JP2002249516A - Production process for epoxidized polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process whereby an epoxidized polymer can be produced safely, efficiently, and industrially advantageously. SOLUTION: To a solution (I) prepared by dissolving a polymer having olefinic double bond and a quaternary ammonium salt in a water-immiscible organic solvent, an aqueous solution (II) containing a tungsten compound (A) selected from ammonium tungstate and phosphorus tungstic acid and phosphoric acid (B), the content of phosphoric acid (B) being at least 0.25 mol per g-atom of tungsten metal atom contained in the tungsten compound (A), and an aqueous hydrogen peroxide solution (III) are added and reacted in the substantial absence of an alkali metal ion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an epoxidized polymer. The epoxidized polymer obtained by the production method of the present invention is useful as a raw material, an adhesive and the like of a UV curable resin for sealants and coating applications.

[0002]

2. Description of the Related Art As a method for producing a polymer having an epoxy group, a method of epoxidizing a polymer having an olefinic double bond is useful. As a method of epoxidizing a polymer having an olefinic double bond, a method of epoxidizing with a peracid such as formic acid is known [“Polymer”
s for Advanced Technologies, Vol. 7, pp. 67-72 (19
96) "), however, a peracid such as formic acid is relatively expensive, and an acid such as formic acid present in the reaction system causes the epoxy group in the produced epoxidized polymer to ring-open. However, there is a problem that the epoxidation selectivity of the epoxidized polymer is reduced.

On the other hand, the following methods (1) to (4) are known as methods for epoxidizing a polymer having an olefinic double bond using inexpensive hydrogen peroxide. I have. (1) Journal of Polymer Science: Part A: Polymer
Chemistry, 29 , 1183-1189 (1991) (hereinafter abbreviated as Reference 1), isolated from a reaction mixture obtained by adding phosphoric acid and trioctylmethylammonium chloride to a mixture of tungstic acid and hydrogen peroxide. A method for epoxidizing a styrene-butadiene-styrene triblock copolymer using the obtained oxo complex of tungsten is described. (2) US Pat. No. 5,789,512 (hereinafter abbreviated as Document 2) discloses an unsaturated polymer in the presence of tungstic acid or a salt thereof, phosphoric acid or a salt thereof and at least one type of phase transfer catalyst. Epoxidation with hydrogen peroxide is described. (3) JP-A-5-247016 (hereinafter abbreviated as Document 3) discloses (a) one or more oxidation catalysts selected from tungstic acids and molybdic acids, and (b) a fourth alkyl group containing a long-chain alkyl group. A method is described in which a glycidyl ester having a cyclohexene ring is epoxidized with hydrogen peroxide in the presence of a secondary ammonium salt or a phosphonium salt having a long-chain alkyl group and (c) a phosphate anion. (4) JP-A-5-247120 (hereinafter abbreviated as Reference 4) discloses a two-phase dicyclopentadiene (meth) acrylate using hydrogen peroxide, a phosphoric acid compound, a tungstate compound and an onium salt. Methods for epoxidizing polymers are described.

[0004]

However, in the method described in Document 1, the oxo complex of tungsten must be isolated and then used in the epoxidation reaction, so that the operation is complicated and such a complex is required. It is necessary to use a halogenated hydrocarbon, which is considered to have a problem on the environment, as a solvent in the synthesis and epoxidation reaction of the compound. Reference 2 does not particularly describe the details of the method of adding each component used in the reaction. Reference 2 shows an example in which the epoxy value is 18
2.7 mg KOH / g (Example 1), 183.3 mg KOH / g
Example 2 discloses a method for producing polybutadiene of 172.8 mgKOH / g (Example 3), but only about 20% of the double bonds in polybutadiene are epoxidized. The present inventors further tried to increase the epoxidation rate of double bonds in polybutadiene,
The gelation of the reaction mixture proceeded, and the desired epoxidized polymer could not be obtained. In addition, in the method of the example of Reference 2, generation of oxygen due to decomposition of hydrogen peroxide is remarkable. For this reason, it was recognized that a large amount of hydrogen peroxide had to be used, and there was a problem in safety.

[0005] Reference 3 discloses an aqueous solution prepared by dissolving a salt of tungstic acid and phosphoric acid in water in an organic solvent solution of a reaction raw material and a quaternary ammonium salt and adjusting the pH using sodium carbonate. And while stirring,
A method for performing epoxidation by adding hydrogen peroxide is disclosed. However, the presence of alkali metal ions in the reaction system promotes the decomposition of hydrogen peroxide. For this reason, it was recognized that a large amount of hydrogen peroxide had to be used, and there was a problem in safety. In addition, the method described in Reference 3
An attempt was made to apply to a polymer having no cyclohexene ring in general.
It was found that the reaction mixture gelled and the desired epoxidized polymer could not be obtained. Literature 4 discloses, as a method for adding each component used in the reaction, (i) dissolving a hydrogen peroxide solution and an onium salt in which a phosphoric acid compound and a tungstic acid compound or a condensate of a phosphoric acid compound and a tungstic acid compound are dissolved. After mixing a water-insoluble solvent with water and adding a dicyclopentadiene (meth) acrylate polymer to perform epoxidation; and (ii) water in which an onium salt and a dicyclopentadiene (meth) acrylate polymer are dissolved. A method for performing epoxidation by mixing a solvent insoluble in water with a phosphoric acid compound and a tungstic acid compound, or a hydrogen peroxide solution in which a condensate of a phosphoric acid compound and a tungstic acid compound is dissolved. However, since hydrogen peroxide and a tungstate compound were mixed and then used in the reaction, oxygen was continuously generated in the reaction system, and it was recognized that there was a problem in terms of safety. This method also requires the use of a large amount of hydrogen peroxide.

[0006] As described above, the methods described in Literatures 1 to 4 are not advantageous for industrially implementing a method for producing a polymer having an epoxy group. The present invention has been made in view of the above circumstances, and has as its object to provide a method for producing an epoxidized polymer safely, efficiently, and industrially advantageously.

[0007]

Means for Solving the Problems The present inventors have disclosed documents 1 to 3.
The method described in No. 4 was studied from the viewpoint of further improvement. Regarding a method of performing epoxidation using a tungsten compound, a phosphoric acid compound and hydrogen peroxide in the presence of a quaternary ammonium salt, many documents are known in addition to the above-mentioned documents. Reports on active species and the like have been made. However, the details of the reaction have not been completely elucidated. Therefore, optimizing the reaction conditions according to the purpose requires a lot of trial and error even at present. When the present inventors are configured to satisfy all of the following four points (a) to (d), the decomposition of hydrogen peroxide is reduced, and the epoxidation degree of the epoxidized polymer as a product is increased. And that the stability of the product is maintained. Also, of the mixture after the reaction,
It was also found that the liquid separation property between the aqueous layer and the organic layer containing the product was extremely good, and that the product could be efficiently isolated.

(A) Using ammonium tungstate and / or phosphotungstic acid as a tungsten compound and phosphoric acid as a phosphoric acid compound, an aqueous solution containing both a tungsten compound and phosphoric acid is prepared. (B) The amounts of the above-mentioned tungsten compound and phosphoric acid are set to a specific ratio. (C) A solution prepared by dissolving a polymer having an olefinic double bond and a quaternary ammonium salt in an organic solvent immiscible with water is added with the aqueous solution prepared in (a) and an aqueous hydrogen peroxide solution. To react. (D) performing the reaction substantially in the absence of alkali metal ions.

That is, the present invention relates to a method for preparing a solution (I) obtained by dissolving a polymer having an olefinic double bond and a quaternary ammonium salt in an organic solvent immiscible with water. It contains a tungsten compound (A) selected from acids and phosphoric acid (B), and the content of phosphoric acid (B) is 0.25 mol or more per gram atom of tungsten metal atom contained in the tungsten compound (A). An aqueous solution (II) of the formula (I) and an aqueous solution (III) of hydrogen peroxide are added and reacted substantially in the absence of alkali metal ions.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer in the present invention includes an oligomer. As the polymer having an olefinic double bond, the olefinic double bond may be contained in an amount of 1 to 100 mol% based on all monomer units constituting the polymer.
What is contained is mentioned.

The olefinic double bond of the polymer having an olefinic double bond may have either a cis or trans structure, or both may be mixed. The distribution of the olefinic double bond in the polymer having an olefinic double bond is not particularly limited, for example, a regular distribution, a block-like distribution, a random distribution, a tapered distribution, and some of these are For example, a mixed distribution may be used.

When the polymer having an olefinic double bond has a side chain, the olefinic double bond may be contained in either the main chain or the side chain of the polymer. From the viewpoint of the stability of the polymer, it is preferable that 50 mol% or more of all the olefinic double bonds of the polymer having an olefinic double bond is contained in the main chain.

The polymer having an olefinic double bond is
It may be produced by various polymerization methods such as radical polymerization, ionic polymerization, coordination polymerization, and metathesis polymerization.

Examples of the polymer having an olefinic double bond include polydienes such as polybutadiene and polyisoprene; polyalkenes obtained by ring-opening metathesis polymerization of cycloalkenes such as cyclopentene, cyclohexene and cyclooctene; and isoprene-butadiene block copolymers. Polymer, styrene-butadiene block copolymer,
A block containing a polydiene block such as a styrene-isoprene block copolymer, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene- (isoprene / butadiene) -styrene block copolymer. Copolymer; random copolymer composed of diene such as styrene-butadiene random copolymer and styrene-isoprene random copolymer and other polymerizable monomers; diene such as styrene-butadiene taper copolymer and other Tapered copolymers composed of polymerizable monomers; partially hydrogenated products thereof; and the like. The polymer having an olefinic double bond has a hydroxyl group, an alkoxy group,
It may further have a functional group such as a carbonyl group, a carboxyl group, an ester group, an amide group and a halogen atom.

The molecular weight of the polymer having an olefinic double bond is not particularly limited, but is usually a number average molecular weight (Mn).
Is preferably in the range of 1,000 to 1,000,000.

In the present invention, ammonium tungstate and / or phosphotungstic acid are used as the tungsten compound (A). In the present invention, phosphoric acid (B) is used as the phosphoric acid compound. By using these compounds in combination, the liquid separation property of the reaction mixture at the end of the reaction can be improved, and the epoxidized polymer can be efficiently produced. The tungsten compound (A) is used in an amount of 0.0001 to 1 mol per mol of the olefinic double bond of the polymer having the olefinic double bond.
Preferably used in the range of 0.05 mol, 0.0
More preferably, it is used in the range of 001 to 0.02 mol.

In the present invention, an aqueous solution (II) containing the above-mentioned tungsten compound (A) and phosphoric acid (B) is prepared. By this operation, a tungsten complex serving as a precursor of the reactive species in the epoxidation reaction can be surely formed in advance.

In the present invention, the amount of phosphoric acid used is 0.25 mol or more per gram of tungsten metal atoms contained in the tungsten compound (A). If the amount of phosphoric acid used is less than 0.25 mol per gram atom of tungsten metal atom, the reaction rate and catalyst life of the epoxidation reaction decrease, and the production efficiency of the epoxidized polymer decreases. The amount of phosphoric acid to be used is preferably 0.5 mol or more per gram atom of tungsten metal atom contained in the tungsten compound (A). The upper limit of the amount of phosphoric acid used is not particularly limited. However, in consideration of the stability of the obtained epoxidized polymer under the reaction conditions and the liquid separation property of the reaction mixture at the end of the reaction, the tungsten compound is usually used. It is preferably 20 mol or less per gram atom of tungsten metal atom contained in A).
More preferably, it is not more than mol.

In the aqueous solution (II) containing a tungsten compound and phosphoric acid, the amount of water used is p
From the viewpoint of adjusting H to an appropriate range, the amount is preferably 1 to 1000 times, more preferably 10 to 500 times the weight of the tungsten compound (A). The aqueous solution (II) is preferably prepared at a temperature in the range from 10 ° C to 80 ° C.

The pH of the aqueous solution (II) is from 0.1 to 4.5.
, And more preferably in the range of 0.5 to 4 from the viewpoint of reaction rate and operability. If the pH of the aqueous solution (II) is too low, the epoxidation reaction progresses violently, which is not only difficult to control, but also
The stability of the desired epoxidized polymer decreases. If the pH of the aqueous solution (II) is too high, the stability of hydrogen peroxide is impaired, and the epoxidation selectivity per hydrogen peroxide is significantly reduced.

The quaternary ammonium salt used in the present invention is preferably insoluble in water from the viewpoint of reaction efficiency. Examples thereof include tetrapentylammonium chloride, tetrahexylammonium chloride, tetraheptylammonium chloride and tetraoctylammonium chloride. , Trihexylmethylammonium chloride, trihexylethylammonium chloride, trihexylpropylammonium chloride,
Triheptylmethylammonium chloride, triheptylethylammonium chloride, triheptylpropylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride, tetrapentylammonium bromide, tetrahexylammonium bromide, bromide Tetraheptyl ammonium, tetraoctylammonium bromide,
Trihexylmethylammonium bromide, trihexylethylammonium bromide, trihexylpropylammonium bromide, triheptylmethylammonium bromide, triheptylethylammonium bromide, triheptylpropylammonium bromide, trioctylmethylammonium bromide, odor Trioctylethylammonium iodide, trioctylpropylammonium bromide, tetrapentylammonium iodide, tetrahexylammonium iodide, tetraheptylammonium iodide, tetraoctylammonium iodide, trihexylmethylammonium iodide, trihexylethylammonium iodide , Trihexylpropyl ammonium iodide, triheptyl methyl ammonium iodide, triheptyl ethyl ammonium iodide, iodide Heptyl propyl ammonium, trioctyl methyl ammonium iodide, trioctyl ethyl ammonium, trioctyl methyl ammonium iodide, hydrogen tetrapentylammonium sulfate,
Tetrahexyl ammonium hydrogen sulfate, tetraheptyl ammonium hydrogen sulfate, tetraoctyl ammonium hydrogen sulfate, trihexyl methyl ammonium hydrogen sulfate, trihexyl ethyl ammonium hydrogen sulfate, trihexyl propyl ammonium hydrogen sulfate, triheptyl methyl ammonium hydrogen sulfate, triheptyl hydrogen sulfate Examples include ethylammonium, triheptylpropylammonium hydrogen sulfate, trioctylmethylammonium hydrogensulfate, trioctylethylammonium hydrogensulfate, and trioctylpropylammonium hydrogensulfate. Among these, trioctylmethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium iodide, and trioctylmethylammonium hydrogen sulfate are preferred.

The amount of the quaternary ammonium salt is not particularly limited. However, from the viewpoint of economy and liquid separation of the reaction mixture at the end of the reaction, the amount of the quaternary ammonium salt is preferably 1 gram atom of the tungsten metal atom contained in the tungsten compound (A). On the other hand, it is preferably in the range of 0.01 to 10 mol, more preferably in the range of 0.01 to 5 mol, and particularly preferably in the range of 0.1 to 3 mol.

In the present invention, the quaternary ammonium salt is used by dissolving in a water-immiscible organic solvent. When the quaternary ammonium salt is added to an aqueous solution (II) containing a tungsten compound (A) and phosphoric acid (B) without being dissolved in an organic solvent immiscible with water, an insoluble tungsten salt compound is formed. This can significantly inhibit the reaction or significantly reduce the liquid separation of the reaction mixture after the reaction.

The water-immiscible organic solvent that can be used is not particularly limited as long as it does not inhibit the reaction. Examples thereof include pentane, hexane, heptane, octane, nonane, decane,
Aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane and 2,6-dimethylcyclooctane; and aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene and cumene. Among them, hexane, heptane, octane, cyclohexane, toluene and xylene are preferred.
The amount of the solvent used depends on the solubility of the polymer having an olefinic double bond in the solvent to be subjected to the reaction.
It is preferably in the range of 1 to 200 times by weight, and from the viewpoint of reactivity and operability, is preferably in the range of 1 to 100 times by weight,
More preferably, it is in the range of 1 to 20 times by weight.

In the present invention, a commercially available aqueous solution in the form of an aqueous solution can be used as it is or as diluted with water. For example, an aqueous solution of 10 to 60% by weight of hydrogen peroxide can be easily obtained industrially. Although the concentration of hydrogen peroxide is not particularly limited, it is usually preferably from 0.01 to 60% by weight, more preferably from 0.1 to 50% by weight, from the viewpoint of reaction efficiency and safety. preferable. The amount of hydrogen peroxide used depends on the desired amount of the epoxy group to be introduced in the epoxidized polymer as a product, but the amount of hydrogen peroxide used in the polymer having an olefinic double bond is different. It is preferably in the range of 0.001 to 10 mol, more preferably in the range of 0.03 to 1.2 mol, per 1 mol of the heavy bond. For example, when it is desired to epoxidize most of the olefinic double bond contained in the polymer having an olefinic double bond, the amount of hydrogen peroxide used is changed to the olefinic double bond contained in the polymer. 1 to
The range is preferably 10 mol, preferably 1 to 2 mol, and more preferably 1 to 1.2 mol.

In the present invention, the tungsten compound (A) and the phosphoric acid are added to a solution (I) obtained by dissolving a polymer having an olefinic double bond and a quaternary ammonium salt in an organic solvent immiscible with water. An epoxidation reaction is performed by adding an aqueous solution (II) containing (B) and an aqueous solution of hydrogen peroxide (III). The method of adding the aqueous solution (II) and the aqueous hydrogen peroxide solution (III) is that both are directly mixed before the addition of the polymer having an olefinic double bond and the quaternary ammonium salt to the solution. If not, any method may be used.

In the production method of the present invention, for example, the above aqueous solution (II) is added to a solution (I) containing a polymer having an olefinic double bond and a quaternary ammonium salt.
An epoxidation reaction can be carried out by adding an aqueous solution of hydrogen peroxide (III) with vigorous stirring. At this time, it is desirable to add the aqueous hydrogen peroxide solution (III) after adding all of the aqueous solution (II).

Further, according to the production method of the present invention, an aqueous solution (II) and an aqueous hydrogen peroxide solution (III) are added to a solution (I) containing a polymer having an olefinic double bond and a quaternary ammonium salt. It can also be carried out by adding epoxidation reactions simultaneously.

In the present invention, it is necessary to carry out the reaction substantially in the absence of alkali metal ions. The presence of alkali metal ions promotes the decomposition of hydrogen peroxide, not only increasing the amount of hydrogen peroxide used, but also causing the reaction mixture to gel. The term "substantially absent" as used in the present invention means that the amount of the alkali metal ion present in the reaction system is 1 to the total weight of the polymer having an olefinic double bond.
It means that it is 00 ppm or less.

In the production method of the present invention, the reaction pressure is not particularly limited, but is preferably in the range of usually 80 kPa to 1 MPa from the viewpoint of preventing the evaporation of the solvent.
Further, the production method of the present invention, from the viewpoint of safety, nitrogen,
It is preferable to carry out the reaction under an atmosphere of an inert gas such as argon. In the production method of the present invention, the reaction temperature is not particularly limited, but from the viewpoint of reaction rate and safety,
Usually, it is in the range of 0 to 140 ° C, preferably in the range of 40 to 100 ° C, and more preferably in the range of 50 to 100 ° C.

The present inventors have confirmed that in the production method of the present invention, a binuclear complex of tungsten and a small amount of a tetranuclear complex are present in the reaction mixture. In addition, the present inventors have confirmed that the tetranuclear complex of tungsten exists in the reaction mixture in the methods described in the above-mentioned references 1 to 4. Also, in the methods described in these documents,
No binuclear complex of tungsten could be detected. As described above, the presence of the binuclear complex of tungsten in the reaction mixture is a difference between the methods described in the above References 1 to 4 and the production method of the present invention. The mechanism by which good reaction results can be achieved by the method of the present invention is not clear, but it is presumed to be partly due to the presence of a binuclear complex of tungsten in the reaction mixture.

After the completion of the reaction, the epoxidized polymer can be separated from the reaction mixture by a usual isolation and purification operation. For example, the reaction mixture is allowed to stand to separate into an organic layer and an aqueous layer, the aqueous layer is removed, and the obtained organic layer is washed with water, an aqueous solution of sodium hydrogen sulfite, an aqueous solution of sodium sulfite, and then re-used. It can be carried out by performing a known operation for isolating a polymer from a solution, such as precipitation, removal of a solvent under heating, removal of a solvent under reduced pressure, and removal of a solvent by steam (steam stripping).

In order to increase the stability of the product epoxidized polymer, it is desirable to minimize the amount of the tungsten compound mixed in the product. For that purpose, it is important to remove the catalyst efficiently in the isolation operation.

Efficient removal of the catalyst is achieved by separating from the aqueous layer,
It can be carried out by bringing the organic layer, which has been washed with water, an aqueous solution of sodium hydrogen sulfite, an aqueous solution of sodium sulfite or the like, into contact with activated carbon or a basic substance.

The raw material constituting the activated carbon is not particularly limited, and for example, those made from coconut shell, synthetic resin, coke, pitch, etc. can be suitably used. In addition, the shape of the activated carbon is not particularly limited, and a form such as powder, granule, fiber, or molded body can be appropriately selected.

Examples of the basic substance include a basic ion exchange resin; ion-exchanged zeolites such as sodium-exchanged Y-type zeolite and potassium-exchanged Y-type zeolite; sodium hydroxide, potassium hydroxide, calcium hydroxide, water Hydroxides of alkali metals or alkaline earth metals such as magnesium oxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; alkali metal carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate Hydrogen salts; alkali metal salts of organic acids such as potassium acetate, sodium acetate, sodium propionate and potassium propionate; ammonia; organic bases such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine and the like. Among these, basic ion exchange resins, alkali metal or alkaline earth metal carbonates,
It is preferred to use alkali metal bicarbonate,
It is more preferred to use alkali metal or alkaline earth metal carbonates. The basic substance is desirably used in the form of an aqueous solution from the viewpoint of efficiently performing the contact operation with the organic layer and the separation operation after the contact.

The amount of the activated carbon and the amount of the basic substance used are not particularly limited, but are usually 1 to 100 times the weight of the tungsten compound (A) used in the epoxidation reaction. Preferably, it is more preferably used in a range of 5 to 50 times by weight in consideration of economy and operability.

From the organic layer after contact with activated carbon or a basic substance, as described above, reprecipitation, removal of the solvent under heating, removal of the solvent under reduced pressure, removal of the solvent by steam (steam stripping) The epoxidized polymer, which is a product, can be obtained by performing a known operation for isolating a polymer from a solution, such as the method described in (1).

The epoxidized polymer obtained by the method of the present invention has an epoxy group content of 1 to 100 mol% based on all monomer units constituting the polymer. The distribution of the epoxy groups contained in the epoxidized polymer obtained by the method of the present invention is not particularly limited, for example, a regular distribution,
A block-shaped distribution, a random distribution, a tapered distribution, a distribution in which some of these are mixed, and the like can be given. The epoxy group may be contained in either the main chain or the side chain of the epoxidized polymer. However, from the viewpoint of the stability of the epoxidized polymer, 70% by mole or more of all epoxy groups in the epoxidized polymer. Is preferably contained in the main chain, and more preferably 80 mol% or more is contained in the main chain.

Examples of the epoxidized polymer obtained by the method of the present invention include epoxidized polydienes such as epoxidized polybutadiene and epoxidized polyisoprene; and polyalkenes obtained by ring-opening metathesis polymerization of cycloalkene such as cycloheptene and cyclooctene. Epoxidized polymer of isoprene butadiene block copolymer, styrene-butadiene block copolymer, styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene (Isoprene / butadiene)-
Epoxidized polymer of a block copolymer containing a polydiene block such as a polymer on a styrene block; from a diene such as a styrene butadiene random copolymer or a styrene-isoprene random copolymer and another polysynthetic monomer Epoxidized polymer of random copolymer; epoxidized polymer of tapered copolymer obtained from diene such as styrene-butadiene tapered copolymer and other polymerizable monomer; epoxy such as partially hydrogenated product thereof Polymerized polymer;
Of unsaturated polyesters obtained from dibasic acids such as terephthalic acid and diols such as 2-butene-1,4-diol, or dibasic acids such as tetrahydrophthalic acid and diols such as 1,4-butanediol; Epoxidized polyesters; obtained from dibasic acids such as terephthalic acid and diamines such as 2-butene-1,4-diamine, or dibasic acids such as tetrahydrophthalic acid and diamines such as 1,4-butanediamine And epoxidized polyamides of unsaturated polyamides.

[0041]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15,000). ) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.32 g were added and completely dissolved with stirring at 60 ° C. The temperature of the solution was raised to 70 ° C.
15 g (0.05 mmol) and 0.33 g of phosphoric acid
(3.3 mmol) dissolved in 20 g of water
After adding an aqueous solution in which H was 3.1, 37.4 g (0.33 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while the obtained mixture was vigorously stirred at 70 ° C. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 4 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 3 minutes. The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous sodium carbonate solution, and further washed with 100 ml of water.
After washing twice, toluene was distilled off under reduced pressure, and the obtained residue was dried at 80 ° C. and 800 Pa for 8 hours. The obtained epoxidized polyisoprene (yield: 30 g) was mixed with ¹
When analyzed by 1 H-NMR, the conversion of the double bond was 89% and the epoxidation rate was 88% (selectivity: 99%).
%)Met. It was found that 98% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the amount of tungsten remaining in the obtained epoxidized polyisoprene was quantified by the following method, it was 21.1 ppm.

Measurement of tungsten content 2 g of epoxidized polyisoprene was precisely weighed in a platinum crucible,
The mixture was heated with an electric heater at 500 ° C. for 3 hours, and further heated to 600 ° C. for incineration. The platinum crucible was once cooled to room temperature, 2 g of sodium carbonate was added, and the mixture was again air-dried at 400 ° C. for 30 minutes, then at 600 ° C. for 30 minutes, further at 800 ° C. for 1 hour, and finally at 900 ° C. for 1 hour. Was heated under the following conditions. After completion of heating, the mixture was cooled to room temperature, and water was added to the residue to adjust the total volume to 100 ml.
The remaining amount of tungsten was measured by P emission analysis.

Example 2 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15,000). ) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.32 g were added and completely dissolved with stirring at 60 ° C. The temperature of this solution was raised to 70 ° C. and phosphotungstic acid 0.11 g
(0.04 mmol) and 0.02 g of phosphoric acid (0.2
0 mmol) was dissolved in 10 g of water and an aqueous solution having a pH of 2.5 was added.
30% hydrogen peroxide aqueous solution 3
7.4 g (0.33 mol) was added dropwise over 3 hours.
After the completion of the dropwise addition of the aqueous solution of hydrogen peroxide, the reaction mixture was
The mixture was stirred at 0 ° C. for 4 hours, and the stirring was stopped. After stopping stirring, 6
The time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 0 ° C. was about 1 minute. Separate and remove the aqueous layer,
The organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and further twice with 100 ml of water. Then, toluene was distilled off under reduced pressure, and the obtained residue was treated at 80 ° C. and 800 Pa. Dried for 8 hours. The obtained epoxidized polyisoprene (30 g yield) was purified with ¹ H-NM.
When analyzed by R, the conversion of the double bond was 88.
%, And the epoxidation rate was 87% (selectivity 99%).
It was found that 97% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained polyisoprene was analyzed by the same method as in Example 1, it was 12.1 ppm.

COMPARATIVE EXAMPLE 1 In Example 1, ammonium tungstate 0.1
Sodium tungstate 0.13g instead of 5g
The reaction was carried out in the same manner as in Example 1 except that (0.44 mmol) was used. During the reaction, components insoluble in the yellow organic layer (toluene layer) and the aqueous layer were separated, and the reaction was carried out at 60 ° C. It took about 15 minutes to form an interface between the organic layer and the aqueous layer. From this, it can be seen that when ammonium tungstate or phosphotungstic acid is used as in the example, the interface formation time of the reaction mixture after the reaction is completed is shortened, and the liquid separation property is improved. The conversion of double bonds in the obtained epoxidized polyisoprene was 94%.
%, And the epoxidation ratio was 82% (selectivity 87%).
It was found that 91% of the added hydrogen peroxide contributed to the epoxidation reaction. When the residual amount of tungsten was analyzed in the same manner as in Example 1, it was 112 ppm.

Comparative Example 2 The procedure of Example 1 was repeated except that polyisoprene, ammonium tungstate, phosphoric acid, trioctylmethylammonium chloride, toluene and water were simultaneously charged into the reactor. Operation was performed. At the end of the reaction, the reaction mixture was gelled, did not separate into an organic layer and an aqueous layer, and the desired epoxidized polymer could not be obtained.

Comparative Example 3 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15,000). ) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.32 g were added and completely dissolved with stirring at 60 ° C. The temperature of the solution was raised to 70 ° C.
15 g (0.05 mmol) and 0.33 g of phosphoric acid
(3.3 mmol) was dissolved in 20 g of water, and an aqueous solution having a pH of 5.1, which was prepared by adding 0.07 g (0.66 mmol) of sodium carbonate, was added. While stirring, 37.4 g (0.33 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 9 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 54 minutes. The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous sodium carbonate solution and twice with 100 ml of water, and then toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polyisoprene (30 g yield) was added to ¹
When analyzed by 1 H-NMR, the conversion of the double bond was 91% and the epoxidation rate was 73% (selectivity 80
%)Met. It was found that 72% of the added hydrogen peroxide contributed to the epoxidation reaction. When the amount of tungsten remaining in the obtained epoxidized polyisoprene was analyzed by the same method as in Example 1, it was 29.1 ppm.

Comparative Example 4 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15,000). ) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.32 g were added and completely dissolved with stirring at 60 ° C. The temperature of the solution was raised to 70 ° C.
15 g (0.05 mmol) and 9.4 mg of phosphoric acid
(0.01 mmol) was dissolved in 20 g of water, and an aqueous solution having a pH of 4.2 was added. Then, the obtained mixture was vigorously stirred at 70 ° C. while 37.4 g of a 30% aqueous hydrogen peroxide solution was added. (0.33 mmol) was added dropwise over 3 hours. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 6 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 12 minutes. The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous sodium carbonate solution and twice with 100 ml of water, and then toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polyisoprene (30 g yield) was added to ¹
When analyzed by 1 H-NMR, the conversion of the double bond was 83% and the epoxidation rate was 80% (selectivity 96
%)Met. It was found that 81% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained epoxidized polyisoprene was analyzed by the same method as in Example 1, it was 29.4 ppm.

Example 3 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15,000). ) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.32 g were added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and ammonium tungstate · 5
An aqueous solution having a pH of 3.1 prepared by dissolving 0.125 g (0.04 mmol) of hydrate and 0.33 g (3.3 mmol) of phosphoric acid in 20 g of water was added. While vigorously stirring at 70 ° C., 2.26 g (0.02 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 0.5 hours. After the completion of the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 1 hour, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 0.5 minutes.
The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous sodium carbonate solution and twice with 100 ml of water, and then toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours. When the obtained epoxidized polyisoprene (yield 25.5 g) was analyzed by ¹ H-NMR, the conversion of the double bond was 5.3%, and the epoxidation rate was 5.3% (selectivity). 100%). It was found that 98% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained epoxidized polyisoprene was analyzed by the same method as in Example 1, it was 1.2 ppm.

Example 4 A 300 ml three-necked flask equipped with a reflux tube, two dropping funnels, a thermometer and a mechanical stirrer was prepared.
25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), toluene 10
0 g and trioctylmethylammonium chloride 0.3
2 g was added and completely dissolved with stirring at 60 ° C.
This solution was heated to 70 ° C., and 0.125 g (0.04 mmol) of ammonium tungstate pentahydrate and 0.33 g (3.3 mmol) of phosphoric acid were dissolved in 20 g of water to adjust the pH to 3. 1 and an aqueous 30% hydrogen peroxide solution (37.4 g, 0.33 mol) were simultaneously dropped from separate dropping funnels (time required: 3 hours).
After completion of the dropwise addition, the reaction mixture was further stirred at 70 ° C. for 4 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 1.5 minutes. The aqueous layer was separated and removed, the organic layer was washed with 100 ml of water, and a 5% aqueous solution of sodium carbonate 100%.
After washing with 100 ml of water and twice with 100 ml of water, toluene was distilled off under reduced pressure.
It was dried for 8 hours under the condition of 00 Pa. When the obtained epoxidized polyisoprene (30 g yield) was analyzed by ¹ H-NMR, the conversion of the double bond was 88%, and the epoxidation rate was 88% (selectivity 100%). . It was found that 99% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained epoxidized polyisoprene was analyzed by the same method as in Example 1, it was 13.1 ppm.

Comparative Example 5 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15,000). ) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.32 g were added and completely dissolved with stirring at 60 ° C, and the resulting solution was heated to 70 ° C. 30% hydrogen peroxide is added to an aqueous solution having a pH of 3.1 prepared by dissolving 0.125 g (0.04 mmol) of ammonium tungstate pentahydrate and 0.33 g (3.3 mmol) of phosphoric acid in 20 g of water. An aqueous solution was prepared by adding 37.4 g (0.33 mol) of an aqueous solution. This added liquid was added dropwise to the toluene solution containing polyisoprene and trioctylmethylammonium chloride obtained above at 70 ° C. over 3 hours. During the dropping, oxygen continued to be generated from the additive solution. After the addition, the reaction mixture was further stirred at 70 ° C. for 4 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 1.5 minutes. The aqueous layer was separated and removed, the organic layer was washed with 100 ml of water, and a 5% aqueous solution of sodium carbonate 10
After washing with 0 ml and twice with 100 ml of water,
The toluene was distilled off under reduced pressure.
It was dried under the condition of 800 Pa for 8 hours. When the obtained epoxidized polyisoprene (yield 28 g) was analyzed by ¹ H-NMR, the conversion of double bonds was 71%.
The epoxidation rate was 66% (selectivity 93%). It was found that 42% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained epoxidized polyisoprene was analyzed by the same method as in Example 1, it was 11.4 ppm.

Example 5 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with a styrene-isoprene-styrene triblock copolymer (styrene content: 32%, number average molecular weight). : 30000) 25
g, toluene 100 g and trioctylmethylammonium chloride 0.20 g were added and completely dissolved with stirring at 60 ° C. The temperature of this solution was raised to 70 ° C., and 0.093 g of ammonium tungstate pentahydrate (0.03 g) was added.
mmol) and 0.22 g (2.2 mmol) of phosphoric acid
Was dissolved in 20 g of water, and an aqueous solution having a pH of 3.3 was added. The resulting mixture was vigorously stirred at 70 ° C. while 26.9 g (0.2%) of a 30% aqueous hydrogen peroxide solution was added.
3 mol) was added dropwise over 3 hours. After the completion of the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 8 hours, and the stirring was stopped. After the stirring is stopped, it takes about 1 hour at 60 ° C. until the interface between the organic layer (toluene layer) and the aqueous layer is formed.
Minutes. The aqueous layer was separated and removed.
After washing with 100 ml of a 5% aqueous solution of sodium carbonate and twice with 100 ml of water, toluene was distilled off under reduced pressure.
It dried for 8 hours under the conditions of a. When the obtained epoxidized styrene-isoprene-styrene triblock copolymer (yield 29 g) was analyzed by ¹ H-NMR, the conversion of the double bond was 92% and the epoxidation rate was 91%.
(Selectivity 99%). 96 of the added hydrogen peroxide
% Was found to have contributed to the epoxidation reaction. In addition,
When the remaining amount of tungsten in the obtained epoxidized styrene-isoprene-styrene triblock copolymer was analyzed by the same method as in Example 1, it was 9 ppm.

Example 6 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with polyoctenylene (manufactured by Huls America, number average molecular weight: 6).
0000) 25 g, toluene 100 g and trioctylmethylammonium chloride 0.15 g were added and completely dissolved at 70 ° C. with stirring. The temperature of this solution was raised to 80 ° C., and ammonium tungstate pentahydrate 0.07
8 g (0.025 mmol) and 0.17 g of phosphoric acid
(1.7 mmol) dissolved in 20 g of water
After adding an aqueous solution in which H was 3.5, 26.2 g (0.23 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while the resulting mixture was vigorously stirred at 80 ° C. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 80 ° C. for 6 hours, and the stirring was stopped. After stopping the stirring, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 2 minutes. The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water.
P-17 (trade name, manufactured by Kuraray Chemical Co., Ltd.)] 12
g was added and stirred at 50 ° C. for 1 hour. Activated carbon was removed by a filter, and toluene was distilled off from the obtained filtrate under reduced pressure, and the residue was dried at 80 ° C. and 800 Pa for 8 hours. When the obtained epoxidized polyoctenylene (yield 28 g) was analyzed by ¹ H-NMR, the conversion of the double bond was 100%, and the epoxidation rate was 10%.
0% (selectivity 100%). It was found that 99% of the added hydrogen peroxide contributed to the epoxidation reaction.
When the amount of tungsten remaining in the obtained epoxidized polyoctenylene was analyzed by the same method as in Example 1, it was 7.3 ppm.

Example 7 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with cis-
25 g of polybutadiene (Nipol-BR, manufactured by Zeon Corporation, number average molecular weight: 30,000), cyclohexane 10
0 g and trioctylmethylammonium chloride 0.3
2 g was added and completely dissolved with stirring at 60 ° C.
This solution was heated to 70 ° C., and 0.15 g (0.05 mmol) of ammonium tungstate and 0.3% of phosphoric acid were added.
After adding an aqueous solution having a pH of 3.1 prepared by dissolving 3 g (3.3 mmol) in 20 g of water, the resulting mixture is vigorously stirred at 70 ° C. while stirring a 30% aqueous hydrogen peroxide solution. 1 g (0.46 mol) was added dropwise over 4 hours. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 2 hours, and the stirring was stopped. After the stirring was stopped, the time required for forming an interface between the organic layer (cyclohexane layer) and the aqueous layer at 60 ° C. was about 2.5 minutes. The aqueous layer was separated and removed, the organic layer was washed with 100 ml of water and 5%
Wash with 100 ml of aqueous sodium carbonate solution, then add 10
After washing twice with 0 ml, cyclohexane was distilled off under reduced pressure.
Dried for hours. When the obtained epoxidized polybutadiene (yield 33.2 g) was analyzed by ¹ H-NMR, the conversion of the double bond was 100%, and the epoxidation rate was 98.5% (selectivity 98%). Met. It was found that 98% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained epoxidized polybutadiene was analyzed by the same method as in Example 1, it was 14.1 ppm.

In the above reaction, a small amount of the reaction mixture at one hour after the completion of the addition of hydrogen peroxide was sampled and analyzed by ³¹ P-NMR.
₈ H ₁₇ ) ₃ CH ₃ N] ₂ [HPO ₄ {WO (O ₂ ) ₂ } ₂ ] and a peak corresponding to the tungsten dinuclear complex represented by the formula [(C ₈ H ₁₇ ) ₃ CH ₃ N] ₃ [ PO
₄ {WO (O ₂ ) ₂ } ₄ ], the presence of a peak corresponding to the tetranuclear tungsten complex was confirmed. Note that the peak of ³¹ P-NMR was assigned to the binuclear complex represented by the formula [(C ₈ H ₁₇ ) ₃ CH ₃ N] ₂ [HPO ₄ {WO (O ₂ ) ₂ } ₂ ] and the formula [(C _{8 H 17) 3 CH 3 N} ] 3 [PO 4 {WO (O
₂ ) ₂ } ₄ ], the tetranuclear complex represented by the literature [Inorga
nic Chemistry, 33 , 871-878 (1994) and Inorganic
Chemistry, 30 , 4409-4415 (1991)] and prepared by comparing them with the chemical shift values of ³¹ P-NMR measured separately.

Comparative Example 6 The procedure of Example 7 was repeated, except that cis-polybutadiene, ammonium tungstate, phosphoric acid, trioctylmethylammonium chloride, cyclohexane and water were simultaneously charged into the reactor. Was performed. The reaction mixture at the end of the reaction is gelled,
There was no separation into an organic layer and an aqueous layer, and the desired epoxidized polymer could not be obtained.

Comparative Example 7 In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of cis-polybutadiene (Nipol-BR, manufactured by Zeon Corporation, number average molecular weight: 30,000), chloroform 114
g and trioctylmethylammonium chloride 0.32
g was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and 0.11 g (0.33 mmol) of sodium tungstate and 0.06 g of phosphoric acid were added.
g (0.6 mmol) was dissolved in 10 g of water, and an aqueous solution having a pH of 3.3 was added. The resulting mixture was stirred vigorously at 70 ° C. while 30% aqueous hydrogen peroxide solution was added. 2 g (0.09 mol) was added dropwise over 4 hours. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 80 ° C. for 12 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (chloroform layer) and the aqueous layer was formed at 60 ° C. was about 18 minutes. The aqueous layer was separated and removed. The organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous sodium carbonate solution, and further washed with 100 ml of water.
After washing twice with l, chloroform was distilled off under reduced pressure.
The obtained residue was dried at 80 ° C. and 800 Pa for 8 hours. The resulting epoxidized polybutadiene (yield 2
When 5.8 g) was analyzed by ¹ H-NMR, the conversion of the double bond was 19% and the epoxidation rate was 17%.
(Selectivity 89%). 88 of the added hydrogen peroxide
% Was found to have contributed to the epoxidation reaction. In addition,
The amount of tungsten remaining in the obtained epoxidized polybutadiene was analyzed by the same method as in Example 1.
It was 4 ppm.

In the above reaction, a small amount of the reaction mixture at one hour after the completion of the addition of hydrogen peroxide was sampled and analyzed by ³¹ P-NMR.
₈ H ₁₇ ) ₃ CH ₃ N] ₃ [PO ₄ {WO (O ₂ ) ₂ } ₄ ]. The presence of a peak corresponding to the tetranuclear tungsten complex was confirmed, but the formula [(C
₈ H ₁₇ ) ₃ CH ₃ N] ₂ [HPO ₄ {WO (O ₂ ) ₂ } ₂ ] No peak corresponding to the binuclear tungsten complex could be confirmed.

Comparative Example 8 A 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer was charged with cis-
25 g of polybutadiene (Nipol-BR, manufactured by Zeon Corporation, number average molecular weight: 30,000), chloroform 114
g and trioctylmethylammonium chloride 0.32
g was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and 0.11 g (0.33 mmol) of sodium tungstate and 0.06 g of phosphoric acid were added.
g (0.6 mmol) was dissolved in 10 g of water, and an aqueous solution having a pH of 3.3 was added. The resulting mixture was stirred vigorously at 70 ° C. while stirring a 30% aqueous hydrogen peroxide solution. 1 g (0.46 mol) was added dropwise over 4 hours. After the dropwise addition of the aqueous hydrogen peroxide solution, the reaction mixture was further stirred at 70 ° C. for 2 hours, and the stirring was stopped. The reaction mixture was gelled, did not separate into an organic layer and an aqueous layer, and the desired epoxidized polymer could not be obtained.

Reference Example 1 [Production of poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester)] In a 500-ml three-necked flask equipped with a dropping funnel, a reflux tube and a mechanical stirrer, 41.2 g of 1,4-cyclohexanedimethanol ( 0.29 mol) and 88.5 g (0.58 mol) of tetrahydrophthalic anhydride
After l) was added and 150 g of toluene was added and dissolved, the mixture was heated at 120 ° C. for 5 hours. After cooling to room temperature,
0.8 g of benzyltrimethylammonium chloride
(0.004 mol) and dissolved, then 85
% Sodium hydroxide powder 41g (0.85mol)
Was added, and 66.9 g of epichlorohydrin (0.7 m
ol) was added dropwise at 40 ° C. over 8 hours, and the mixture was further heated and stirred for 5 hours. After the reaction mixture was washed with water, low-boiling substances were removed under reduced pressure, and 135.2 g of poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) was obtained.
(83% yield).

Example 8 A 300 ml three-necked flask equipped with a reflux tube, two dropping funnels, a thermometer, and a mechanical stirrer was prepared.
25 g of poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) produced in Reference Example 1
(0.018 mol), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride, and
Dissolve completely while stirring at ℃. 70 ° C
To ammonium tungstate pentahydrate 0.
125 g (0.04 mmol) and phosphoric acid 0.33 g
(3.3 mmol) dissolved in 20 g of water
An aqueous solution in which H is 3.1 and 9.06 g (0.08 mol) of a 30% aqueous hydrogen peroxide solution were simultaneously dropped from separate dropping funnels (time required: 3 hours). After completion of the dropwise addition, the reaction mixture was further stirred at 70 ° C. for 4 hours, and the stirring was stopped. After the stirring was stopped, the time until the interface between the organic layer (toluene layer) and the aqueous layer was formed at 60 ° C. was about 1.5 minutes.
The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous sodium carbonate solution and twice with 100 ml of water, and then toluene was distilled off under reduced pressure. The residue was dried at 60 ° C. and 800 Pa for 8 hours. When the obtained epoxidized poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) [yield: 26.0 g] was analyzed by ¹ H-NMR, the conversion of the double bond was 100%, and the epoxidation rate was 100%. 98% (selectivity 98%). It was found that 99% of the added hydrogen peroxide contributed to the epoxidation reaction. In addition, when the residual amount of tungsten in the obtained epoxidized poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) was analyzed by the same method as in Example 1, it was 9.1 ppm.

Comparative Example 9 In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g (0.01 g) of the poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) prepared in Reference Example 1 was added.
8 mol), 100 g of toluene and 0.09 g of cetylpyridinium chloride were completely dissolved with stirring at 60 ° C. 0.17 g (0.51 mmol) of sodium tungstate and 0.27 g of phosphoric acid were added to this solution.
g (0.27 mmol) was dissolved in 1.8 g of water, and pH was adjusted using 0.05 g (0.47 mmol) of sodium carbonate.
After the aqueous solution adjusted to 3 was added, 9.05 g of a 30% aqueous hydrogen peroxide solution was added to the resulting mixture while stirring vigorously.
(0.08 mol) was added dropwise over 3 hours, and the mixture was further reacted for 3 hours. After stopping the stirring, the time until the interface between the organic layer (toluene layer) and the aqueous layer is formed at 60 ° C. is about 39.5.
Minutes. The aqueous layer was separated and removed.
After washing with 100 ml of a 5% aqueous solution of sodium carbonate and then twice with 100 ml of water, toluene was distilled off under reduced pressure.
It dried for 8 hours under the conditions of a. The obtained epoxidized poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) [yield: 25.6 g] was added to ¹ H-NM.
When analyzed by R, the conversion of the double bond was 95%.
And the epoxidation ratio was 71% (selectivity 75%). It was found that 70% of the added hydrogen peroxide contributed to the epoxidation reaction. The amount of tungsten remaining in the obtained epoxidized poly (cyclohexanedimethyltetrahydrophthalate diglycidyl ester) was determined in Example 1.
When analyzed by the same method as in, it was 89.3 ppm.

Example 9 By the same operation as in Example 1, polyisoprene (LIR
-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15
000) 25 g of epoxidation reaction was performed. After separating the reaction mixture into an organic layer and an aqueous layer, the aqueous layer was separated and removed. After the organic layer was washed three times with 100 ml of water, the toluene was distilled off under reduced pressure.
It was dried for 8 hours under the condition of Pa. When the obtained epoxidized polyisoprene (30 g in yield) was analyzed by ¹ H-NMR, the epoxidation ratio of the double bond was 88%. The residual amount of tungsten in the obtained epoxidized polyisoprene was 412 ppm.

[0064]

According to the present invention, there is provided a method for producing an epoxidized polymer safely, efficiently and industrially advantageously.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J100 AB02Q AR04P AR05P AS02P AS03P CA01 CA04 CA31 HA29 HB34 HB42 JA15

Claims (6)

[Claims] 1. A solution (I) obtained by dissolving a polymer having an olefinic double bond and a quaternary ammonium salt in an organic solvent immiscible with water is selected from ammonium tungstate or phosphotungstic acid. An aqueous solution containing a tungsten compound (A) and phosphoric acid (B), and having a phosphoric acid (B) content of 0.25 mol or more per gram atom of tungsten metal atom contained in the tungsten compound (A) ( A method for producing an epoxidized polymer, characterized by adding II) and an aqueous solution of hydrogen peroxide (III) and reacting the mixture substantially in the absence of alkali metal ions. 2. The method according to claim 1, wherein the water-immiscible organic solvent is an aliphatic hydrocarbon or an aromatic hydrocarbon. 3. The method according to claim 1, wherein the quaternary ammonium salt is insoluble in water. 4. The production method according to claim 1, wherein the pH of the aqueous solution (II) is 0.1 to 4.5. 5. The production method according to claim 1, wherein the pH of the aqueous solution (II) is 0.5 to 4. 6. A method for producing an epoxidized polymer, comprising the following steps 1 and 2. Step 1: Polymer having olefinic double bond and fourth polymer
The solution (I) obtained by dissolving a quaternary ammonium salt in an organic solvent immiscible with water contains a tungsten compound (A) selected from ammonium tungstate or phosphotungstic acid and phosphoric acid (B), and An aqueous solution (II) in which the content of (B) is 0.25 mol or more per gram atom of tungsten metal atom contained in the tungsten compound (A) and an aqueous hydrogen peroxide solution (III) are added, Reacting in the absence of alkali metal ions. Step 2: a step of separating the reaction mixture obtained in Step 1 into an organic layer and an aqueous layer, and then performing a post-treatment including contacting the organic layer with activated carbon or a basic substance.