JP2010265425A - High polymer of oxirane compound, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ring-opening polymerization catalyst capable of obtaining a polymer of an oxirane compound having a high molecular weight in the polymerization of the oxirane compound, and especially a method for producing a high molecular weight material by a simple method without containing a complex process for preparing the polymerization catalyst. <P>SOLUTION: This method for producing the polymer of the oxirane compound in the ring-opening polymerization reaction of the oxirane compound is provided by using (A) montmorillonite and (B) an alkylaluminum as the ring-opening polymerization catalysts. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer of an oxirane compound such as ethylene oxide, propylene oxide, epichlorohydrin, and allyl glycidyl ether.

  The polymer of the oxirane compound becomes a polymer with various properties depending on the selection of the oxirane compound used as a raw material. Therefore, rubber parts for automobiles, rubber members for electric and electronic devices, polymers for various plastic blends, solid polymer electrolytes, etc. Is used in a wide range of fields.

  As catalysts for polymerizing oxirane compounds, Lewis acid catalysts such as boron fluoride, aluminum chloride, tin chloride and iron chloride are known. When polymerization is carried out using these catalysts, various side reactions such as chain transfer reactions are involved, so that only a polymer having a relatively low molecular weight (for example, a molecular weight of several thousand to several tens of thousands) can be obtained.

  In order to obtain a high molecular weight polymer useful in a specific field such as rubber industry, a reaction product of iron chloride, propylene oxide and water (patent document 1, non-patent document 1), reaction of alkyl zinc and water. Products (Non-patent Document 2, Patent Document 2), Reaction Products of Alkyl Aluminum and Water (Patent Document 3, Non-Patent Document 2, Non-Patent Document 3, Non-Patent Document 4), Reaction of Alkyl Aluminum and Phosphate Compound Use of a catalyst system in which a third component is added to the product (Patent Document 4, Patent Document 5, Patent Document 6), a reaction product of an organotin compound and a phosphate ester (Patent Document 7, Non-Patent Document 5) Widely known.

  However, these polymerization catalysts which give high polymers of oxirane compounds are not industrially efficient because the preparation method is complicated and a catalyst preparation tank is required.

  For example, in the polymerization catalyst using iron chloride described in Non-Patent Document 1, iron chloride is reacted with propylene oxide under cooling conditions, followed by hydrolysis at 40 ° C. for 24 hours, and further at 80 ° C. under reduced pressure for 3 hours. Prepared by baking for hours. Such a complicated operation and a long reaction time are required.

  On the other hand, in order to obtain a reaction product of alkylzinc or alkylaluminum described in Non-Patent Document 2 with water, the catalyst preparation tank must be cooled to 0 ° C. and reacted for 4 to 24 hours. Takes a long time. In addition, preparation of the reaction product of triisobutylaluminum, orthophosphoric acid and N-methylmorpholine described in Patent Document 4 also requires cooling of the reaction tank and several hours of reaction time.

  Preparation of the polymerization catalyst described in Non-Patent Document 5 required calcination (200 ° C.) for 10 hours or more and catalyst purification after calcination.

US Patent 2,706,181 Shoko 36-3394 US Patent 3,135,705 Japanese Patent Publication No.56-8852 Japanese Patent Publication No.56-51171 Patent 3,937,830 US Patent 3,773,694

Polymer 1989, 30, 1709-1713 J. et al. Polym. Sci .: Part A-1 1969, 7, 525-567 Polym. J. et al. 1990, 22, 326-330 J. et al. App. Polym. Sci. 2001, 80, 2446-2454 J. et al. Polym. Sci. Part A: Polym. Chem. 2007, 45, 3032-3041

  Various polymerization catalysts that give high polymers of oxirane compounds have been studied so far, but the preparation involves complicated steps, requires a catalyst preparation tank, and requires a long reaction time. Therefore, there is always a need for a high polymerization catalyst of an oxirane compound that is prepared by a simpler method.

  In view of the above problems, an object of the present invention is to provide a ring-opening polymerization catalyst capable of obtaining a high molecular weight oxirane compound polymer in the polymerization of an oxirane compound, which is particularly troublesome in the preparation of the polymerization catalyst. The present invention is to provide a production method which gives a high molecular weight body by a simple method without requiring any simple process or equipment.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a high molecular weight oxirane compound polymer by adding alkylaluminum to montmorillonite, which is a representative mineral of smectite. It has been found that a catalyst is provided and the present invention has been completed.

That is, the present invention
[1] A method for producing an oxirane compound polymer, characterized by using a catalyst for the polymerization of an oxirane compound comprising (A) montmorillonite and (B) an alkylaluminum compound represented by the general formula (1);

(In the formula, n is an integer of 1 to 3, R is a linear or branched alkyl group having 1 to 10 carbon atoms, X is a halogen atom or a hydrogen atom, and Al is an aluminum metal atom. Shown);
[2] The method for producing an oxirane compound polymer according to Item 1, wherein (A) montmorillonite is in the form of at least one clay mineral selected from organic bentonite, bentonite, acidic clay, and activated clay;
[3] The oxirane compound subjected to the ring-opening polymerization reaction is a method for producing a polymer of a monomer containing one or more oxirane compounds represented by the following general formula (2), [1] or [ 2] for producing an oxirane compound polymer;

(In the formula, m is 0 or 1. R is a hydrogen atom or an alkyl group, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group, or a (meth) acryloyl group, each of which may have a substituent. And the substituent is a halogen atom, a methoxy group, an ethoxy group or a methoxyethoxy group);

[4] The method for producing an oxirane compound polymer according to the above [1] to [3], wherein the polymer of the oxirane compound is produced by suspension precipitation polymerization in an organic solvent in which the polymer of the obtained oxirane compound is insoluble. ;

[5] An oxirane compound polymer obtained by the method for producing an oxirane compound polymer according to the above [1] to [4], and containing 0.1 to 10 wt% of montmorillonite;

  By using the production method of the present invention, it is possible to easily obtain a high molecular weight oxirane compound polymer without requiring a complicated polymerization catalyst preparation in the production of the oxirane compound polymer. The oxirane compound polymer obtained by the polymerization catalyst of the present invention is a high-quality oxirane in a very wide range of fields such as automotive rubber parts, rubber members for electric and electronic devices, polymers for various plastic blends, and polymer solid electrolytes. It can be used as a compound polymer.

Hereinafter, the configuration of the present invention will be described in detail.
Polymerization Catalyst The polymerization catalyst of the present invention comprises (A) montmorillonite (B) an alkylaluminum compound.

(A) Montmorillonite (A) Montmorillonite is a representative mineral of smectite, which is a kind of layered silicate mineral, but in the present invention, it may be used in the form of a clay mineral containing montmorillonite. Clay minerals containing montmorillonite include bentonite, organic bentonite (bentonite in which cations existing between montmorillonite crystal layers are ion-exchanged with cations such as quaternary ammonium ion, phosphonium ion, imidazolium ion), acidic clay , Activated clay and the like, and organic bentonite is preferable.

Specific examples of (A) montmorillonite used in the present invention include, in addition to montmorillonite that is usually sold as a reagent, Bengel, Bengel HV, Bengel HVP, Bengel F, Bengel FW, Bengel Bright 11 manufactured by Hojun Co., Ltd. , Wengel A, Wengel W-100, Wengel W-100U, Wengel W-200U, Wengel W-300U, Wengel W-300HP, Wengel SH, Multiben, Esben, Esben C, Esben E, Esben W, Esben W, Esben WX , Organite, Organite D, Organite T, Sven NX, Sven NX80, Sben NZ, Sven NZ70, Galeon Earth, Mizuka Ace, Ben Clay MK-1, Ben Clay SL, Kunimine Industries, Ltd. Kunipia F, etc. Smecton and the like, which can be used in either alone or in combinations of two or more, depending on the monomeric oxirane compound used.

  (A) As addition amount of a montmorillonite, it is preferable that it is 0.3-20 wt% with respect to the oxirane compound to superpose | polymerize, and it is more preferable that it is 0.5-10 wt%.

The (B) used in the alkylaluminum compound present invention (B) an alkylaluminum compound, may be exemplified alkylaluminum compound represented by the following general formula (I).

(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and n is an integer of 1 to 3).
As a hydrocarbon group, a C1-C8 (preferably C1-C6) alkyl group is preferable, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, sec -Butyl group, tert-butyl group, normal pentyl group, normal hexyl group, normal heptyl group, normal octyl group and the like.

  Specific examples of the (B) alkylaluminum compound used in the present invention are trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride. , Ethylaluminum dichloride, aluminum trichloride, aluminum tribromide, aluminum trifluoride, aluminum triiodide, etc., which may be used alone or in combination of two or more depending on the monomer oxirane compound used. it can.

  The mixing ratio of the (A) montmorillonite (B) alkylaluminum compound is 10 to 150 parts by weight, more preferably 30 to 100 parts by weight with respect to 100 parts by weight of (A) montmorillonite. When the mixing ratio is within these ranges, a high polymerization activity of the catalyst for the oxirane compound can be obtained, and a polymer of a high molecular weight oxirane compound can be obtained.

Polymerization method The method for producing a polymer of an oxirane compound of the present invention is characterized in that a monomer oxirane compound is polymerized using the above-mentioned polymerization catalyst, and the oxirane compound monomer and polymer are both soluble organic compounds. A solution polymerization method in which an oxirane compound is polymerized in a solvent, a suspension precipitation polymerization method in which the polymer of the oxirane compound obtained by polymerization is polymerized in an organic solvent, and the resulting polymer is precipitated. Can be appropriately selected. The suspension precipitation polymerization method is preferable in that the concentration of the monomer can be increased during the polymerization, and separation of the polymer after polymerization and the solvent is easy.

  In the polymerization method of the present invention, (A) montmorillonite, (B) an alkylaluminum compound, an oxirane compound, and a solvent are added to a reaction vessel under a nitrogen stream and reacted. The order of addition is not particularly limited. First, (A) montmorillonite and a solvent are added to a reaction vessel, and (B) an alkylaluminum compound is added and stirred, and then an oxirane compound is added. From the viewpoint of

The polymerization temperature is not particularly limited, but is usually in the range of −20 to 150 ° C., preferably 0 to 100 ° C., and is appropriately selected according to the activity of the catalyst, the organic solvent used, and the type of oxirane compound. Selected.
The polymerization reaction time is usually in the range of 1 to 18 hours, preferably 3 to 12 hours, and is appropriately selected according to the activity of the catalyst, the organic solvent used, and the type of oxirane compound.
The polymerization is usually carried out with stirring.

Oxirane Compound A polymerization catalyst comprising (A) montmorillonite and (B) an alkylaluminum compound of the present invention is suitable for polymerization of an oxirane compound. Examples of the oxirane compound that can be polymerized include alkylene oxides such as ethylene oxide, propylene oxide, butene oxide, isobutylene oxide, and butadiene monooxide, epichlorohydrin, epibromohydrin, methacrylic chloride oxide, trifluoromethylethylene oxide, dichloroisobutylene oxide, Substituted alkylene oxides such as styrene oxide, cycloaliphatic epoxides such as cyclohexene oxide and vinylcyclohexene oxide, allyl glycidyl ether, phenyl glycidyl ether, chloroethyl glycidyl ether, methyl glycidyl ether, 2-methoxyethyl glycidyl ether, 2- (2 -Methoxyethoxy) ethyl glycidyl ether, cyclohexyl glycidyl ether Glycidyl ethers such as benzyl glycidyl ether, glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and the like, and homopolymerization using one of these oxirane compounds or copolymerization using two or more Good.
Of these, homopolymerization of an oxirane compound represented by the following general formula (2) or copolymerization of two or more types is preferred because the polymerization rate is high and a high molecular weight polymer can be obtained in a short time.

(In the formula, m is 0 or 1. R is a hydrogen atom or an alkyl group, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group, or a (meth) acryloyl group, each of which may have a substituent. And the substituent is a halogen atom, a methoxy group, an ethoxy group or a methoxyethoxy group.)
Here, as an alkyl group, a C1-C8 (preferably C1-C6) alkyl group is preferable, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group. , Sec-butyl group, tert-butyl group, normal pentyl group, normal hexyl group, normal heptyl group, normal octyl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms (preferably 4 to 6 carbon atoms), such as a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, or cyclooctyl group. Etc.
The aralkyl group is preferably an aralkyl group having 7 to 14 carbon atoms (preferably 7 to 12 carbon atoms), such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group, and the like. Is mentioned.
As the alkenyl group, an alkenyl group having 2 to 8 carbon atoms (preferably 2 to 6 carbon atoms) is preferable, for example, vinyl group, allyl group, 1-propenyl group, 1-methylvinyl group, butenyl group, pentenyl group. Hexenyl group, heptenyl group, octenyl group and the like.

Suspension Precipitation Polymerization Suspension precipitation polymerization is a method in which a monomer oxirane compound is polymerized in the presence of the polymerization catalyst of the present invention in an oxirane compound monomer and an organic solvent inert to the polymerization catalyst. In this method, a polymer of an oxirane compound is deposited.

  The monomer may be soluble or insoluble in an organic solvent, but is preferably soluble. Examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and octane, aromatic hydrocarbons such as benzene, toluene, xylene, diethyl ether, dipropyl ether, methyl butyl ether, dimethoxyethane, and the like. The ethers may be selected as appropriate according to the type of oxirane compound used and the polymerization temperature. Preferably, aliphatic hydrocarbons are used.

  The mixing ratio of the monomer oxirane compound, the organic solvent and the catalyst (the mixture of (A) montmorillonite and (B) the alkylaluminum compound) is usually 10 to 5000 for 100 parts by weight of the oxirane compound. Parts by weight, preferably 100 to 1000 parts by weight, and the catalyst is usually in the range of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

  In the polymerization of the oxirane compound ((A) montmorillonite, (B) in accordance with the oxirane compound to be polymerized (mainly for the purpose of adjusting the yield, weight average molecular weight, crystallinity), Lewis basic compounds such as nitrogen-containing cyclic compounds, phosphines and ketones may be added and used.

  Examples of the Lewis basic compound include alkyl-substituted pyridines such as 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, 4-methylpyridine and 2-methylpyridine; Amino group-containing pyridines such as amino-3-bromopyridine, 4-amino-3-methylpyridine and 2-amino-6-methylpyridine; alkoxypyridines such as 4-ethoxypyridine and 4-methoxypyridine; N-ethyl N-substituted morpholines such as morpholine and N-methylmorpholine; N, N-substituted anilines such as N, N-diethylaniline; 1,10-dimethoxy-3,8-dimethyl-4,7-phenanthroline and the like Substituted phenanthrolines; substituted imidazoles such as 4-methylimidazole; N, N-dimethyl -Substituted toluidines such as -p-toluidine; substituted pyrrolines such as 2-ethyl-2-pyrroline; phosphines such as triphenylphosphine and trimethylphosphine; ketones such as cyclohexanone, acetylacetone and benzoquinone.

  The mixing ratio of the Lewis basic compound to the catalyst is not particularly limited, but is usually 10 to 500 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the catalyst (mixture of (A) montmorillonite and (B) alkylaluminum compound). Is in the range of 20 to 300 parts by weight.

Oxirane Compound Polymer The oxirane compound polymer produced by the method of the present invention has a high molecular weight and is used for rubber parts for automobiles, rubber members for electric and electronic devices, polymers for various plastic blends, polymer solid electrolytes, etc. It can be applied to industrial rubber.
Conventional polymerization catalysts that do not require catalyst preparation tend to have a high frequency of side reactions such as chain transfer reactions, making it difficult to obtain high molecular weight polymers.

  In the catalyst for the polymerization of oxirane compounds of the present invention, the inventors of the present invention have the ability of montmorillonite to act on the oxirane compound by the action of alkylaluminum on the montmorillonite interlayer or surface layer. Unlike the case where it is used for polymerization, it is presumed that a high molecular weight oxirane compound polymer can be obtained without inhibiting the polymerization (growth) reaction by side reactions.

  The oxirane compound polymer obtained by the present invention may be obtained as a nanocomposite material of an oxirane compound polymer and montmorillonite intercalated between montmorillonite layers, improving various physical properties such as heat resistance and strength. Can be expected. In the present invention, an oxirane compound polymer characterized by containing 0.1 to 10 wt% of montmorillonite in the oxirane compound polymer can be exemplified.

The weight average molecular weight of the polymer of the oxirane compound obtained by the method of the present invention varies depending on the monomer oxirane compound used, but is usually 50 × 10 ^{4 to} 500 × 10 ⁴ , preferably 100 × 10 ^{4 to} 300 ×. 10 is in the range of ^4. A polymer having a weight average molecular weight within this range is useful as an industrial rubber because it has good processability and solubility and sufficient strength.

  Here, the weight average molecular weight is obtained by vacuum drying the polymer, dissolving it in dimethylformamide, and calculating the weight average molecular weight of the polymer in terms of polystyrene by gel permeation chromatography. The details of the measuring method will be described in detail in Examples described later.

  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]
Aldrich Montmorillonite (38 mg), dehydrated hexane (2 mL), added 1.0 M triethylaluminum / hexane solution (230 μL) were added to a 30 mL glass Schlenk tube whose inside had been purged with nitrogen, and then stirred. Dehydrated hexane (16 mL) and epichlorohydrin (5.0 g) were added, and the whole was subjected to a polymerization reaction for 3 hours while stirring at 60 ° C. After 3 hours, Montmorillonite (38 mg), dehydrated hexane (2 mL), and 1.0 M triethylaluminum / hexane solution (230 μL) were added, and a polymerization reaction was further performed for 3 hours. A particulate polymer precipitated in the reaction vessel.

[Example 2]
A particulate polymer was obtained by carrying out a polymerization reaction in the same manner as in Example 1 except that Esbben NX80 manufactured by Hojun Co., Ltd. was used instead of Aldrich Montmorillonite.

[Example 3]
A particulate polymer was obtained by carrying out a polymerization reaction in the same manner as in Example 2 except that a 1.0 M triisobutyl aluminum / hexane solution (230 μL) was used instead of the 1.0 M triethyl aluminum / hexane solution. Got.

[Example 4]
Instead of Aldrich's Montmorillonite, a polymerization reaction was performed in the same procedure as in Example 1 except that Organonite D manufactured by Hojun Co., Ltd. was used to obtain a particulate polymer.

[Example 5]
Instead of Aldrich's Montmorillonite, Kunipia F manufactured by Kunimine Industry Co., Ltd. and 2,6-dimethylpyridine (25 mg) were used, except that a polymerization reaction was performed in the same procedure as in Example 1, A polymer was obtained.

[Comparative Example 1]
The polymerization reaction was performed in the same procedure as in Example 1 except that Aldrich Montmorillonite was not used. A viscous semi-solid polymer was obtained.

[Comparative Example 2]
The polymerization reaction was carried out in the same procedure as in Example 1 except that the 1.0 M triethylaluminum / hexane solution was not used. A polymer was not obtained.

[Comparative Example 3]
The polymerization reaction was carried out in the same procedure as in Example 2 except that the 1.0 M triethylaluminum / hexane solution was not used. A polymer was not obtained.

[Comparative Example 4]
The polymerization reaction was performed in the same procedure as in Example 4 except that the 1.0 M triethylaluminum / hexane solution was not used. A polymer was not obtained.

[Comparative Example 5]
The polymerization reaction was performed in the same procedure as in Example 5 except that the 1.0 M triethylaluminum / hexane solution was not used. A polymer was not obtained.

[Comparative Example 6]
A polymerization reaction was carried out in the same procedure as in Example 1 except that zeolite CBV100 (25 mg) manufactured by ZEOLYST was used instead of Aldrich Montmorillonite. A polymer was not obtained.

[Evaluation of polymer]
The obtained polymer was sufficiently dried, and the polymer yield was determined by measuring the weight. The obtained polymer was vacuum dried and then dissolved in dimethylformamide, and the weight average molecular weight of the polymer was calculated in terms of polystyrene by gel permeation chromatography. Details of the measurement conditions are described below.
Weight average molecular weight: Gel permeation chromatography system manufactured by Shimadzu Corporation: SCL-10A (detector is RID-10A), Showa Denko column Shodex KD807, KD806, KD806M, KD803, measurement temperature 60 ° C., solvent DMF.
These results are shown in Table 1.

  As is apparent from the analysis results of the obtained polymers, the molecular weights of the epichlorohydrin polymers obtained in Examples 1 to 5 all showed high numerical values exceeding 1 million in terms of weight average molecular weight. These are suitable for industrial use in rubber applications.

  On the other hand, in the case where the clay mineral containing montmorillonite was not used in Comparative Example 1, a high polymer of epichlorohydrin was not obtained, and it was estimated that epichlorohydrin was cationically polymerized by Lewis acid. In addition, in Comparative Examples 2 to 5, it was found that no epichlorohydrin polymer was obtained when no alkylaluminum was added to the clay mineral containing montmorillonite. Furthermore, it was found that no polymer was obtained when zeolite was used instead of montmorillonite in Comparative Example 6.

  The production method of the high polymerization of the oxirane compound according to the present invention is constituted as described above, and by using this, a high molecular weight polymer can be easily formed without requiring a complicated catalyst preparation or a catalyst preparation tank. Has been obtained. Therefore, by using the production method according to the present invention, high molecular weight oxiranes used in a very wide range of fields such as rubber parts for automobiles, rubber members for electric and electronic devices, polymers for various plastic blends, polymer solid electrolytes and the like. A compound polymer can be easily produced.

Claims (5)

In the ring-opening polymerization reaction of the oxirane compound,
(A) Montmorillonite and (B) the following general formula (1)

Wherein n is an integer of 1 to 3, R is a linear or branched alkyl group having 1 to 10 carbon atoms, X is a halogen atom or a hydrogen atom, and Al is an aluminum metal atom. A method for producing an oxirane compound polymer, wherein the alkylaluminum compound represented by formula (1) is used as a ring-opening polymerization catalyst.   (A) The method for producing an oxirane compound polymer according to claim 1, wherein the montmorillonite is in the form of at least one clay mineral selected from organic bentonite, bentonite, acidic clay, and activated clay. The method for producing an oxirane compound polymer according to claim 1 or 2, wherein the oxirane compound subjected to the ring-opening polymerization reaction contains one or more oxirane compounds represented by the following general formula (2).

(In the formula, m is 0 or 1. R is a hydrogen atom or an alkyl group, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group, or a (meth) acryloyl group, each of which may have a substituent. And the substituent is a halogen atom, a methoxy group, an ethoxy group or a methoxyethoxy group.)   The manufacturing method of the oxirane compound polymer of Claims 1-3 which manufactures the polymer of an oxirane compound by suspension precipitation polymerization in the organic solvent in which the polymer of the obtained oxirane compound is insoluble. An oxirane compound polymer comprising 0.1 to 10 wt% of montmorillonite in an oxirane compound polymer obtained according to the method for producing an oxirane compound polymer according to claim 1.