroxides such as strontium hydroxide or barium hydroxide, lithium carbonate,
Alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate and barium carbonate, and hydrogencarbonate such as potassium hydrogencarbonate, sodium hydrogencarbonate and cesium hydrogencarbonate Salt and the like.

A metal selected from these alkali metals or alkaline earth metals, or a compound of a basic alkali metal or alkaline earth metal is selected according to the acidity of the active hydrogen compound. The alkali metal or alkaline earth metal salt of the active hydrogen compound thus obtained acts as a basic alkali metal or alkaline earth metal compound, and the other active hydrogen compound is converted to the alkali metal or alkaline earth metal. In some cases, it can be converted into a salt of a class of metals.

In an active hydrogen compound having a plurality of active hydrogens, all of the active hydrogens are eliminated to form a metal selected from alkali metals or alkaline earth metals or a basic alkali metal or alkaline earth metal. In some cases, the compound leads to an anion, but in some cases, only a part of the compound is eliminated to become an anion. Of these alkali metal or alkaline earth metal salts of active hydrogen compounds, alkali metal salts of active hydrogen compounds are preferred, and the cation of the alkali metal salt of the active hydrogen compound is lithium, sodium, potassium, rubidium or cesium. The cation chosen is more preferred.

The alkylene oxide is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (3) with an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound. At this time, a salt of a cation of an alkali metal or an alkaline earth metal and an inorganic anion is by-produced. If the by-product salt inhibits the polymerization reaction, the salt is removed by a method such as filtration prior to the polymerization reaction. You can keep it.

Further, a phosphazenium salt of an active hydrogen compound derived from a salt represented by the chemical formula (3) and an alkali metal or alkaline earth metal salt of an active hydrogen compound is isolated in advance, and an alkylene oxide is isolated in the presence of the phosphazenium salt. Can also be polymerized.

As a method for previously obtaining a phosphazenium salt of the active hydrogen compound, a salt represented by the chemical formula (3) is reacted with an alkali metal or alkaline earth metal salt of the active hydrogen compound. The use ratio of the salt is not particularly limited as long as the desired salt is formed, and there is no particular problem even if any salt is excessive. Usually, the amount of the alkali metal or alkaline earth metal salt of the active hydrogen compound to be used is 0.2 to 5 equivalents, preferably 0 to 1 equivalent of the salt of the phosphazenium cation and the inorganic anion. 0.5 to 3 equivalents, more preferably 0.7 to
It is in the range of 1.5 equivalents.

It is also possible to use a solvent to make the contact between them effective. Any solvent may be used as long as it does not inhibit the reaction. Examples thereof include water, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, n-pentane, n-hexane and cyclohexane. Aliphatic or aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform, bromoform, carbon tetrachloride, dichloroethane, orthodichlorobenzene, ethyl acetate, methyl propionate or benzoic acid Esters such as methyl, diethyl ether, tetrahydrofuran,
Ethers such as 1,4-dioxane, ethylene glycol dimethyl ether or triethylene glycol dimethyl ether, nitriles such as acetonitrile or propionitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide or 1,3 Polar aprotic solvents such as -dimethyl-2-imidazolidinone. These solvents are selected depending on the chemical stability of the raw material salt used in the reaction. Preferably, aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether, nitriles such as acetonitrile, N, N -Dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide or 1,3-dimethyl-
Polar aprotic solvents such as 2-imidazolidinone; The solvents may be used alone or in combination of two or more. It is preferable that the raw material salt is dissolved, but it may be in a suspended state. The temperature of this reaction is not uniform depending on the kind, amount and concentration of the salt used, but is usually 150 ° C. or lower, preferably −78 to 80 ° C., more preferably 0 ° C.
~ 50 ° C. The reaction pressure can be reduced, normal pressure or increased pressure, preferably 0.1 to 10 k
gf / cm ² (absolute pressure, the same applies hereinafter to 9.8 to 980 kP
a), more preferably 1 to 3 kgf / cm ² (9
8 to 294 kPa). The reaction time is usually 1
Minutes to 24 hours, preferably 1 minute to 10 hours, more preferably 5 minutes to 6 hours.

When isolating the target phosphazenium salt of the active hydrogen compound from the reaction solution, a conventional method combining conventional means is used. The method is not uniform depending on the type of the target salt, the type and excess ratio of the salt of the two raw materials used, the type and amount of the solvent used, and the like. Usually, the by-product salt of an alkali metal or alkaline earth metal cation and an inorganic anion is precipitated as a solid, so it is used as it is or after a slight concentration, and then subjected to solid-liquid separation by filtration or centrifugation. Then, this is removed, and the liquid is concentrated to dryness to obtain a target salt. If the by-produced salt is still dissolved after concentration, a poor solvent is added as it is or after concentration to precipitate either the by-produced salt or the target salt, or after concentration to dryness, one is extracted. It can be separated by such a method. When the salt of the raw material used in excess is mixed in a large amount with the target salt, the salt can be extracted as it is or after redissolution with another suitable solvent, and separated. Further, if necessary, it can be purified by recrystallization or column chromatography. The desired salt is usually obtained as a high viscosity liquid or solid.

An alkylene oxide is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (3) and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound. At this time,
An active hydrogen compound of the same or different type as the active hydrogen compound constituting the alkali metal or alkaline earth metal salt of the active hydrogen compound or the phosphazenium salt of the active hydrogen compound derived therefrom may be present in the reaction system. When the salt is present, the amount thereof is not particularly limited, but is 1 × 10 ^{−15 to} 5 × 1 with respect to 1 mol of the alkylene oxide.
0 ^-1 mol, preferably in the range of 1 × 10 ^-7 to 1 × 10 ^-1 mol.

In another case of the method for producing the polyoxyalkylene polyol of the present invention, that is, the chemical formula (4)
The case where a polyoxyalkylene polyol is produced by addition-polymerizing an alkylene oxide in the presence of a phosphazenium compound represented by and an active hydrogen compound will be described. Q ⁻ in the phosphazenium compound represented by the chemical formula (4) is a hydroxy anion, an alkoxy anion,
An anion selected from the group consisting of an aryloxy anion and a carboxy anion.

[0051] These Q ^- of, preferably, hydroxy anions, such as methanol, ethanol,
An alkoxy anion derived from an aliphatic alcohol such as n-propanol and isopropanol, for example, an aryloxy anion derived from an aromatic hydroxy compound such as phenol and cresol, and a carboxy derived from formic acid, acetic acid, propionic acid, etc. Is an anion.

Of these, hydroxy anions such as alkoxy anions derived from low boiling alkyl alcohols such as methanol, ethanol and n-propanol, and carboxy anions derived from carboxylic acids such as formic acid and acetic acid are more preferred. More preferred are a hydroxy anion, a methoxy anion, an ethoxy anion and an acetate anion. These phosphazenium compounds may be used alone or as a mixture of two or more.

As a general method for synthesizing the phosphazenium compound represented by the chemical formula (4), first, in the same manner as the method for synthesizing the salt represented by the chemical formula (3), r = 1 in the chemical formula (3). , A phosphazenium chloride wherein T ^r− = Cl ⁻ is synthesized. Then, the phosphazenium chloride is treated with a hydroxide, alkoxide, aryloxide or carboxide of, for example, an alkali metal or an alkaline earth metal, or a method using an ion exchange resin to convert the chloride anion into the desired anion Q. ^-
Can be replaced by Thus, a general phosphazenium compound represented by the chemical formula (4) is obtained.

The active hydrogen compound coexisting with the chemical formula (4) is the same as described in detail above as the active hydrogen compound which gives a salt of an alkali metal or an alkaline earth metal of the active hydrogen compound.

In the method of the present invention in which a monoepoxide compound is subjected to addition polymerization in the presence of a phosphazenium compound represented by the chemical formula (4) and an active hydrogen compound, the excess of the active hydrogen compound usually used in excess remains as it is. However, besides this, water, alcohol, aromatic hydroxy compound or carboxylic acid is by-produced depending on the type of phosphazenium compound. If necessary, these by-products are removed prior to the addition polymerization reaction of the alkylene oxide. Depending on the physical properties of these by-products, conventional methods such as a method of distilling off by heating or reduced pressure, a method of passing an inert gas, and a method of using an adsorbent are used.

The alkylene oxide to be addition-polymerized to the active hydrogen compound in the presence of the phosphazenium compound includes propylene oxide, ethylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, Allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, s
ec-butylphenol glycidyl ether, 2-methyloctyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, trifluoropropylene oxide and the like. These may be used in combination of two or more. Of these, propylene oxide, butylene oxide, styrene oxide and ethylene oxide are preferred. Particularly preferred are propylene oxide and ethylene oxide.

The production of the polyoxyalkylene polyol in the present invention is usually carried out under the following conditions. That is, the phosphazenium compound represented by the chemical formula (3) or (4) per mol of the active hydrogen compound is 5 × 10 ⁻⁵ to 1 mol, preferably 1 × 10 ⁻⁴ to 1 × 10 5.
^-1 mol, more preferably 1 × 10 ⁻³ to 8 × 10 ⁻² mol. When increasing the molecular weight of the polyoxyalkylene polyol, it is preferable to increase the concentration of the phosphazenium compound relative to the active hydrogen compound within the above range. The phosphazenium compound represented by the chemical formula (3) or (4) is 5 × with respect to 1 mol of the active hydrogen compound.
If the amount is less than 10 ^-5 mol, the polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. When the amount of the phosphazenium compound represented by the chemical formula (3) or (4) is more than 1 mol per 1 mol of the active hydrogen compound, the cost of the phosphazenium compound in the production cost of the polyalkylene oxide polymer increases.

The reaction temperature of the alkylene oxide is usually 15 to 160 ° C., preferably 40 to 150 ° C.
More preferably, it is in the range of 50 to 130 ° C. When the reaction temperature of the alkylene oxide is lower than the above range, the concentration of the phosphazenium compound with respect to the active hydrogen compound is preferably increased within the range described above. The method of supplying the alkylene oxide to the active hydrogen compound using the phosphazenium compound charged to the pressure-resistant reactor as a catalyst is a method of supplying a part of the required amount of the alkylene oxide at a time, or continuously or intermittently supplying the alkylene oxide. A supply method is used. In a method in which a part of the required amount of alkylene oxide is supplied collectively, a method in which the reaction temperature at the beginning of the alkylene oxide polymerization reaction is set to a lower temperature within the above range and the reaction temperature is gradually increased after charging the alkylene oxide is preferable. . When the reaction temperature is lower than 15 ° C., the polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. When the reaction temperature exceeds 160 ° C., when propylene oxide is used as the alkylene oxide, the molecular weight distribution of the polyoxyalkylene polyol becomes wide.

The maximum pressure during the reaction of the alkylene oxide is preferably 9 kgf / cm ² (882 kPa, absolute pressure, hereinafter the same). Usually, the reaction of alkylene oxide is carried out by a pressure-resistant reactor. The reaction of the alkylene oxide may be started from a reduced pressure state or from an atmospheric pressure state. When starting the reaction from atmospheric pressure,
It is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. Maximum reaction pressure of alkylene oxide is 9k
If it exceeds gf / cm ² (882 kPa), the molecular weight distribution of the polyoxyalkylene polyol becomes wide. The maximum reaction pressure is preferably 8 kgf / cm ² (784 kP
a), more preferably 6 kgf / cm ² (588 kP
a). When propylene oxide is used as the alkylene oxide, the maximum reaction pressure is 6 kgf
/ Cm ² (588 kPa) is preferred. In the alkylene oxide addition polymerization reaction, a solvent can be used if necessary. Examples of the solvent to be used include aliphatic hydrocarbons such as pentane, hexane, and peptane; ethers such as tetrahydrofuran and dioxane; and aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide. . When a solvent is used, a method of collecting and reusing the solvent after the production is desirable in order not to increase the production cost of the polyoxyalkylene polyol.

The hydroxyl value (hereinafter abbreviated as OHV) of the polyoxyalkylene polyol produced by the method described above is 2 to 100 mgKOH / g. Preferably, it is 5 to 80 mgKOH / g, more preferably 8 to 5 mgKOH / g.
0 mgKOH / g. When the OHV is smaller than 2 mgKOH / g, the production time of the polyoxyalkylene polyol becomes longer. When the OHV is larger than 100 mgKOH / g, the molecular weight distribution of the polyoxyalkylene polyol which we are interested in has no significant difference from the polyoxyalkylene polyol obtained by the conventional KOH catalyst system.

The head-to-tail (H
The head-to-tail binding selectivity is 95% or more. Head-to-Tai
l) If the bond selectivity is less than 95%, the viscosity of the polyoxyalkylene polyol increases.

After addition polymerization of an alkylene oxide to an active hydrogen compound using a phosphazenium compound as a catalyst,
The polyoxyalkylene polyol can be used in Step 2 without removing the phosphazenium compound from the polyoxyalkylene polyol.
When removing the phosphazenium compound from the polyoxyalkylene polyol, usually, hydrochloric acid, phosphoric acid, nitric acid,
Treatment with at least one neutralizing agent selected from inorganic salts such as pyrophosphoric acid, sodium acid pyrophosphate and sulfuric acid, organic acids such as formic acid, acetic acid, oxalic acid, succinic acid, phthalic acid, maleic acid and salicylic acid, and carbon dioxide. Method, adsorption removal method of phosphazenium compound by ion exchange resin, or tomix series, for example, tomix A
D-600, Tomix AD-700 (manufactured by Tomita Pharmaceutical),
Kyoword series, for example, Kyoword 400, Kyoword 500, Kyoword 600, Kyoword 700 (manufactured by Kyowa Chemical Industry), MAGNESOL (DAL
The phosphazenium compound is removed by a method of treating with an adsorbent commercially available under various trade names such as LAS Co., Ltd., and by using the above-described neutralization treatment and the adsorbent in combination. Further, it can also be used after purifying the polyoxyalkylene polyol using water, an organic solvent inert to the polyoxyalkylene polyol, and a mixture thereof.

Next, step 2 will be described. Step 2
Is a step of converting a hydroxyl group in a polyol containing 60 to 100% by weight of the polyoxyalkylene polyol obtained in Step 1 described above into an unsaturated group.

Polyols to be used in addition to the polyoxyalkylene polyol catalyzed by the phosphazenium compound of the present invention include liquid polybutadiene polyol, polytetramethylene glycol, polycaprolactone polyol,
It is at least one kind of polyol selected from polyethylene adipate, polycarbonate polyol, hydrocarbon-based polyol and castor oil-based polyol. Among these, preferred polyols are liquid polybutadiene polyol and polytetramethylene glycol. The molecular weight of these polyols ranges from 1000 to 10,000. When the amount of the polyoxyalkylene polyol using the phosphazenium compound of the present invention as a catalyst is less than 60% by weight, the mechanical properties such as flexibility and extensibility of the resulting polyalkylene oxide polymer decrease.

In order to convert the hydroxyl group in the polyol to an unsaturated group, for example, a method in which the hydroxyl group is converted into an alkoxide of an alkali metal or an alkaline earth metal and then reacted with a compound having an unsaturated group can be exemplified. However, the present invention is not limited only to the method.

Compounds used for converting a hydroxyl group in a polyol into an alkoxide of an alkali metal or an alkaline earth metal include lithium metal, sodium metal, potassium metal, cesium metal, rubidium metal, magnesium metal, calcium metal, and metal metal. Examples of the basic alkali metal or alkaline earth metal compound include amides of alkali metal or alkaline earth metal such as sodium amide, potassium amide, magnesium amide or barium amide, and n -Propyl lithium, n-butyl lithium, vinyl lithium, cyclopentadienyl lithium, ethynyl sodium, n-butyl sodium, phenyl sodium, cyclopentadienyl sodium, ethyl potassium , Cyclopentadienyl potassium, phenyl potassium, potassium benzyl, diethyl magnesium, ethyl isopropyl magnesium, di -n
Organic alkali metals or alkalis such as -butylmagnesium, di-tert-butylmagnesium, vinylmagnesium bromide, phenylmagnesium bromide, dicyclopentadienylmagnesium, dimethylcalcium, potassium acetylide, ethylstrontium bromide, and phenylbarium iodide Earth metal compounds, such as sodium hydride, potassium hydride, calcium hydride, etc., and sodium or potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide Is a hydroxide of an alkali metal or alkaline earth metal such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide, such as sodium hydride, potassium hydride, etc. Alkali metal hydrides, sodium methylate, potassium methylate, cesium methylate,
Alkali metal alkoxides such as sodium ethylate, potassium ethylate and cesium ethylate; or alkali metal or alkaline earth metals such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate and barium carbonate And hydrogencarbonate such as potassium hydrogencarbonate, sodium hydrogencarbonate and cesium hydrogencarbonate. Among these compounds, preferred are hydroxides of alkali metals or alkaline earth metals, alkali metal hydrides and alkali metal alkoxides, most preferably sodium hydride, alkali metal hydrides such as potassium hydride and sodium. Alkali metal alkoxides such as methylate, potassium methylate, cesium methylate, sodium ethylate, potassium ethylate and cesium ethylate.

The alkali metal or alkaline earth metal compound to be used is usually 0.8 to 1.5 equivalents, preferably 0.9 to 1.5 equivalents to 1 equivalent of the hydroxyl group in the polyol.
1.4 equivalents, most preferably 0.95 to 1.3 equivalents. When the amount of the alkali metal or alkaline earth metal compound used is less than 0.8 equivalent relative to 1 equivalent of the hydroxyl group in the polyol, the residual ratio of the hydroxyl group in the unsaturated group-terminated polyalkylene oxide polymer increases. On the other hand, when the amount is more than 1.5 equivalents, the amount of by-product salt increases in a metal removing step after the reaction with the compound having an unsaturated group.

The reaction conditions for converting a hydroxyl group into an alkoxide group are not particularly limited.
0-150 ° C., pressure 50 mmHgabs. (6650
Pa) or less, more preferably 20 mmHgabs. (2
660 Pa) or less, most preferably 10 mmHgab
s. (1330 Pa) or less. The reaction time depends on the reaction scale, but is usually 1 hour to 10 hours.

After converting the hydroxyl group in the polyol to an alkoxide group, the polyol is reacted with a compound having an unsaturated group.
As the compound having an unsaturated group, for example, a compound represented by the following chemical formula (8):

[0070]

Embedded image [In the chemical formula (8), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. R ³ is a divalent organic group, X
Is a halogen atom. ] Is exemplified. Examples of such compounds include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene,
Allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of the compound having an unsaturated group used is 0.8 to 1.9 mol, preferably 0.85 to 1.7 mol, most preferably 0.9 mol to 1 equivalent of the hydroxyl group in the polyol.
１．５1.5 mol. If the amount of the compound is less than 0.8 mol per equivalent of hydroxyl group in the polyol, the unsaturated group content in the unsaturated group-terminated polyalkylene oxide polymer decreases. On the other hand, when the amount exceeds 1.9 mol, the number of compounds having an unreacted unsaturated group increases.

The reaction conditions between the alkoxide-terminated polyalkylene oxide polymer and the compound having an unsaturated group are as follows:
Although not particularly limited, the reaction temperature is usually 20
-160 ° C, preferably 50-150 ° C, most preferably 70-150 ° C. Under atmospheric pressure or 9kg /
The reaction is performed under a pressure of not more than cm ² (882 kPa). The reaction is preferably performed in the presence of an inert gas such as nitrogen or helium for the purpose of preventing coloring of the polyalkylene oxide polymer. The reaction is continued until the terminal alkoxide group of the polymer is converted into an unsaturated group. The reaction time is usually 1 hour to 7 hours, depending on the reaction scale.

An unsaturated group-terminated polyalkylene oxide polymer is produced through Steps 1 and 2, and the alkali metal or alkaline earth metal compound used for introducing the unsaturated group into the polyalkylene oxide polymer is removed. Is preferred. The method for removing an alkali metal or alkaline earth metal compound from an unsaturated group-terminated polyalkylene oxide polymer is usually carried out by using an acid which uses an organic solvent inert to the polymer, water and the alkali metal or alkaline earth metal compound. It is preferably carried out by a neutralized water washing method.

To 100 parts by weight of an unsaturated group-terminated polyalkylene oxide polymer containing an alkali metal or alkaline earth metal compound, the polymer, water and an organic solvent inert to the alkali metal or alkaline earth metal compound are added. After adding 1 to 600 parts by weight and dissolving uniformly, water is added in an amount of 50 to 600 parts by weight based on 100 parts by weight of the unsaturated group-terminated polyalkylene oxide polymer.
A method is preferred in which at least one neutralizing agent selected from inorganic acids or organic acids is added so that H is 4 or less, preferably pH is 3 or less, and the mixture is stirred and separated to form a liquid. A polymer, an organic solvent and water may be simultaneously charged and a predetermined amount of a neutralizing agent may be added.

As the organic solvent to be used, any solvent may be used as long as it is inert to the unsaturated group-terminated polyalkylene oxide polymer, water and the alkali metal or alkaline earth metal compound. Such organic solvents include, for example, aliphatic, alicyclic, aromatic hydrocarbons, ketones, alcohols, ethers and halides thereof, for example, butanes, pentanes, hexanes, Heptanes, octanes, nonanes,
Decane, dodecane, cyclohexane, cyclopentane, benzene, toluene, xylene, acetone, methyl ethyl ketone, isopropanol, butanol, pentanol, methyl ether, ethyl ether, isopropyl ether, methylene chloride, chloroform and the like. These organic solvents may be used alone or in combination of two or more.

As the neutralizing agent, for example, hydrochloric acid, phosphoric acid,
Nitric acid, pyrophosphoric acid, sodium acid pyrophosphate, sulfuric acid,
Inorganic salts such as sodium phosphite and sodium sulfite; and organic acids such as formic acid, acetic acid, oxalic acid, acetic acid, succinic acid, phthalic acid, maleic acid, salicylic acid, and adipic acid. These neutralizing agents may be used alone or in combination of two or more. The neutralizing agent is added until the pH of the aqueous layer is 4 or less, preferably 3 or less. When the pH of the aqueous layer is higher than 4, the separation time between the unsaturated group-terminated polyalkylene oxide polymer layer and the aqueous layer becomes longer.

For recovering the unsaturated group-terminated polyalkylene oxide polymer layer from the aqueous layer, a method used for general liquid separation such as centrifugation and standing liquid separation can be applied. Although the alkali metal or alkaline earth metal compound and the neutralizing agent are extracted in the aqueous layer, the separated unsaturated group-terminated polyalkylene oxide polymer layer also contains a small amount of water, an alkali metal or alkaline earth metal compound, Since a neutralizing agent or an organic solvent is contained, the above-mentioned adsorbent, for example, Tomix AD-600, Tomix A
D-700 (manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward series, such as Kyoward 400, Kyoward 500, Kyoward 600, Kyoward 700 (Kyowa Chemical Industry), MAGNESOL (manufactured by DALLAS), and the like. It is preferable to purify the unsaturated group-terminated polyalkylene oxide polymer by performing dehydration under reduced pressure and organic solvent treatment after performing the treatment with the adsorbent.
When the adsorbent is used, it is usually used in an amount of 0.01 to 100 parts by weight of the unsaturated group-terminated polyalkylene oxide polymer.
Use ~ 3 parts by weight of adsorbent. The conditions for the reduced pressure treatment are not particularly limited, but are usually 50 to 160 ° C. and the pressure is 50 mmHgabs. (6650 Pa) or less, preferably 10 mmHgabs. (1330 Pa) Performed for 2 to 8 hours under the following conditions.

The unsaturated group-terminated polyalkylene oxide polymer thus obtained has a molecular weight of 3,000 to 3,000.
A range of 0.000 is preferred. Further, the content of phosphorus derived from the phosphazenium compound used as a catalyst for the polyoxyalkylene polyol is preferably 100 ppm or less. More preferably, it is 80 ppm or less. The polymer can be copolymerized with a vinyl monomer or the like by utilizing the reactivity of the unsaturated group, and can be made into a rubber-like elastic body using a curable resin or a curing catalyst. Alternatively, it can be used as a resin modifier as a high molecular weight plasticizer. Further, it can be used as a raw material of a hydrolyzable silicon group-containing polyalkylene oxide polymer in which an unsaturated group terminal is converted into a hydrolyzable silicon group.

Next, a method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer will be described. The polymer is obtained by (step 3) a step of producing a polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound using a phosphazenium compound as a catalyst; (Step 5) converting the unsaturated group-terminated polyalkylene oxide polymer obtained in step 4 into a silicon represented by the chemical formula (1) or (2). It is prepared from the step of reacting a compound with at least one compound.

Steps 3 and 4 are the same as the methods of Steps 1 and 2 described above. In step 5, a silicon compound having a specific structure represented by the chemical formula (1) or (2) is reacted with an unsaturated group-terminated polyalkylene oxide polymer. R ¹ in the chemical formula (1) is a substituted or unsubstituted monovalent organic group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and when two or more R ¹ are present,
R ¹ may be different from each other. Examples of the organic group include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, and 3-
Pentyl, 2-methyl-1-butyl, isopentyl, t
ert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl- 1-
Examples thereof include aliphatic or aromatic hydrocarbon groups such as hexyl, tert-octyl, nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl. As the halogenated hydrocarbon group, for example, an alkyl group having one or more chlorine atoms, fluorine atoms and the like and having the above carbon number is preferable. Further, R ¹ may be a triorganosiloxy group.

X in the chemical formula (1) is a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, Xs may be different from each other. As a specific example of X, for example,
Hydroxyl group, halogen group, alkoxy group such as methoxy group and ethoxy group, acyloxy group such as acetoxy group, ketoxime group such as acetoxymate group and dimethylketoxime group, amino group, amide group, aminooxy group, mercapto group, alkenyl Oxy group and the like. Particularly preferred X
Is a methoxy group or an ethoxy group. A is 1 to 3
Is an integer. In particular, when X is a hydroxyl group, a is an integer of 1 to 2, and preferably a is 1.

Examples of the silicon hydride compound represented by the chemical formula (1) include silicon halide compounds such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane, and trimethoxysilane and triethoxysilane. , Methylmethoxysilane, phenyldimethoxysilane, 1,3,3,5
Alkoxysilicon compounds such as 5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane, acyloxysilicon compounds such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane, bis (dimethylketoximate) methylsilane, bis (Cyclohexyl ketoximate) methyl silane, ketoximate silicon compounds such as bis (diethyl ketoximate) trimethylsiloxysilane, dimethylsilane, trimethylsiloxymethylsilane, 1,1-dimethyl-2,2-dimethyldisiloxane and the like Examples thereof include silicon compounds and alkenyloxysilanes such as methyltri (isopropenyloxy) silane, but are not limited to these compounds. These compounds may be used alone or in combination of two or more.

The amount of the silicon compound represented by the chemical formula (1) is 0.9 to 2.5 mol, preferably 0.1 to 2.5 mol per equivalent of the unsaturated group in the unsaturated group-terminated polyalkylene oxide polymer. 9-2.2 mol, most preferably 1.0-
1.9 mol. The reaction between the unsaturated group-terminated polyalkylene oxide polymer and the silicon compound represented by the chemical formula (1) is usually performed in the presence of an inert gas such as nitrogen or helium in the presence of a conventionally known platinum compound, rhodium compound, The reaction is carried out using a Group VIII transition metal compound such as a palladium compound as a catalyst at a reaction temperature of 40 to 130 ° C. for 1 hour to 8 hours, depending on the reaction scale. At this time, it may be under atmospheric pressure or under pressure. Examples of the catalyst include chloroplatinic acid, fine-particle platinum, fine-particle platinum adsorbed on a carbon powder carrier, platinum-alumina, and platinum-olefin complex. These catalysts are used in an amount of 0.001 to 3 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the unsaturated group-terminated polyalkylene oxide polymer.
Use 1 to 2 parts by weight. Further, as the unsaturated group-terminated polyalkylene oxide polymer to be reacted with the silicon compound, two or more kinds of polymers having different molecular weights may be used in combination.

It is desirable to remove the catalyst remaining in the hydrolyzable silicon-containing polyalkylene oxide polymer obtained by the above-described method. The method for removing the catalyst is not particularly limited, but is generally performed by filtration, filtration after the adsorbent treatment described above, or the like. When the catalyst is used in the form of a solution, the solvent is preferably removed by a reduced pressure treatment. Also, when an unreacted silicon compound is present, it is recovered by a reduced pressure treatment operation or the like. Since the chain extension reaction or the cross-linking reaction of the hydrolyzable silicon group-containing polyalkylene oxide polymer proceeds due to the moisture in the air, it is preferable to carry out the dehydration operation under reduced pressure again after the above-mentioned operation.

Next, the reaction between the silicon compound represented by the chemical formula (2) and the unsaturated group-terminated polyalkylene oxide polymer will be described. R ¹ , X and a in the chemical formula (2) are the same as those described in detail in the chemical formula (1). R ² in the chemical formula (2) is a divalent organic group having 1 to 20 carbon atoms,
W is a mercapto group. The reaction conditions and purification conditions for the silicon compound and the unsaturated group-terminated polyalkylene oxide polymer are the same as those in the method using the silicon compound of the above-mentioned chemical formula (1).

In the hydrolyzable silicon group-containing polyalkylene oxide polymer produced by such a method,
Some or all of the hydrolyzable group X can be further converted to another hydrolyzable group or hydroxyl group. For example, when X is a halogen group, it can be converted to an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group or a hydroxyl group. 1 in the hydrolyzable silicon group-containing polyalkylene oxide polymer
The average number of hydrolyzable silicon groups in the molecule is 1.6 or more,
In particular, it is preferably 1.9 or more. The molecular weight of the polymer is 3,000 to 35,000, preferably 5,000 to 28,000, and most preferably 5,000 in order to improve workability and physical properties of the obtained cured product.
~ 25,000. Furthermore, the content of phosphorus derived from the phosphazenium compound in the hydrolyzable silicon group-containing polyalkylene oxide polymer after the purification step is 100 p.
pm or less, preferably 80 ppm or less. The content of phosphorus derived from the phosphazenium compound in the hydrolyzable silicon-containing polyalkylene oxide polymer is 100 pp
If it exceeds m, the change in viscosity of the polymer over time will increase.

Next, a moisture-curable composition containing the hydrolyzable silicon-containing polyalkylene oxide polymer obtained by the production method of the present invention as a curing component will be described.
The moisture-curable composition of the present invention may contain a curing catalyst, an antistatic agent, a physical property improver such as a silane coupling agent, a filler, a reinforcing agent, a plasticizer, an anti-sagging agent, a coloring agent, an anti-aging agent, depending on the purpose. Various additives such as an agent, a flame retardant, and a fluorine-containing hydrocarbon compound may be blended.

The curing catalyst is a catalyst for curing the hydrolyzable silicon group-containing polyalkylene oxide polymer to a solid having rubbery elasticity, and a conventionally known silanol condensation catalyst can be used. Examples of such a catalyst include titanates such as tetrabutyl titanate and tetrapropyl titanate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, tin laurate,
Tin carboxylate such as tin ferzatic acid, dibutyltin oxide, reaction product of dibutyltin oxide and phthalic acid ester, dibutyltin diacetyl acetate, aluminum triacetyl acetate, aluminum trisethyl acetate, diisopropoxy aluminum, ethyl acetoacetate Organic chelating compounds such as zirconium tetraacetyl acetate and titanium tetraacetyl acetate, lead octylate, iron naphthenate, bismuth-tris (neodecanoate), bismuth-tris (2-ethylhexoate) and the like. Bismuth compounds are mentioned. Furthermore, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine,
Diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine,
Benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,
Diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 (hereinafter abbreviated as DBU) and the like. Examples thereof include amine compounds and their carboxylate salts. Further, reaction products of these amine compounds and epoxy resins, and silicon compounds having an amino group, for example, γ-
Aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane and the like can be mentioned. These metal and amine compound catalysts may be used alone or in combination of two or more. These curing catalysts are generally used in an amount of 0.001 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the hydrolyzable silicon-containing polyalkylene oxide polymer of the present invention.
Use 0 to 1 part by weight.

The antistatic agent is used to reduce the adhesion of dust to the surface of the cured product due to static electricity, and conventionally known compounds can be used. For example, nonionic antistatic agents such as polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, glycerin partial fatty acid ester, sorbitan partial fatty acid ester, alkyl sulfonate, alkyl benzene Sulfonate, alkyl sulfate,
Anionic antistatic agents such as alkyl phosphates;
Cationic antistatic agents such as quaternary ammonium chloride, quaternary ammonium sulfate and quaternary ammonium nitrate; amphoteric antistatic agents such as alkyl betaine type, alkyl imidazoline type and alkyl alanine type; polyvinylbenzyl type cation; Examples thereof include an antistatic agent based on a chargeable resin such as a polyacrylic acid type cation.
These antistatic agents are usually 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the hydrolyzable silicon-containing polyalkylene oxide polymer of the present invention.
Use 8 parts by weight.

The physical property improver refers to a compound used for improving the adhesion of the cured product to the substrate or the mechanical properties, and usually includes a silane coupling agent. Examples of such a compound include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, and N- (β-aminoethyl) Aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, dimethyldiisopropenoxysilane, methyl Triisopropenoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane,
Trimethylsilanol, diphenylmethylsilanol,
Dimethylphenylsilanol and the like. These property improvers may be used alone or in combination of two or more. These physical property improvers are used usually in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention. .

As the filler, fumed silica, silica, silicic anhydride, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, talc, titanium oxide, barium sulfate, bentonite, ferric oxide,
Hydrogenated castor oil; zinc stearate; These fillers may be used alone or in combination of two or more. The amount of the polyalkylene oxide polymer of the present invention is 10%.
It is usually 10 to 200 parts by weight, preferably 15 to 100 parts by weight, based on 0 parts by weight.

As the reinforcing agent, carbon black as a black filler, white carbon or silica as a white filler, silica,
Examples include silicates such as kaolin, bentonite, finely divided anhydrous silicic acid, barite, gypsum, bone powder, and dolomite. These reinforcing agents may be used alone or in combination of two or more. In addition, the amount thereof is usually 1 to 200 parts by weight, based on 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention,
Preferably it is 6 to 100 parts by weight.

Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, dipeptyl phthalate, diisodecyl phthalate, dioctyl adipate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, dioctyl sebacate, tricresyl phosphate, tributyl phosphate, and chlorinated paraffin. , Petroleum ether,
Diethylene glycol dibenzoate, triethylene glycol dibenzoate, etc., or a molecular weight of 4000
高分子 12,000 high molecular weight compounds. Examples of such high molecular weight compounds include polyoxyalkylene compounds, polyester compounds, polystyrene,
Examples thereof include poly-α-methylstyrene, poly (styrene-acrylonitrile) copolymer, polybutadiene, polyisoprene, polybutene, and the unsaturated group-terminated polyalkylene oxide polymer of the present invention. It is preferable that these high molecular weight compounds have few hydrophilic functional groups such as a hydroxyl group and a carboxyl group. When a high-molecular-weight plasticizer is used, the amount thereof is 0.1 to 6 parts by weight based on 100 parts by weight of the hydrolyzable silicon-containing polyalkylene oxide polymer of the present invention. These plasticizers may be used alone or in combination of two or more. The addition amount is usually 0.1 to 70 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention.

Examples of the anti-dripping agent include compounds such as hydrogenated castor oil compounds, calcium stearate, aluminum stearate, barium stearate and the like. The addition amount is usually 0.1 to 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention.
The amount is from 01 to 20 parts by weight, preferably from 0.1 to 10 parts by weight.

As the coloring agent, conventionally known inorganic pigments, organic pigments and dyes can be used according to the purpose. The addition amount thereof is usually 0.01 part by weight based on 100 parts by weight of the hydrolyzable silicon-containing polyalkylene oxide polymer of the present invention.
To 30 parts by weight, preferably 0.1 to 20 parts by weight.

Examples of the stabilizer include an antioxidant, an ultraviolet absorber, and a heat stabilizer. The antioxidant is not particularly limited. For example, butylhydroxyanisole, t
-Butylhydroxytoluene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-
Hydroxybenzyl) benzene, 3,9-bis [2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl]
-2,4,8,10-tetraoxaspiro (5,5) undecane, distearylthiodipropionate and the like. Examples of the ultraviolet absorber include pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. As a heat stabilizer, Tris (2, 4
-Di-t-butylphenyl) phosphite, triphenyl phosphite, trilauryl phosphite and the like. The addition amount of each of these is preferably 100 to 8000 ppm with respect to 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention.

Examples of the flame retardant include tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, Daihachi Chemical company CR
-505 and CR-507, P manufactured by Monsanto Chemical Co., Ltd.
hosagard 2XC-20 and C-22-R,
Examples include Fyrol-6, ammonium polyphosphate, diethyl bishydroxyethylaminoethyl phosphate, and dibromopropanol manufactured by Stoffer Chemical Company. The amount used is 0.05 to 30 parts by weight, preferably 0.2 to 20 parts by weight, per 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention.

Examples of the fluorine-containing hydrocarbon compound include a conventionally known compound having a perfluorohydrocarbon group having 1 to 20 carbon atoms or a compound containing silicon in the perfluorohydrocarbon group. The amount of the compound to be used is generally 0.01 to 20 parts by weight, preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention. Further, for the purpose of suppressing the change over time of the viscosity of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention, the polymer may be a lower alcohol such as methanol or ethanol, γ-
Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyl An alkoxysilane compound such as trimethoxysilane, dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, vinyltrimethoxysilane, or vinyldimethylmethoxysilane may be added. These compounds can be used alone or in combination of two or more. The amount used is 0.001 to 5 parts by weight, preferably 0.003 to 4 parts by weight, per 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention.

The organic solvent inert to the hydrolyzable silicon-containing polyalkylene oxide polymer of the present invention includes, for example, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl Ketone and the like. These organic solvents can be used alone or in combination of two or more. The amount used is 0.1 to 30 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention.
0 parts by weight.

The hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention may further contain a fungicide such as bis (tri-n-butyltin) oxide, an organic solvent inert to the polymer, if necessary. An antifoaming agent can be used.
After preparing the cured product composition, it is preferable that the composition be brought into contact with a water removing agent such as synthetic zeolite, activated alumina and silica gel to sufficiently remove water.

The above-mentioned moisture-curable composition can be applied to a one-pack type curable composition in which all the components are mixed in advance, hermetically sealed and preserved, and cured by moisture in the air after application.
In addition, a two-part curable composition in which a curing agent in which each of the above-described components and water are previously blended and a main ingredient in which various components are blended with the hydrolyzable silicon-containing polyalkylene oxide polymer of the present invention before use is used. Also applicable to

The moisture-curable composition of the present invention comprises an adhesive, a pressure-sensitive adhesive, a paint, a coating agent, a sealing material, a waterproofing agent,
It can be used for various applications such as casting elastics and spraying agents.

[0103]

EXAMPLES Examples and comparative examples of the present invention are shown below.
Embodiments of the present invention will be clarified, but the present invention is not limited to these embodiments. The hydroxyl value (hereinafter abbreviated as OHV; unit: mgKOH / g) of the polyoxyalkylene polyols of Examples and Comparative Examples is JIS K-1557.
It was determined by the method described.

In the synthesis of polyoxyalkylene polyol, the following phosphazenium compounds were used as alkylene oxide polymerization catalysts. A phosphazenium compound (hereinafter abbreviated as P5NMe2OH);
MILLI was converted to tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride {[(Me ₂ N) ₃ P = N] ₄ P ⁺ Cl ⁻ } manufactured by Ka.
A 2.5% by weight aqueous solution was prepared using water (hereinafter, abbreviated as ultrapure water) adjusted to have a specific resistance of 16 MΩ-cm using -Q Labo (a small ultrapure water apparatus manufactured by Japan Millipore Limited). Then, tetrakis [tris (dimethylamino) phosphoranylideneamino] was placed in a polycarbonate cylindrical column filled with ion exchange resin Levatit MP-500 (manufactured by Bayer) whose exchange group was changed to a hydroxyl group with a 1N sodium hydroxide aqueous solution. A 2.5% by weight aqueous solution of phosphonium chloride was subjected to SV (Space) at 23 ° C.
Velocity) was 0.7 (1 / hr), and the solution was passed through the column from the bottom in an ascending flow, and ion exchange was performed with tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide. Further, ultrapure water was passed through the column filled with the ion exchange resin, and the phosphazenium compound remaining in the column was recovered. afterwards,
An aqueous solution of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide was added to 80
° C, degree of vacuum 60 mmHgabs. (7980 Pa) for 2 hours, at 80 ° C., 1 mmHgabs. (13
3 Pa) by performing dehydration under reduced pressure for 7 hours to obtain powdered tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[
(Me ₂ N) ₃ P = N] ₄ P ⁺ OH ⁻ ｝ was obtained. The yield determined by weight measurement of the compound after drying was 97%.
¹ H-NMR using tetramethylsilane in deuterated dimethylformamide solution as an internal standard (400 MH manufactured by JEOL Ltd.)
zNMR) was 2.6 ppm (d, J = 9.
9 Hz, 72H). Elemental analysis: C 38.2
8, H 9.82, N 29.43, P 19.94
(Theoretical values C 38.09, H 9.72, N 29.6
1, P 20.46). The phosphazenium compound is (1,1,1,1) in the order of a, b, c and d in the chemical formula (2), R is a methyl group, and Q ^- is O
H ^-is a hydroxy anion.

Comparison with the phosphazenium compound of the present invention
Include USP 5,144,093 (column 4, line 52-
Column 5, lines 4) double metal cyanide complex
Body [Zn_Three[Co (CN)₆]_Two・ 2.48DME ・ 4.6
5H_TwoO 0.94ZnCl _Two; Hereinafter abbreviated as DMC
You. DME is an abbreviation for dimethoxyethane. )
Cesium hydroxide (50% by weight
Of cesium aqueous solution) to the polymerization of alkylene oxide
The catalyst was used. Further, in a comparative example, Patent No.-02558
No. 165, the molecular weight is increased by a molecular weight increasing reaction.
Synthesized oxyalkylene oxide polymer and hydrolysis
Of Functional Silicon Group-Containing Polyalkylene Oxide Polymer
Was done.

An apparatus for synthesizing a polyoxyalkylene polyol, an unsaturated group-terminated polyalkylene oxide polymer and a hydrolyzable silicon group-containing polyalkylene oxide polymer includes a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, and a monomer such as alkylene oxide. A pressure-resistant autoclave (manufactured by Nitto Koatsu) having an internal volume of 1.0 L and 2.5 L equipped with an oxide loading port was used. Hereinafter, the synthesis device is abbreviated as an autoclave.

The concentration (unit: mol%) of the terminal unsaturated group of the unsaturated group-terminated polyalkylene oxide polymer of each of Examples and Comparative Examples was determined by JEOL's 400 MHz ¹ H nuclear magnetic resonance (N
(MR) using a heavy chloroform solution as a solvent. The number average molecular weight of the unsaturated group-terminated polyalkylene oxide polymer was measured by gel permeation chromatography (hereinafter abbreviated as GPC).
The measurement conditions are shown below. Measurement and analysis equipment: LC-6A system manufactured by Shimadzu Corporation Detector: RID-6A manufactured by Shimadzu Corporation Differential refractometer Separation column: Shodex GPC manufactured by Showa Denko KK
KF series, KF-801, 802, 802.5, 8
Eluent: Tetrahydrofuran for liquid chromatogram, Flow rate: 0.8 ml / min, Column temperature: 40 ° C. Further, the viscosity of the hydrolyzable silicon-group-containing polyalkylene oxide polymers of Examples and Comparative Examples (hereinafter referred to as “viscosity”) , Η (unit: poise / 25 ° C.) is JIS K-730.
It was determined by the method described in 1.

Example 1 Polyalkylene oxide polymer A 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
Into a four-necked flask of 1 l, 0.020 mol of P5NMe2OH and 0.04 mol of toluene were added to 1 mol of dipropylene glycol, and nitrogen was introduced through a capillary tube at 85 ° C. and 20 mmHgabs. (2660 Pa), dehydration under reduced pressure and detoluene operation were performed for 3 hours. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. (1330P
From the reduced pressure state of a), at a reaction temperature of 110 ° C. and a maximum pressure of 5 kgf / cm ₂ (490 kPa) during the reaction, the OH
Multistage addition polymerization of propylene oxide was performed until V became 14.0 mgKOH / g. When there is no change in the internal pressure of the autoclave, 105 ° C., 10 mmHgab
s. (1330 Pa) under reduced pressure for 30 minutes to obtain a crude polyoxyalkylene polyol. The phosphazenium compound in the crude polyoxyalkylene polyol is neutralized with hydrochloric acid (in the form of an 8% by weight aqueous solution),
As a result of measuring HV, it was 14.1 mgKOH / g. Next, 1.02 equivalents of sodium methoxide (manufactured by Wako Pure Chemical Industries, Ltd., in the form of a 28% methanol solution) was added to 1 equivalent of hydroxyl groups in the crude polyoxyalkylene polyol containing the phosphazenium compound, After replacing the nitrogen in the autoclave, 130 ° C, 1m
mHgabs. Under a condition of (133 Pa), a methanol removal operation under reduced pressure was performed for 3 hours to convert a hydroxyl group in the polyol into a sodium alkoxide. After the temperature was lowered to 45 ° C., 1.1 equivalents of allyl chloride [Wako Pure Chemical Industries, Ltd.] was used for 1.1 equivalents of hydroxyl groups in the crude polyoxyalkylene polyol.
And the temperature was raised to 130 ° C., and the reaction was carried out at the same temperature for 3 hours. Then, the temperature was lowered to 100 ° C,
mHgabs. (1330 Pa) The pressure was reduced under the following conditions for 30 minutes to obtain a crude unsaturated group-terminated polyalkylene oxide polymer. The polymer was taken out of the autoclave, and 300 parts by weight of ion-exchanged water was charged into 100 parts by weight of the polymer in a 5-liter separating funnel equipped with a stirrer. N-
Hexane was added and stirred for another 20 minutes. Next, phosphoric acid (in the form of a 75.1% by weight aqueous solution) was added until the pH of the aqueous layer reached 2.9, and the mixture was stirred for 1 hour, and subjected to stationary liquid separation. Thereafter, the aqueous layer was removed, and 5 parts by weight of KW-700SN (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added to 100 parts by weight of the polymer, followed by stirring for 3 hours. After filtration through a 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to remove the adsorbent, 105 ° C., 10 mmHgabs. (1330 Pa)
The mixture was dried under reduced pressure for 4 hours under the following conditions to recover an unsaturated group-terminated polyalkylene oxide polymer. The number average molecular weight by GPC was 8,250, and the terminal unsaturation ratio by NMR was 98.0 mol%. Next, the obtained unsaturated group-terminated polyalkylene oxide polymer was charged into an autoclave and subjected to nitrogen substitution. Then, 2.83 parts by weight of methyldimethoxysilane and hexachloroplatinic acid / 6 water were added to 100 parts by weight of the polymer. 0.05 parts by weight of a 1.3 M isopropanol solution of a Japanese product [manufactured by Wako Pure Chemical Industries, Ltd.] was added, and a reaction was performed at 100 ° C. for 3 hours. Then, at the same temperature, 10 mmHgabs. (1330 Pa) After performing decompression treatment under the following conditions for 1 hour, 2 parts by weight of an adsorbent KW-500 (manufactured by Kyowa Chemical Industry Co., Ltd.) is added to 100 parts by weight of the polymer, and the mixture is stirred for 2 hours. Was done. Next, 5C filter paper (adjusted particle size 1) manufactured by Advantech Toyo Co., Ltd.
μ), filtration under reduced pressure was performed to purify the hydrolyzable silicon group-containing polyalkylene oxide polymer. The viscosity (η) of the hydrolyzable silicon group-containing polyalkylene oxide polymer was 158 poise / 25 ° C.

Example 2 Polyalkylene oxide polymer B 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
In a four-necked flask of 1 l, 0.022 mol of P5NMe2OH and 0.08 mol of toluene were added to 1 mol of dipropylene glycol, and nitrogen was introduced through a capillary tube at 85 ° C. and 20 mmHgabs. (2660 Pa), vacuum dehydration and toluene removal operations were performed for 4 hours. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. (1330P
From the reduced pressure state of a), at a reaction temperature of 110 ° C. and a maximum pressure of 5 kgf / cm ² (490 kPa) during the reaction, the OH
Multistage addition polymerization of propylene oxide was performed until V reached 11.0 mgKOH / g. When there is no change in the internal pressure of the autoclave, 105 ° C., 10 mmHgab
s. (1330 Pa) under reduced pressure for 30 minutes to obtain a crude polyoxyalkylene polyol. Phosphazenium compound is converted to hydrochloric acid (in the form of an 8% by weight aqueous solution)
And the OHV was measured. As a result, 11.3 mg KOH
/ G. Subsequently, 1.02 equivalent of sodium methoxide (manufactured by Wako Pure Chemical Industries, Ltd., in the form of a 28% methanol solution) with respect to 1 equivalent of hydroxyl group in the crude polyoxyalkylene polyol containing the phosphazenium compound.
And after purging with nitrogen in the autoclave, 13
0 ° C., 1 mmHgabs. (133 Pa) and 4
Hydroxyl group in the polyol was converted to sodium alkoxide by performing decompression methanol operation for a time. After the temperature was lowered to 45 ° C., 1.2 equivalents of allyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were charged per equivalent of hydroxyl groups in the crude polyoxyalkylene polyol, and the temperature was raised to 130 ° C. 3
A time reaction was performed. Thereafter, the temperature was lowered to 100 ° C., and at the same temperature, 10 mmHgabs. (1330 Pa) The pressure was reduced under the following conditions for 30 minutes to obtain a crude unsaturated group-terminated polyalkylene oxide polymer. The polymer was taken out of the autoclave, and 400 parts by weight of ion-exchanged water was charged into 100 parts by weight of the polymer in a 5-liter separatory funnel equipped with a stirrer. Of n-hexane was added, and the mixture was further stirred for 20 minutes. Next, sulfuric acid (in the form of a 5% by weight aqueous solution) was added until the pH of the aqueous layer reached 2.5, and the mixture was stirred for 3 hours, and subjected to stationary liquid separation. Thereafter, the aqueous layer was removed, and 6 parts by weight of KW-700SN (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added to 100 parts by weight of the polymer, followed by stirring for 3 hours. After filtration through a 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to remove the adsorbent, 105 ° C., 10 mmHgabs. (1330 Pa)
The mixture was dried under reduced pressure for 4 hours under the following conditions to recover an unsaturated group-terminated polyalkylene oxide polymer. The number average molecular weight by GPC was 11,300, and the terminal unsaturation by NMR was 97.5 mol%. Next, the obtained unsaturated group-terminated polyalkylene oxide polymer was charged into an autoclave and subjected to nitrogen substitution. Then, 2.07 parts by weight of methyldimethoxysilane and hexachloroplatinic acid / 6 water were added to 100 parts by weight of the polymer. Japanese products [Wako Pure Chemical Industries, Ltd.
Was added and 0.05 parts by weight of a 1.3 M isopropanol solution was added, and the reaction was carried out at 100 ° C. for 4 hours. Then, at the same temperature, 10 mmHgabs. (1330 Pa) After performing decompression treatment under the following conditions for 1 hour, the temperature was lowered to 50 ° C., and 5 parts by weight of adsorbent KW-5 was added to 100 parts by weight of the polymer.
00 [manufactured by Kyowa Chemical Industry Co., Ltd.], 50 parts by weight of n-hexane and 10 parts by weight of ion-exchanged water were added, and the mixture was stirred for 2 hours. Then, vacuum filtration was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd.
105 ° C., 10 mmHgabs. (1330 Pa) Decompression hexane and dehydration were performed under reduced pressure for 3 hours under the following conditions to purify the hydrolyzable silicon group-containing polyalkylene oxide polymer. The viscosity (η) of the hydrolyzable silicon group-containing polyalkylene oxide polymer is 210 poise / 25 ° C.
Met. The following shows a comparative example. In Comparative Example 1, the above-mentioned double metal cyanide complex (DMC) was used as a polymerization catalyst for alkylene oxide. The addition polymerization of an alkylene oxide was attempted on an active hydrogen compound (dipropylene glycol in this comparative example) as a polymerization initiator using DMC as a catalyst, but as described in JP-A-4-59825. Addition polymerization of an alkylene oxide to an active hydrogen compound having no propylene oxide added thereto was difficult, so that a polyoxyalkylene polyol catalyzed by potassium hydroxide was used as an initiator, and then D
Polyoxyalkylene polyol was synthesized using MC catalyst.

Comparative Example 1 Polyalkylene Oxide Polymer C Propylene oxide was added to propylene glycol.
Polypropylene polyol Diol400 [Mitsui Toatsu
0.03 parts by weight per 100 parts by weight
Double metal cyanide complex (DMC) was added,
10 mmHgabs. (1330 Pa) 3 under the following conditions
Dehydration under reduced pressure was performed for hours. Next, the compound is placed in an autoclave.
After charging the product and purging with nitrogen, 10 mmHgab
s. (1330 Pa) to a reaction temperature of 110
° C, maximum pressure during reaction 4kgf / cm ^Two(392kP
Under the condition of a) until OHV becomes 14.0 mgKOH / g
Performs multi-stage addition polymerization of propylene oxide to form DMC
To obtain a crude polyoxypropylene polyol containing
Was. 100 parts by weight of the polyoxypropylene polyol
2.8 parts by weight of 30% by weight potassium methylate
(KOMe) solution in methanol
The reaction was run at 90 ° C., 20 mm Hgabs. (2660 Pa)
For 2 hours. Then, 3 parts by weight of water and AD-
5 parts by weight of 600NS (manufactured by Tomita Pharmaceutical Co., Ltd.)
Stir for 2 hours under nitrogen atmosphere.
Vacuum filtration using 5C filter paper (retained particle size 1μ) manufactured by Co., Ltd.
Was done. After filtration, 120 ° C., 10 mmHgabs.
(1330 Pa) Dehydration under reduced pressure for 2 hours under the following conditions,
DMC removal processing was performed. Polio after DMC removal operation
The OHV of the xyalkylene polyol is 14.2 mg KO
H / g. The crude pork containing DMC is then
For 1 equivalent of hydroxyl group in lioxyalkylene polyol
1.02 equivalent of sodium methoxide [Wako Pure Chemical Industries, Ltd.
Form of 28% methanol solution manufactured by Co., Ltd.]
After nitrogen replacement in the autoclave, 130 ° C, 1m
mHgabs. (133 Pa) under reduced pressure for 3 hours
Perform methanol operation to determine the hydroxyl groups in the polyol
Alkoxide. After cooling to 45 ° C, the crude
Per equivalent of hydroxyl group in polyoxyalkylene polyol
To 1.1 equivalents of allyl chloride [Wako Pure Chemical Industries, Ltd.
), Heated to 130 ° C, and reacted at the same temperature for 3 hours.
Was done. Then, the temperature was lowered to 100 ° C,
mHgabs. (1330Pa) 30 minutes under the following conditions
After performing a vacuum treatment, the crude unsaturated group-terminated polyalkylene oxide
A side polymer was obtained. Remove the polymer from the autoclave.
Into a 5-liter separatory funnel equipped with a stirrer.
300 parts by weight ion exchange for 100 parts by weight of polymer
After charging water and stirring sufficiently, 300 parts by weight of n-
Hexane was added and stirred for another 20 minutes. Next
Until the pH of the aqueous layer reaches 2.5 (75.
% Aqueous solution) and stirred for 1 hour.
Then, stationary liquid separation was performed. After that, remove the water layer and adsorb
KW-700SN [Kyowa Chemical Industry Co., Ltd.]
Add 5 parts by weight to 100 parts by weight of the polymer and stir for 3 hours.
Stirring was performed. Advantech Toyo 5C filter paper
(Retention particle size 1μ) to remove the adsorbent by filtration.
Thereafter, at 105 ° C., 10 mmHgabs. (1330 Pa)
Dry under reduced pressure for 4 hours under the following conditions,
The alkylene oxide polymer was recovered. GPC
Number average molecular weight is 8080, terminal unsaturation by NMR
The rate was 96.8 mol%. Next, the unsaturated base powder obtained
Autoclaving polyalkylene oxide polymer
After performing nitrogen replacement, 100 parts by weight of the polymer was
2.89 parts by weight of methyldimethoxysilane and
Hexachloroplatinic acid hexahydrate (Wako Pure Chemical Industries, Ltd.)
Add 0.05 parts by weight of 1.3M isopropanol solution.
Then, the reaction was performed at 100 ° C. for 3 hours. After that, the same temperature
At 10 mmHgabs. (1330 Pa) The following conditions
After 1 hour under reduced pressure, and 100 parts by weight of the polymer
2 parts by weight of adsorbent KW-500 [Kyowa Chemical Industry
Was added, and the mixture was stirred for 2 hours. Next,
5C filter paper manufactured by Dovantec Toyo Co., Ltd.
μ), and filter under reduced pressure.
The alkylene oxide polymer was purified. Water content
Viscosity of degradable silicon-containing polyalkylene oxide polymer
The degree (η) was 198 poise / 25 ° C.

Comparative Example 2 Polyalkylene oxide polymer D 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
cesium hydroxide (in the form of a 50% by weight aqueous solution of cesium hydroxide) was added to 1 mol of dipropylene glycol in a four-necked flask of 1 l at 105 ° C., 10 mmHgabs while introducing nitrogen through a capillary tube. .
(1330 Pa) Dehydration under reduced pressure was performed for 3 hours under the following conditions. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. (13
The multistage addition polymerization of propylene oxide was carried out from a reduced pressure of 30 Pa) at a reaction temperature of 110 ° C. and a maximum pressure during the reaction of 5 kgf / cm ² (490 kPa) until the OHV became 14.0 mgKOH / g. 105 ° C, 10 mmHg when the internal pressure of the autoclave stops changing.
abs. (1330 Pa) under reduced pressure for 20 minutes to obtain a crude polyoxyalkylene polyol. Cesium in the crude polyoxyalkylene polyol was neutralized with hydrochloric acid (in the form of an 8% by weight aqueous solution), and the OHV was measured. As a result, it was 14.6 mgKOH / g. Next, 1.02 equivalents of sodium methoxide (manufactured by Wako Pure Chemical Industries, Ltd., in the form of a 28% methanol solution) was added to one equivalent of hydroxyl groups in the crude polyoxyalkylene polyol containing cesium, followed by autoclave. After replacing with nitrogen in 130 ° C., 1 mmHgabs. (133Pa)
Under the conditions described above, methanol removal under reduced pressure was performed for 3 hours to convert the hydroxyl group in the polyol into sodium alkoxide. 4
After the temperature was lowered to 5 ° C., 1.1 equivalents of allyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) per 1 equivalent of hydroxyl groups in the crude polyoxyalkylene polyol was charged, and the temperature was raised to 130 ° C. For 3 hours. Thereafter, the temperature was lowered to 100 ° C., and at the same temperature, 10 mmHgabs. (1330P
a) A reduced pressure treatment was performed for 30 minutes under the following conditions to obtain a crude unsaturated group-terminated polyalkylene oxide polymer. The polymer was taken out of the autoclave and equipped with a stirrer.
300 parts by weight of ion-exchanged water was added to 100 parts by weight of the polymer in a separating funnel of 1 liter, and after sufficiently stirring, 300 parts by weight of n-hexane was added.
Stirring was performed for 0 minutes. Next, phosphoric acid (in the form of a 75.1% by weight aqueous solution) was added until the pH of the aqueous layer reached 2.9, and the mixture was stirred for 1 hour, and subjected to stationary liquid separation. Thereafter, the aqueous layer was removed and the adsorbent KW-700SN was removed.
5 parts by weight of [Kyowa Chemical Industry Co., Ltd.] was added to 100 parts by weight of the polymer, and the mixture was stirred for 3 hours. After filtration through a 5C filter paper (retained particle size: 1μ) manufactured by Advantech Toyo Co., Ltd. to remove the adsorbent, 105 ° C, 10 mmHg
abs. (1330 Pa) The mixture was dried under reduced pressure for 4 hours under the following conditions to recover an unsaturated group-terminated polyalkylene oxide polymer. The number average molecular weight by GPC is 795.
0, The terminal unsaturation by NMR was 97.6 mol%. Next, the obtained unsaturated group-terminated polyalkylene oxide polymer was charged into an autoclave and subjected to nitrogen substitution. Then, 2.94 parts by weight of methyldimethoxysilane and hexachloroplatinic acid.6 were added to 100 parts by weight of the polymer.
A hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) of 1.3 M-isopropanol solution was added in an amount of 0.05 part by weight, and the mixture was reacted at 100 ° C. for 3 hours. Then, at the same temperature, 10 mmHgabs.
(1330 Pa) After performing decompression treatment under the following conditions for 1 hour, 2 parts by weight of the adsorbent K was added to 100 parts by weight of the polymer.
W-500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 2 hours. Next, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the hydrolyzable silicon group-containing polyalkylene oxide polymer. The viscosity (η) of the hydrolyzable silicon group-containing polyalkylene oxide polymer is 162 poise /
25 ° C

Comparative Example 3 Polyalkylene oxide polymer E 640 g of polyoxypropylene diol having an average molecular weight of 3200 [Diol-3200 manufactured by Mitsui Toatsu Chemicals, Inc.]
Was added to a nitrogen-purged autoclave, 17.32 g of sodium methoxide (manufactured by Wako Pure Chemical Industries, Ltd., in the form of a 28% methanol solution, the same applies hereinafter) was added, and the autoclave was further purged with nitrogen. After, 130 ° C,
1 mmHgabs. Under a condition of (133 Pa), dehydration operation under reduced pressure was performed for 2 hours to convert a hydroxyl group in the polyol into a sodium alkoxide. When the pressure in the autoclave is 1 mmHgabs. (1330 Pa), 10.2 g of dichloromethane was added, and the reaction was carried out at 130 ° C. for 4 hours. Then, 5.78 g of sodium methoxide was added, and 130 ° C., 1 mmHgabs. (133 Pa), the mixture was subjected to methanol removal under reduced pressure for 1 hour, and then 16.0 g of allyl chloride was added under the same pressure, and
The reaction was carried out at a temperature of 2 hours. After the completion of the reaction, the polymer was taken out of the autoclave, and 300 parts by weight of ion-exchanged water was added to 100 parts by weight of the polymer in a 5-liter separatory funnel equipped with a stirrer, and sufficiently stirred. Later 3
00 parts by weight of n-hexane was added, and the mixture was further stirred for 20 minutes. Next, phosphoric acid (in the form of a 75.1% by weight aqueous solution) was added until the pH of the aqueous layer reached 2.9,
Stirring was performed for 1 hour, and liquid separation was performed while standing. Thereafter, the aqueous layer was removed, and 5 parts by weight of KW-700SN (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added to 100 parts by weight of the polymer, followed by stirring for 3 hours. After filtration through a 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to remove the adsorbent, 105 ° C., 10 mmHgabs. (1
It dried under reduced pressure for 4 hours under the following conditions to recover the unsaturated group-terminated polyalkylene oxide polymer. The number average molecular weight by GPC was 7,980, and the terminal unsaturation ratio by NMR was 97.5 mol%. Next, the obtained unsaturated group-terminated polyalkylene oxide polymer was charged into an autoclave and subjected to nitrogen substitution.
2.93 parts by weight of methyldimethoxysilane and hexachloroplatinic acid hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 1.3 M-isopropanol solution was added to 0.0 part by weight of 0.03 parts by weight.
5 parts by weight were added, and the reaction was performed at 100 ° C. for 3 hours. Then, at the same temperature, 10 mmHgabs. (1330 Pa)
After performing a pressure reduction treatment for 1 hour under the following conditions, the polymer 10
2 parts by weight of the adsorbent KW-500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 0 parts by weight, and the mixture was stirred for 2 hours. Next, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the hydrolyzable silicon group-containing polyalkylene oxide polymer.
The viscosity (η) of the hydrolyzable silicon group-containing polyalkylene oxide polymer was 189 poise / 25 ° C. Further, for the purpose of examining the productivity of polyoxyalkylene polyol by the phosphazenium compound of the present invention, the polymerization activity of propylene oxide was determined. A comparison was made. Since the double metal cyanide complex (DMC) forms a complex structure, the detailed polymerization active site of the alkylene oxide is unknown. Then, the polymerization activity of propylene oxide with the phosphazenium compound (P5NMe2OH) used in the example and the cesium hydroxide (CsOH) used in the comparative example was determined. Before the polymerization of propylene oxide, the number of moles of the catalyst present in the polymerization initiator is determined (hereinafter, this value is abbreviated as a mole). Next, the amount of propylene oxide reacted until the target OHV was reached (hereinafter, this value is abbreviated as bg), and the reaction time [hereinafter, this value is c minutes (m
in. Abbreviated). ]. bg in amol and cmin. Is defined as the polymerization activity of propylene oxide (unit: g / mol · min.). Dipropylene glycol was used as a polymerization initiator. The propylene oxide polymerization activity at a reaction temperature of 80 ° C. by P5NMe2OH thus determined was 490 g / mol · m
in. (Example 3), 8.7 g / mol · in CsOH
min. (Comparative Example 4).

The hydrolyzable silicon-group-containing polyalkylene oxide polymers obtained in Examples and Comparative Examples were sealed in a metal container under a nitrogen atmosphere and stored in an oven at 50 ° C. for 30 days. A comparison was made. Examples, polyoxyalkylene polyol obtained in Comparative Examples (hereinafter, referred to as
Abbreviated as polyol. ), The number average molecular weight (hereinafter abbreviated as Mn) of the unsaturated group-terminated polyalkylene oxide polymer (hereinafter abbreviated as the unsaturated polymer) and the terminal unsaturation. Saturation rate (unit;
Mol%) and the viscosity immediately after the production of the hydrolyzable silicon group-containing polyalkylene oxide polymer (hereinafter abbreviated as the hydrolyzable polymer) and after standing at 50 ° C. for 30 days (abbreviated as η, unit: poise). / 25 ° C) [Table 1]
Summarized in Furthermore, Table 2 shows the polymerization activity (unit: g / mol · min.) Of propylene oxide with a phosphazenium compound and a cesium hydroxide catalyst.
In Table 1, DPG is dipropylene glycol as an initiator, Diol 400 is a polyol obtained by addition-polymerizing an alkylene oxide to propylene glycol, and Di is
ol3200 is an abbreviation for a polyol having an average molecular weight of 3200 obtained by addition polymerization of propylene glycol with an alkylene oxide. In addition, propylene oxide is abbreviated as PO. The phosphazenium compound used as a catalyst is converted to PZ
, And double metal cyanide complex is abbreviated as DMC, and cesium hydroxide is abbreviated as CsOH. Comparative Example 3 shows an unsaturated group-terminated polyalkylene oxide polymer and a hydrolyzable silicon group-containing polyalkylene oxide polymer synthesized by a molecular weight increasing reaction.

[0114]

[Table 1]

[0115]

[Table 2] Example, Comparative Example After synthesizing an unsaturated group-terminated polyalkylene oxide polymer using a polyoxyalkylene polyol catalyzed by the phosphazenium compound of the present invention, further hydrolyzable silicon reacted with a specific hydrolyzable silicon compound Group-containing polyalkylene oxide polymer,
Double metal cyanide complex (DMC), cesium hydroxide (C
sOH) and a system using a molecular weight increasing reaction, the viscosity is low, and the change in viscosity after standing at 50 ° C. for 30 days is small. In particular, the viscosity over time of the hydrolyzable silicon group-containing polyalkylene oxide polymer produced using DMC as a catalyst is large (Comparative Example 1). The hydrolyzable silicon group-containing polyalkylene oxide polymer obtained by the production method of the present invention has a lower viscosity than conventional polymers, so that plasticizers, organic solvents and the like can be reduced, and workability can be improved. Is excellent. Furthermore, the propylene oxide polymerization activity of the phosphazenium compound of the present invention is higher than that of cesium hydroxide-based compounds, and it is excellent in productivity of polyoxyalkylene polyol and polyalkylene oxide polymer.

Next, in order to clarify the effects of the hydrolyzable silicon group-containing polyalkylene oxide polymer of the present invention, a one-pack type cured product was prepared and evaluated for mechanical properties and appearance. The present invention is not limited to these examples. Examples 4 to 5, Comparative Examples 5 to 7 Based on 100 parts by weight of the hydrolyzable silicon-containing polyalkylene oxide polymer obtained in Examples and Comparative Examples,
Glycidoxypropylmethyldiethoxysilane 1.5
Parts by weight, 150 parts by weight of calcium carbonate (manufactured by Sankyo Flour Milling Co., Ltd., trade name: Escalon # 2000), 55 parts by weight of dioctyl phthalate (manufactured by Kyowa Hakko Kogyo Co., Ltd.), hydrogenated castor oil [manufactured by Ito Oil Co., Ltd., product Name: Custer wax] 5
Parts by weight, phenolic antioxidant [Ouchi Shinko Chemical Co., Ltd.
Nocrack-SP], 1 part by weight, 4 g of tin octylate and 2 g of propylene glycol monomethyl ether solution of 50% by weight of laurylamine were charged into a stirrer equipped with a high-viscosity mixing mixer, and sufficiently stirred. Was done. Next, the curable composition was charged into a paint roll to prepare a sheet having a thickness of 3 mm. Then at 23 ° C,
It was left in a constant temperature room at a relative humidity of 65% for one week, and physical properties were measured. Mechanical properties were performed according to JIS A-5758. The curability of the curable composition was measured by a method.
Further, the tack (stickiness) on the surface of the cured product was evaluated by finger touch. When there was no tack, it was evaluated as 、, when there was a little tack, it was evaluated with △, and when the tack was large, it was evaluated with x. [Table 3]
Shows the measurement results of physical properties.

[0117]

[Table 3] From Examples and Comparative Examples, the cured product of the hydrolyzable silicon-containing polyalkylene oxide polymer using the polyoxyalkylene polyol catalyzed by the phosphazenium compound of the present invention is a double metal cyanide complex (DMC),
Compared to a system using cesium hydroxide (CsOH) as a catalyst, it is flexible and highly extensible. In the system using the polyoxyalkylene polyol of the present invention, the cured product has less tackiness (stickiness) and less surface contamination.

[0118]

According to the examples and comparative examples, after synthesizing an unsaturated group-terminated polyalkylene oxide polymer using a polyoxyalkylene polyol catalyzed by the phosphazenium compound of the present invention, it is further reacted with a specific hydrolyzable silicon compound. The hydrolyzable silicon group-containing polyalkylene oxide polymer thus obtained has a viscosity lower than that of a system using a double metal cyanide complex (DMC), cesium hydroxide (CsOH) and a molecular weight increasing reaction, and is 30 ° C at 50 ° C. Little change in viscosity after standing for days. In particular, the viscosity over time of the hydrolyzable silicon group-containing polyalkylene oxide polymer produced using DMC as a catalyst is large (Comparative Example 1). Since the hydrolyzable silicon-containing polyalkylene oxide polymer obtained by the production method of the present invention has a lower viscosity than conventional polymers, it is possible to reduce the amount of a plasticizer, an organic solvent, and the like. Excellent in nature. Furthermore, the propylene oxide polymerization activity of the phosphazenium compound of the present invention is higher than that of cesium hydroxide-based compounds, and it is excellent in productivity of polyoxyalkylene polyol and polyalkylene oxide polymer. Further, a cured product of a hydrolyzable silicon-containing polyalkylene oxide polymer using a polyoxyalkylene polyol catalyzed by the phosphazenium compound of the present invention is a double metal cyanide complex (DM
C), which is flexible and highly extensible as compared with a system using cesium hydroxide (CsOH) as a catalyst. In the system using the polyoxyalkylene polyol of the present invention, the cured product has less tackiness (stickiness) and less surface contamination. Due to these features, the polyalkylene oxide polymer of the present invention can be used in a wide range of fields such as elastomers, adhesives, adhesives, paints, coatings, sealing materials, waterproofing agents, cast elastics, spraying agents, and the like. is there.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 71/02 C08L 71/02 (72) Inventor Uji Sangi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Masaaki Aoki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Saku Izukawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemical Co., Ltd. Inside

Claims (3)

[Claims] (1) a step of producing a polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound using a phosphazenium compound as a catalyst;
(Step 2) a step of converting a hydroxyl group in a polyol containing 60 to 100% by weight of the polyoxyalkylene polyol obtained in Step 1 into an unsaturated group; Manufacturing method. 2. (Step 3) a step of producing a polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound using a phosphazenium compound as a catalyst;
(Step 4) a step of converting a hydroxyl group in the polyol containing 60 to 100% by weight of the polyoxyalkylene polyol obtained in Step 3 to an unsaturated group, (Step 5) an unsaturated group-terminated polyalkylene obtained in Step 4 The oxide polymer is represented by the chemical formula (1): [R1 in the chemical formula (1) is a substituted or unsubstituted monovalent organic group or halogenated hydrocarbon group having 1 to 20 carbon atoms,
When two R ¹ are present, R ¹ may be different from each other. X is a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, Xs may be different from each other. a
Is an integer of 1 to 3. Or the chemical formula (2) [Chemical formula 2] [R ¹ in the chemical formula (2) is a substituted or unsubstituted monovalent organic group or halogenated hydrocarbon group having 1 to 20 carbon atoms,
When two R ¹ are present, R ¹ may be different from each other. X is a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, Xs may be different from each other. a
Is an integer of 1 to 3. R ² is a divalent organic group having 1 to 20 carbon atoms, and W is a mercapto group. Reacting with at least one compound of the silicon compound represented by:
A method for producing a hydrolyzable silicon group-containing polyalkylene oxide polymer, comprising: 3. A moisture-curable composition comprising the hydrolyzable silicon-containing polyalkylene oxide polymer produced by the method according to claim 2 as a curing component.