JP2003183382A - Polymerization catalyst for oxirane compound and manufacturing method of polymer of oxirane compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization catalyst showing excellent activity in suspension polymerization and to provide a method of manufacturing a high molecular weight polymer of an oxirane compound in high productivity in the presence of the catalyst. <P>SOLUTION: The polymerization catalyst for the oxirane compound is one suitable for suspension polymerization of the oxirane compound in an organic solvent in which the polymer is insoluble wherein the catalyst is a reaction product of (A) an alkylaluminum compound, (B) an oxonic acid compound of phosphorus having at least one hydroxyl group in a molecule and (C) a nitrogen-containing cyclic compound having pKa of 6 to 8 and ratio of (A) the alkylaluminum compound to (B) the oxirane compound having at least one OH group in the molecule is such that the alkylaluminum is 0.65 to 0.95 molecule per one hydroxyl group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerization catalyst suitable for producing a polymer of an oxirane compound such as ethylene oxide, epichlorohydrin and allyl glycidyl ether by suspension precipitation polymerization, and an oxirane compound using the polymerization catalyst. The present invention relates to a method for producing the polymer.

[0002]

2. Description of the Related Art Polymers of oxirane compounds are polymers having various properties depending on the type of oxirane compound used as a raw material.
It is used in a very wide range of fields such as rubber members for electric and electronic devices, polymers for various plastic blends, and polymer solid electrolytes.

The industrial production method of the oxirane compound polymer includes solution polymerization in which the oxirane compound is polymerized in an organic solvent in which the monomer and polymer are soluble, and oxirane compound in the organic solvent in which the polymer is insoluble. Suspension precipitation polymerization is known in which the polymer is polymerized to precipitate a particulate polymer. Among them, the latter polymerization method has the advantage that the concentration of the monomer can be increased during the polymerization and the polymer and the solvent after the polymerization can be easily separated, but on the other hand, it is necessary to select a specific catalyst and solvent. There is.

As a catalyst capable of polymerizing an oxirane compound, those having a function of a Lewis acid such as boron fluoride, aluminum chloride, tin chloride and iron chloride are known. Polymerization using these catalysts gives a polymer having a relatively low molecular weight (for example, a molecular weight of thousands to tens of thousands).

In order to obtain a high molecular weight polymer useful in a specific field such as the rubber industry, a reaction product of an alkylzinc and water, a reaction product of an organotin compound and a phosphoric acid ester as a catalyst,
It is known to use reaction products of alkylaluminum and water, reaction products of alkylaluminum and phosphoric acid compounds, and the like. Particularly, as a catalyst using alkylaluminum, a reaction product of alkylaluminum and water,
Further, a catalyst to which a chelating agent such as acetylacetone is added (see, for example, J. Polym. Sci. A-1, 7, 525 (1969)), a reaction product of an alkylaluminum and a phosphoric acid compound, an amine compound, an organic phosphorus A catalyst to which a third component consisting of a compound and / or an organic arsenic compound is added (Japanese Patent Publication No.
6-27534), or a catalyst obtained by adding an N-substituted morpholine such as N-ethylmorpholine to the reaction product of an alkylaluminum and a phosphoric acid compound (Japanese Patent Publication No. Sho 5).
6-8852) and 1,8-
A catalyst containing diazabicyclo [5,4,0] -7-undecene (see Japanese Patent Publication No. 56-51171) has been proposed as an excellent catalyst for obtaining a high molecular weight oxirane compound polymer. As a catalyst for obtaining a high-molecular weight oxirane compound polymer by suspension precipitation polymerization, the present inventors have previously prepared an amine compound having a specific pKa value in a reaction product of an alkylaluminum and an oxo acid compound of phosphorus. The added catalyst was proposed (Japanese Patent Application No. 2000-193798).
The present invention is an extension of this prior invention and intends to further improve the production efficiency.

[0006]

However, the prior art relating to the catalyst using the above alkylaluminum is as follows.
Most of them are solution polymerization, and when suspension precipitation polymerization of an oxirane compound is carried out in the presence of these catalysts, a high molecular weight polymer may not be obtained in some cases, or the precipitated polymer may be in a particulate form. Since it solidifies without being formed, there are problems that stirring cannot be performed in the reaction device, and the polymer cannot be taken out from the reaction device.

An object of the present invention is to produce a high molecular weight oxirane compound polymer more effectively and with higher production efficiency by further improving a catalyst using an alkylaluminum suitable for suspension precipitation polymerization. It's about providing a way to do it.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, the reaction product of an alkylaluminum compound and an oxo acid compound of phosphorus has been further added with 6 to 6 as a third component. With a catalyst containing a nitrogen-containing cyclic compound having a pKa value of 8, the adhesion of the polymer to the reaction vessel wall during suspension precipitation polymerization was significantly reduced only when the alkylaluminum and phosphorus oxoacid compound were present in a specific ratio. Then, they found that the production efficiency was improved, and completed the present invention.

The catalyst for polymerizing an oxirane compound according to the present invention is a catalyst which can significantly reduce the adhesion of the polymer to the wall of the reaction tank when the oxirane compound is subjected to suspension precipitation polymerization in an organic solvent in which the polymer is insoluble. Wherein (A) an alkylaluminum compound, (B) a oxoacid compound of phosphorus having at least one OH group in the molecule, and (C) pK
a6 to 8 of a nitrogen-containing cyclic compound, the ratio of the (A) alkylaluminum compound and (B) the phosphorus oxo acid compound having at least one OH group in the molecule is such that the OH of the oxo acid compound is Alkylaluminum 0.65 to 1 mol of the group (when the oxo acid compound contains water, the sum of OH groups of the oxo acid compound and OH groups of water)
It is characterized by being in the range of 0.95 mol.

In the method for producing an oxirane compound polymer according to the present invention, the monomer oxirane compound is subjected to suspension precipitation polymerization in an organic solvent in which the polymer is insoluble in the presence of the catalyst having the above-mentioned characteristics, to obtain an oxirane compound. Is a method for producing the polymer.

The structure of the present invention will be described in detail below.

The alkylaluminum compound used in the catalyst according to the present invention has the general formula (R ₇ ) _p AlX _3-p (wherein R ₇ is a lower alkyl group, for example 1 to 6 carbon atoms).
Is an alkyl group, X is a halogen atom or a hydrogen atom, and p is 1, 1.5, 2 or 3. ) Is a compound represented by.

Examples of the alkylaluminum compound include triethylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride [Et
₃ Al ₂ Cl ₃ ], triisobutylaluminum,
Diisobutylaluminum hydride, tri-n-butylaluminum, tri-n-propylaluminum, etc. may be mentioned, and these may be used alone or in combination of two or more depending on the monomer oxirane compound used. it can.

Further, the oxo acid compound of phosphorus used in the catalyst according to the present invention contains at least one O in the molecule.
It has an H group. Examples of phosphorus oxoacid compounds include inorganic phosphoric acids such as phosphorous acid, diphosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, and polyphosphoric acid; nitrilotris (methylenephosphonic acid), 1-hydroxyethane- Examples thereof include organic phosphoric acids such as 1,1-diphosphonic acid; acidic phosphoric acid esters which are partial esterified products of alcohols and phosphoric acid. The acidic phosphoric acid ester is represented by the general formula O = P (OR ₈ ) _q (OH) _{3 -q} (wherein R ₈ is a lower alkyl group, for example, having 1 to 6 carbon atoms).
Is an alkyl group, q is 1 or 2. ), And examples thereof include acidic methyl phosphate, acidic ethyl phosphate, acidic propyl phosphate, acidic isopropyl phosphate, and acidic butyl phosphate. Furthermore, as the oxo acid compound of phosphorus, phosphoric acid, and / or, it is represented by the following general formula _[II], H 3 PO ₄ equivalent in a 90 to 110 wt% polyphosphoric acid _(H 3 PO ₄ equivalent of 100 wt% Of which is usually referred to as condensed phosphoric acid)
Polymerization activity of the resulting catalyst with respect to the oxirane compound is increased, which is preferable.

[0015]

[Chemical 4] (In the formula, n is an integer of 2 to 10.)

There is no problem even if a small amount of water is present in the phosphoric acid or the mixture of polyphosphoric acid. However, if the water content of the phosphoric acid or the mixture of polyphosphoric acid is large, the catalytic reaction is inhibited and the polymerization activity is lowered. Since it tends to decrease, in the present invention, it is equivalent to H ₃ PO ₄ , and preferably 83% by weight or more,
More preferably, 90% by weight or more of phosphoric acid or a mixture of polyphosphoric acid is used.

The nitrogen-containing cyclic compound used in the catalyst according to the present invention may be a compound containing a nitrogen atom as a ring-constituting atom and / or a compound containing a ring substituent. The nitrogen-containing cyclic compound having a pKa of 6 to 8 is 25
A compound having a pKa value in the range of 6 to 8, preferably 6.2 to 7.8, measured in an aqueous solution at 0 ° C. Examples of such a nitrogen-containing cyclic compound include 2,4,6-trimethylpyridine, 2,3,6-trimethylpyridine,
2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3-ethyl-6-methylpyridine, 4-isopropylpyridine, 2-propyl Alkyl-substituted pyridines such as pyridine and 2,3,5,6-tetramethylpyridine; 4-amino-3-bromomethylpyridine, 4-amino-3-bromopyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6
-Amino group-containing pyridines such as methylpyridine, 2-aminopyridine, 3-aminopyridine, 3-bromo-4- (dimethylamino) pyridine, 3-bromo-4-methylaminopyridine, and 4- (dimethylamino) pyridine ;
Alkoxypyridines such as 4-ethoxypyridine and 4-methoxypyridine; N-substituted morpholines such as N-ethylmorpholine and N-methylmorpholine; N, N-diethylaniline, N-tert-butylaniline, N,
Substituted anilines such as N-diethylaniline; 1,10-
Dimethoxy-3,8-dimethyl-4,7-phenanthroline, 1,2,3,8,9,10-hexamethyl-4,
Substituted phenanthrolines such as 7-phenanthroline; 1
-Substituted imidazoles such as methyl imidazole and 4-methyl imidazole; Substituted toluidines such as N, N-diethyl-o-toluidine and N, N-dimethyl-p-toluidine; 2-cyclohexyl-2-pyrroline, 2-ethyl Substituted pyrrolines such as 2-pyrroline; 1-aminoisoquinoline, 2-aminoquinoline, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) pyrrolidine, 4-chloro-2-nitrophenol, etc. Can be mentioned. Further, it is preferable to use an alkyl-substituted pyridine represented by the following general formula [I] because the catalytic activity is high and the molecular weight of the resulting oxirane compound polymer is large.

[0018]

[Chemical 5] (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅
May be the same or different from each other and are a hydrogen atom or a lower alkyl group, for example, an alkyl group having 1 to 6 carbon atoms. )

Examples of the alkyl-substituted pyridine represented by the general formula [I] include 2,4,6-trimethylpyridine and 2,2.
3,6-trimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3-ethyl-6-methylpyridine, 4 -Isopropylpyridine, 2-propylpyridine, 2,3,5,6-
Tetramethyl pyridine etc. can be mentioned. Preferred alkyl-substituted pyridines are pyridines which are alkyl-substituted in at least the 2- and / or 6-positions. A particularly preferred compound is 2,4,6-trimethylpyridine.

When the above-mentioned alkylaluminum compound, phosphorus oxoacid compound and nitrogen-containing cyclic compound are reacted to synthesize the catalyst of the present invention, the ratio of alkylaluminum to phosphorus oxoacid compound is such that the phosphorus oxoacid compound is Depending on the number of moles of OH groups in the molecule (when the oxo acid compound contains water, the sum of the OH groups of the oxo acid compound and the OH groups of water), the alkylaluminum compound 0. 65 to 0.95 mol, preferably 0.7 to 0.9
Within the range of 3 moles. When this ratio goes out of the above range,
When used in suspension precipitation polymerization, the amount of the polymer attached to the wall of the reaction vessel increases, which is not preferable. The ratio of the nitrogen-containing cyclic compound is preferably 0.01 to 0.5 mol, and more preferably 0.
It is from 03 to 0.25 mol. If the proportion of the nitrogen-containing compound is out of this range, the polymerization activity of the resulting catalyst for the oxirane compound tends to decrease.

The reaction sequence of these three raw materials is not particularly limited, and an alkylaluminum compound and a phosphorus oxoacid compound may be reacted first, and then the reaction product may be reacted with a nitrogen-containing cyclic compound. Alternatively, the alkylaluminum compound and the nitrogen-containing cyclic compound may be reacted first, and then the reaction product may be reacted with a phosphorus oxoacid compound, and there is no great difference in the polymerization activity of the obtained catalyst with respect to the oxirane compound. Absent. The reaction temperature of each of the above reactions is appropriately selected depending on the alkylaluminum compound or phosphorus oxo acid compound used,
It is usually in the range of -20 ° C to 120 ° C. The catalyst synthesis reaction is preferably carried out in a solvent-free or inert solvent under an atmosphere of an inert gas such as nitrogen gas. Although the inert solvent is not particularly limited, for example, hexane, heptane,
Aliphatic hydrocarbons such as cyclohexane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, dipropyl ether, methylbutyl ether, dimethoxyethane, etc. Or as a mixed solvent of two or more kinds.

The catalyst obtained by the reaction of the alkylaluminum, the oxo acid compound of phosphorus, and the nitrogen-containing cyclic compound is very suitable for the suspension precipitation polymerization of an oxirane compound. Examples of the oxirane compound which can be polymerized include alkylene oxides such as ethylene oxide, propylene oxide, butene oxide, isobutylene oxide and butadiene monoxide; epichlorohydrin,
Substituted alkylene oxides such as epibromhydrin, methacryl chloride oxide, trifluoromethylethylene oxide, dichloroisobutylene oxide and styrene oxide; cycloaliphatic epoxides such as cyclohexene oxide and vinylcyclohexene oxide; allyl glycidyl ether, phenyl glycidyl ether, chloroethyl Glycidyl ether, methyl glycidyl ether, 2
-Glycidyl ethers such as methoxyethyl glycidyl ether, 2- (2-methoxyethoxy) ethyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether; glycidyl acrylate,
Examples thereof include glycidyl esters such as glycidyl methacrylate. Of these, the following general formula [II
I] homopolymerization of the oxirane compound or 2
Copolymerization of at least one species is preferable because the polymerization rate is high and the molecular weight of the obtained polymer is large.

[0023]

[Chemical 6] (In the formula, m is 0 or 1. R ₆ is a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group or a (meth) acryloyl group. , The substituent is halogen,
It is a methoxy group, an ethoxy group or a methoxyethoxy group. )

The polymerization method according to the present invention comprises suspension precipitation polymerization of a monomer oxirane compound in the presence of the above catalyst in an organic solvent which is inactive to the monomer and does not dissolve the resulting polymer. And a method for producing a polymer of an oxirane compound.

The monomer may be soluble or insoluble in an organic solvent, but it is preferable that at least a part thereof is soluble. Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, cyclohexane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; diethyl ether, dipropyl ether, methylbutyl ether, dimethoxyethane and the like. Examples thereof include ethers, which are appropriately selected depending on the type of oxirane compound used and the polymerization temperature. Aliphatic hydrocarbons are preferably used.

The mixing ratio of the monomer oxirane compound, the organic solvent and the catalyst is usually within the range of 100 to 1000 parts by weight of the organic solvent and 0.01 to 5 parts by weight of the catalyst with respect to 100 parts by weight of the oxirane compound. It is preferable. The polymerization temperature is not particularly limited, but is usually -20 ° C.
To 150 ° C., and is appropriately selected depending on the activity of the catalyst, the organic solvent used and the type of the oxirane compound. The polymerization is usually carried out under stirring.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Specific modes for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. [Example 1] 39 ml of triisobutylaluminum was placed in a glass flask having a volume of 300 ml whose interior was replaced with nitrogen.
Then, 81 ml of hexane was added, and the whole was stirred. Phosphoric acid (equivalent to 100% by weight of H ₃ PO ₄ ) 6.0
A solution prepared by dissolving 8 g in 180 ml of diethyl ether was gradually added to a hexane solution of triisobutylaluminum under stirring while controlling the reaction temperature to about 5 ° C. to react them with each other (phosphoric acid addition ratio). Is O of phosphoric acid
Triisobutylaluminum 0.8 per mole of H group
Equivalent to 3 moles). 2,4,6-trimethylpyridine (pKa = 7.4) was added to this reaction solution as a nitrogen-containing cyclic compound.
3) 1.5 ml was added with stirring, and stirring was continued at 60 ° C. for 1 hour. Thus, the catalyst was prepared.

1.8 liters of epichlorohydrin and 9 liters of hexane were placed in a 20-liter stainless steel reaction vessel whose inside was replaced with nitrogen, and the whole amount of the above catalyst was added thereto, and the whole was polymerized at 20 ° C. for 6 hours while stirring. The reaction was carried out. A particulate polymer having a diameter of about 1 mm was deposited in the reaction tank. The amount of polymer adhering to the wall of the reaction tank was 2.8.
%Met. The amount of polymer adhering to the reaction vessel wall was calculated by the following formula:

[Formula 1]

Example 2 As a nitrogen-containing cyclic compound,
2,4-dimethylpyridine (pKa = 6.74) 1.5
A catalyst was prepared by the same procedure as in Example 1 except that ml was used, and the catalyst was used for the polymerization reaction. A particulate polymer having a diameter of about 1 mm was deposited in the reaction tank. The amount deposited on the wall was 3.6%.

[Example 3] N was used as a nitrogen-containing cyclic compound.
-A catalyst was prepared in the same procedure as in Example 1 except that 1.5 ml of ethylmorpholine (pKa = 7.7) was used, and a polymerization reaction was performed using the catalyst. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction tank. The amount deposited on the wall was 5.2%.

Example 4 Phosphoric acid (H ₃ PO ₄ 100
A catalyst was prepared by the same procedure as in Example 1 except that the amount added (corresponding to wt%) was 7.24 g (corresponding to 0.70 mol of triisobutylaluminum to 1 mol of OH group of phosphoric acid). Then, this was used to carry out a polymerization reaction. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction tank. The amount deposited on the wall was 4.8%.

Example 5 Phosphoric acid (H ₃ PO ₄ 100
A catalyst was prepared in the same procedure as in Example 1 except that the amount of (wt%) was 5.47 g (corresponding to 0.93 mol of triisobutylaluminum to 1 mol of OH group of phosphoric acid). Then, this was used to carry out a polymerization reaction. A particulate polymer having a diameter of about 1.0 mm was deposited in the reaction tank. The amount deposited on the wall was 6.1%.

[Example 6] As an oxo acid compound of phosphorus,
21 g of ethyl acid phosphate (21% by weight of phosphorus content), which is a partial ethyl ester of phosphoric acid (OH of ethyl acid phosphate)
0.83 triisobutylaluminum per mole of base
A catalyst was prepared by the same procedure as in Example 1 except that (corresponding to mol) was used, and the catalyst was used for the polymerization reaction. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction tank. The amount deposited on the wall was 5.9%.

Example 7 As an oxo acid compound of phosphorus,
Phosphoric acid in the form of an aqueous solution (equivalent to 85% by weight of H ₃ PO ₄ )
A catalyst was prepared in the same procedure as in Example 1 except that 5.4 g (corresponding to 0.83 mol of triisobutylaluminum relative to 1 mol of the sum of OH groups of phosphoric acid and OH groups of water) was used. A polymerization reaction was carried out using this. A particulate polymer having a diameter of about 1 mm was deposited in the reaction tank. The amount deposited on the wall was 5.9%.

Example 8 37 ml of triethylaluminum was used as the alkylaluminum compound, and 10.7 g of phosphoric acid (corresponding to 100% by weight of H ₃ PO ₄ ) was added thereto.
The procedure was the same as in Example 1, except that 0.83 mol of triethylaluminum (corresponding to 1 mol of OH group of phosphoric acid) and 2.7 ml of 2,4,6-trimethylpyridine were added. A catalyst was prepared and a polymerization reaction was carried out using the catalyst. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction tank. The amount deposited on the wall was 4.8%.

Example 9 A catalyst was prepared by the same procedure as in Example 1, and then, as an oxirane compound, 1.5 liters of epichlorohydrin and 0.6 of ethylene oxide.
The polymerization reaction was carried out in the same procedure as in Example 1 except that liter was used. A particulate copolymer having a diameter of about 1 mm was deposited in the reaction tank. The amount deposited on the wall was 4.1%.

Example 10 A catalyst was prepared by the same procedure as in Example 1, except that 0.8 liters of propylene oxide, 0.9 liters of ethylene oxide and 120 ml of allyl glycidyl ether were used as oxirane compounds. The polymerization reaction was carried out in the same procedure as in Example 1. A particulate terpolymer having a diameter of about 1 mm was deposited in the reaction tank. The amount deposited on the wall was 4.9%.

Example 11 Example 1 was repeated except that a catalyst was prepared by the same procedure as in Example 1 and 1.8 liters of styrene oxide was used as the oxirane compound.
The polymerization reaction was carried out in the same procedure as described above. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction tank. The amount deposited on the wall was 6.3%.

Comparative Example 1 Phosphoric acid (H ₃ PO ₄ 100
A catalyst was prepared in the same procedure as in Example 1, except that the amount of (wt%) was 5.07 g (corresponding to 1.00 mol of triisobutylaluminum to 1 mol of OH group of phosphoric acid). Then, this was used to carry out a polymerization reaction. A particulate polymer having a diameter of about 1.0 mm was deposited in the reaction tank. The amount deposited on the wall was 12.4%.

Comparative Example 2 Phosphoric acid (H ₃ PO ₄ 100
A catalyst was prepared by the same procedure as in Example 1 except that the amount of (wt%) was 8.45 g (corresponding to 0.60 mol of triisobutylaluminum to 1 mol of OH groups of phosphoric acid). Then, this was used to carry out a polymerization reaction. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction tank. The adhered amount on the wall was 16.8%.

[Comparative Example 3] As a nitrogen-containing cyclic compound,
A catalyst was prepared in the same procedure as in Example 1 except that 1.5 ml of 1,8-diazabicyclo [5,4,0] -7-undecene (pKa = 12.5) was used, and this was used. The polymerization reaction was carried out. A large granular polymer having a diameter of about 8 mm was deposited in the reaction tank. The adhered amount on the wall was 18.5%.

[Comparative Example 4] As a nitrogen-containing cyclic compound, 2
A catalyst was prepared by the same procedure as in Example 1 except that 1.5 ml of -ethylpyridine (pKa = 5.89) was used, and the polymerization reaction was carried out using this. A large granular polymer having a diameter of about 15 mm was deposited in the reaction tank. The amount deposited on the wall was 26.2%.

[Evaluation of Polymer] The obtained polymer (including the material adhering to the reaction vessel wall) was sufficiently dried in vacuum, and the weight was measured to determine the polymer yield. The obtained polymer was vacuum dried and then dissolved in dimethylformamide, and the molecular weight of the polymer was determined by gel permeation chromatography.
Furthermore, the weight average molecular weight was calculated in terms of standard polystyrene. The results of these evaluations are shown in Table 1.

[0044]

[Table 1]

As is apparent from the appearance of the precipitated polymer, when the epichlorohydrin was polymerized using the catalysts obtained in Examples 1 to 8, a fine particle homopolymer was obtained and adhered to the wall. The quantity is also decreasing. Further, as is clear from Table 1, in these Examples, the polymer yield and the molecular weight of the obtained polymer both showed high numerical values. In each of Examples 9 to 11 in which (co) polymerization was carried out using a different kind of monomer, a particulate polymer was obtained with a small amount of adhered wall, and in these Examples, the polymer yield was also obtained. The molecular weights of the polymers were both high.

On the other hand, the value of alkylaluminum is 0.65 to 0.
In Comparative Example 1 and Comparative Example 2 which are out of the range of 95 mols, although the polymer in particle form is obtained, the amount of adhesion on the wall is large. In Comparative Example 3 using 1,8-diazabicyclo [5,4,0] -7-undecene and Comparative Example 4 using 2-ethylpyridine, the polymer yield and the molecular weight of the polymer are considerably high, It can be seen that the polymer is obtained in the form of large granules and that these compounds are not suitable as catalysts for suspension precipitation polymerization.

[0047]

The oxirane compound polymerization catalyst according to the present invention is constituted as described above, and by using this, a high molecular weight polymer can be obtained with high production efficiency.
Moreover, the amount of the polymer attached to the wall of the reaction tank is small. Therefore, by using the catalyst according to the present invention, rubber parts for automobiles,
It is possible to efficiently and easily produce a high-quality oxirane compound polymer used in a very wide range of fields such as rubber members for electric and electronic devices, polymers for blending various plastics, and polymer solid electrolytes.

Continued front page    (72) Inventor Yumi Shimizu             1-10-8 Edobori, Nishi-ku, Osaka City, Osaka Prefecture             Within Daiso Corporation (72) Inventor Mikio Yuka             1-10-8 Edobori, Nishi-ku, Osaka City, Osaka Prefecture             Within Daiso Corporation F-term (reference) 4J005 AA04 BB01 BB04

Claims (6)

[Claims] 1. An (A) alkylaluminum compound,
(B) a reaction product of a phosphorus oxo acid compound having at least one OH group in the molecule and (C) a nitrogen-containing cyclic compound having a pKa of 6 to 8; The proportion of the phosphorus oxo acid compound having at least one OH group in the
It is characterized by being in the range of 0.65 to 0.95 mol of alkylaluminum per 1 mol of the group (when the oxo acid compound contains water, the sum of OH groups of the oxo acid compound and OH groups of water). , A catalyst for polymerization of an oxirane compound for a reaction of suspension precipitation polymerization of an oxirane compound in an organic solvent in which the polymer is insoluble. 2. The catalyst for polymerizing an oxirane compound according to claim 1, wherein the nitrogen-containing cyclic compound (C) having a pKa of 6 to 8 is an alkyl-substituted pyridine represented by the following general formula [I]. [Chemical 1] (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅
May be the same or different from each other and are a hydrogen atom or a lower alkyl group. ) 3. The catalyst for polymerization of an oxirane compound according to claim 3, wherein the nitrogen-containing cyclic compound (C) pKa6 to 8 is 2,4,6-trimethylpyridine. 4. The (B) oxo acid compound of phosphorus having at least one OH group in the molecule is phosphoric acid and / or is represented by the following general formula [II], and is 9 equivalent to H ₃ PO _4.
The catalyst for polymerizing an oxirane compound according to any one of claims 1 to 3, which is a mixture of polyphosphoric acid in an amount of 0 to 110% by weight. [Chemical 2] (In the formula, n is an integer of 2 to 10.) 5. The oxirane compound is represented by the following general formula [II
The catalyst for polymerization of an oxirane compound according to any one of claims 1 to 4, which is a compound represented by the formula [I]. [Chemical 3] (In the formula, m is 0 or 1. R ₆ is a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group or a (meth) acryloyl group. , The substituent is halogen,
It is a methoxy group, an ethoxy group or a methoxyethoxy group. ) 6. An oxirane compound is subjected to suspension precipitation polymerization in the presence of a catalyst in an organic solvent in which the polymer is insoluble,
A method for producing a polymer of an oxirane compound, wherein
5. A method for producing an oxirane compound polymer, which comprises using the catalyst according to any one of 1 to 5.