JP2008024731A - Manufacturing method of epoxidized polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially advantageously manufacturing an epoxidized polymer safely with a small amount of a catalyst in a short time with sufficiently reduced side reactions efficiently in a high yield with a light environmental load. <P>SOLUTION: The manufacturing method of the epoxidized polymer comprises a step for introducing an epoxy group by oxidizing a polymer bearing a carbon-carbon double bond by hydrogen peroxide as an oxidant using a catalyst comprised of (A) a salt of a group VI metal oxide, (B) a phosphonic acid compound and (C) a surfactant. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an epoxidized polymer. More specifically, the present invention relates to a method for producing an epoxidized polymer in which an epoxy group is introduced by oxidizing a polymer containing a carbon-carbon double bond.

  As a method for producing an epoxidized polymer, a method of epoxidizing a polymer having a carbon-carbon double bond is useful. As a method for epoxidizing a polymer having a carbon-carbon double bond, a method for epoxidation using hydrogen peroxide and a method for epoxidation using a peracid such as peracetic acid are known.

  In Patent Document 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. A method is disclosed in which an aqueous solution (II) containing a tungsten compound (A) and phosphoric acid (B) and a hydrogen peroxide aqueous solution (III) are added and reacted substantially in the absence of alkali metal ions. Yes.

Patent Document 2 shows a polymer having an olefinic double bond and Q ₂ {HPO ₄ [WO (O ₂ ) ₂ ] ₂ } (wherein Q represents a quaternary ammonium group). A method is disclosed in which a hydrogen peroxide aqueous solution is added to a solution obtained by dissolving a tungsten dinuclear peroxide complex in an aliphatic hydrocarbon or an aromatic hydrocarbon and reacted.

  Furthermore, Non-Patent Document 1 describes an epoxidation reaction of a polymer having a carbon-carbon double bond with a peracid.

On the other hand, Non-Patent Documents 2 and 3 include sodium tungstate (Na ₂ WO ₄ ), methyl trioctylammonium hydrogen sulfate ([CH ₃ (n-C ₈ H ₁₇ ) ₃ N] HSO ₄ ) and aminomethylphosphonic acid ( A method of epoxidizing a low molecular weight olefin compound using a catalyst system comprising NH ₂ CH ₂ PO ₃ H ₂ ) and hydrogen peroxide is disclosed.

JP 2002-249516 A JP 2002-371113 A Polymers for Advanced Technologies, Vol. 7, p. 67-72 (1996) Kazuhiko Sato and Yoko Sakurai, “Development of environmentally friendly oxidation reaction using hydrogen peroxide solution”, Catalyst, Vol. 46, no. 5, 2004, p. 328-333 Ryoji Noyori, Masao Aoki and Kazuhiko Sato, Chem. Commun. , 2003, 1977-1986

  However, in the methods of Patent Documents 1 and 2, there are restrictions on the order in which the catalyst is added and the dropping rate of the hydrogen peroxide solution, and the reaction conditions such as desirable in an inert gas atmosphere must be strict. The method 2 also has a problem that it is difficult to produce a tungsten binuclear peroxide complex.

  Furthermore, in the method of Non-Patent Document 1, an acid such as acetic acid and formic acid present in the reaction system tends to cause a ring-opening reaction of the generated epoxy group. In addition, when implemented industrially, it is difficult to remove these organic acids from the produced polymer, the burden on the environment is large, and the danger due to the use of highly explosive organic peracids. There was a problem.

  Non-Patent Documents 2 and 3 disclose the epoxidation of a low molecular weight olefin compound, but do not disclose the application of this reaction to a polymer. The reactivity and reaction conditions differ between low molecular weight olefinic compounds and carbon-carbon double bonds in the polymer. The methods shown in Non-Patent Documents 2 and 3 are based on an oxidation reaction of a low-molecular-weight olefin compound without using an organic solvent, such as polymers, polymer solutions, and emulsions that are solid or high-viscosity liquids. Application to a polymer in a dispersed state was not assumed.

  In view of such circumstances, the present invention produces an epoxidized polymer safely, in a short time with a small amount of catalyst, with a sufficiently reduced side reaction, efficiently in a high yield, industrially advantageous, and with low environmental impact. It aims to provide a way to do.

  That is, the method for producing an epoxidized polymer of the present invention uses a catalyst comprising hydrogen peroxide as an oxidant and (A) a group VI metal oxide salt, (B) a phosphonic acid compound, and (C) a surfactant. And a step of introducing an epoxy group by oxidizing a polymer containing a carbon-carbon double bond.

  According to the present invention, it is possible to efficiently produce an epoxidized polymer in a short time with a small amount of catalyst, with few side reactions such as gelation of a polymer chain, molecular chain breakage, and diol formation, in a high yield. it can. Further, coloring of the product is suppressed, and the epoxidized polymer can be produced safely with less environmental load, which is industrially advantageous.

<Polymer containing carbon-carbon double bond>
The polymer in the present invention includes an oligomer. As a polymer containing a carbon carbon double bond, what contains 0.1-100 mol% of carbon carbon double bonds based on all the monomer units which comprise this polymer is mentioned.

  The carbon-carbon double bond of the polymer containing the carbon-carbon double bond is preferably formed by a polymerization reaction of a diene monomer.

  The carbon-carbon double bond of the polymer containing the carbon-carbon double bond may have either a cis or trans structure, or both may be mixed. There is no particular restriction on the distribution of carbon-carbon double bonds in polymers containing carbon-carbon double bonds, for example, regular distribution, block-shaped distribution, random distribution, tapered distribution, and some of these are mixed. Distribution.

  When a polymer containing a carbon-carbon double bond has a side chain, the carbon-carbon double bond may be contained in either the main chain or the side chain of the polymer, but the stability of the resulting epoxidized polymer From the viewpoint, it is preferable that 50 mol% or more of all the carbon-carbon double bonds of the polymer containing the carbon-carbon double bond is contained in the main chain.

  The polymerization method for the polymer containing a carbon-carbon double bond is not particularly limited, but any method such as addition polymerization or condensation polymerization may be used. As a reaction method, radical polymerization, ionic polymerization, coordination polymerization, metathesis polymerization, etc. For example, it may be produced by various polymerization methods. Examples of ionic polymerization methods include anionic polymerization and cationic polymerization.

  Examples of the polymer containing a carbon-carbon double bond include polydienes such as polybutadiene and polyisoprene; polyalkenes obtained by ring-opening metathesis polymerization of cycloalkene such as cyclopentene, cyclohexene, and cyclooctene; isoprene-butadiene block copolymer, styrene -Butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene- (isoprene / butadiene) -styrene block copolymer, etc. Block copolymer containing polydiene block; random copolymer comprising diene and other polymerizable monomers such as styrene-butadiene random copolymer, styrene-isoprene random copolymer; Down - tapered copolymer consisting diene and other polymerizable monomers such as butadiene tapered copolymer; and these partially hydrogenated product thereof. Examples of the copolymer of acrylate ester and diene, such as a copolymer of ethyl acrylate, butyl acrylate and isoprene, and butadiene, include ethylene-propylene-diene rubber, isoprene rubber, and chloroprene rubber. It can be illustrated. The polymer containing a carbon-carbon double bond may further have a functional group such as a hydroxyl group, an alkoxy group, a carbonyl group, a carboxyl group, an ester group, an amide group, or a halogen atom in the molecular chain or at the molecular end. , Aromatic vinyl, acrylic acid and its ester, methacrylic acid and its ester, vinyl carboxylate, ethylene derivative and the like may be copolymerized.

  Although there is no restriction | limiting in particular in the molecular weight of the polymer containing a carbon carbon double bond, Usually, it is preferable that it is the range of 1,000-1,000,000 as a number average molecular weight (Mn). More preferably, it is 3,000 to 500,000, and most preferably 5,000 to 300,000.

<Catalyst>
In the present invention, a catalyst comprising (A) a group VI metal oxide salt, (B) a phosphonic acid compound and (C) a surfactant is used.

  (A) Although there is no restriction | limiting in particular as a salt of a VI group metal oxide, A tungstate and a molybdate can be illustrated.

  Among these, tungstate is preferable. The salt is preferably an alkali metal salt or an alkaline earth metal salt. More preferred is sodium tungstate.

  (A) 0.01-20 mol% is preferable with respect to the target epoxy group introduction amount, and 0.1-10 mol% is more preferable with respect to the usage-amount of the salt of VI group metal oxide. Most preferably, it is 2-5 mol%.

(B) The phosphonic acid compound is not particularly limited as long as it is a compound derived from phosphonic acid (indicated by (HO) ₂ PH (= O)) and phosphonic acid.

  Among these, a phosphonic acid compound containing an amino group is preferred, aminoalkylphosphonic acid is more preferred, and aminomethylphosphonic acid is most preferred.

  (B) The usage-amount of a phosphonic acid compound is 0.01-20 mol% with respect to the target epoxy group introduction amount, and 0.1-10 mol% is further more preferable. Most preferably, it is 0.5-3 mol%.

  The surfactant (C) may be any of anionic, cationic, zwitterionic and nonionic surfactants, and is not particularly limited.

  Examples of the anionic surfactant include salts of carboxylic acid, sulfonic acid, phosphoric acid and the like. Examples of the cationic surfactant include ammonium salts. Examples of zwitterionicity include amine oxide, amino acid, ammonium sulfonic acid and the like. Examples of nonionic surfactants include ester-based, polyethylene glycol-based, and amine-based surfactants.

  Specific examples of the surfactant (C) include tetrapentylammonium chloride, tetrahexylammonium chloride, tetraheptylammonium chloride, trioctylmethylammonium chloride, tetrapentylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide. , Trioctylmethylammonium bromide, tetrapentylammonium iodide, tetrahexylammonium iodide, tetraheptylammonium iodide, trioctylmethylammonium iodide, tetraheptylammonium hydrogensulfate, trioctylmethylammonium hydrogensulfate, triethylhydrogensulfate Quaternary ammonium salts such as benzylammonium; tetrabutylphosphonium chloride, tetrapentylphosphonium chloride, trioctylmethylphosphonate , Pentyltriphenylphosphonium chloride, heptyltriphenylphosphonium chloride, octyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, tetrapentylphosphonium bromide, trioctylmethylphosphonium bromide, pentyltriphenylphosphonium bromide, heptyltribromide bromide Phenylphosphonium, octyltriphenylphosphonium bromide, tetrabutylphosphonium iodide, tetrapentylphosphonium iodide, trioctylmethylphosphonium iodide, pentyltriphenylphosphonium iodide, heptyltriphenylphosphonium iodide, octyltriphenylphosphonium iodide, etc. And quaternary phosphonium salts.

  Of these, quaternary ammonium salts or quaternary phosphonium salts are preferred. More preferred are quaternary ammonium hydrogen sulfate or quaternary phosphonium hydrogen sulfate. More preferably, it is a quaternary alkyl ammonium hydrogen sulfate or a quaternary alkyl phosphonium hydrogen sulfate. Most preferred are trioctylmethylammonium hydrogensulfate and trioctylmethylphosphonium hydrogensulfate.

  (C) Although the usage-amount of surfactant does not have a restriction | limiting in particular, 0.01-20 mol% is preferable with respect to the target epoxy group introduction amount, and 0.1-10 mol% is further more preferable. Most preferably, it is 0.5-3 mol%. In the case of a surfactant whose molecular weight is not clear, 0.01% to 10% is preferable and 0.1 to 5% is more preferable on a mass basis with respect to a polymer containing a carbon-carbon double bond.

<Hydrogen peroxide>
In the present invention, hydrogen peroxide in the form of a commercially available aqueous solution can be used as it is or diluted with water. For example, a 10 to 60% by mass aqueous hydrogen peroxide solution can be easily obtained industrially. The concentration of hydrogen peroxide is not particularly limited, but from the viewpoint of reaction efficiency and safety, it is usually preferably in the range of 0.01 to 60% by mass, and more preferably 5 to 60% by mass. An even more preferred concentration is 15-50% by weight, most preferably 30-40% by weight.

The amount of hydrogen peroxide to be used is not particularly limited, but in the epoxidized polymer that is a product, it varies depending on the desired amount of introduced epoxy groups, the required reaction rate, and the like. It also depends on the level of side reactions such as decomposition of hydrogen oxide. It is preferably in the range of 1 to 1,000 moles per mole of carbon-carbon double bonds to be converted to epoxy groups, contained in the polymer containing carbon-carbon double bonds, It is more preferable that the molar range. It is more preferably 1 to 50 mol times, still more preferably 1 to 20 mol times, and most preferably 1 to 5 times mol. If the amount is less than the above amount, the reaction rate may be slow, and if it is too large, the reaction rate may be excessive, or a large excess of hydrogen peroxide may remain after the reaction.

<Reaction conditions, etc.>
In the present invention, the epoxidation reaction is carried out using hydrogen peroxide as an oxidizing agent and a catalyst comprising (A) a group VI metal oxide salt, (B) a phosphonic acid compound and (C) a surfactant. Hydrogen peroxide and the method for adding the catalyst are not particularly limited.

  The production method of the present invention can be carried out, for example, by adding the above catalyst to a polymer containing a carbon-carbon double bond and then adding hydrogen peroxide with vigorous stirring to cause an epoxidation reaction. At this time, it is desirable to add hydrogen peroxide after adding all of the catalyst.

  The production method of the present invention can also be carried out by simultaneously adding a catalyst and hydrogen peroxide to a polymer containing a carbon-carbon double bond and causing an epoxidation reaction.

  The production method of the present invention may be carried out in an epoxidation reaction inert solvent in which a polymer containing a carbon-carbon double bond is dissolved at 30 ° C. in an amount of 1% by mass or more. You may carry out by the dispersion state of a diameter of 10 micrometers or less.

  The epoxidation reaction inert solvent is not particularly limited, but a nonpolar or polar solvent that is relatively inert to the oxidation / reduction reaction is preferable. Nonpolar solvents can include aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof, and polar solvents can include ethers, esters, and the like.

  Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, cyclooctane, 2,6-dimethylcyclooctane; benzene, toluene, xylene, mesitylene, ethylbenzene, cumene And aromatic hydrocarbons.

  Of these, hydrocarbon solvents having 5 to 12 carbon atoms are preferable, and hexane, heptane, octane, cyclohexane, toluene, and xylene are more preferable. Most preferred are cyclohexane, normal hexane and toluene.

  The amount of the epoxidation reaction inert solvent used varies depending on the solubility of the polymer containing a carbon-carbon double bond to be subjected to the reaction in the solvent. From the viewpoint of reactivity and operability, the range is preferably from 1 to 100 times by mass, and more preferably from 1 to 20 times by mass.

  The reaction can be performed in a dispersion state in which a polymer containing a carbon-carbon double bond has an average particle size of 10 μm or less, but the dispersion medium in this case is not particularly limited, and water or an organic solvent can be used. It is preferable to use water. In order to obtain a good dispersion state, commonly used emulsifiers such as polyvinyl alcohol and alkylbenzene sulfonate can be added.

  In the production method of the present invention, the pH during the reaction is preferably in an acidic state of 2 or more and less than 7, and more preferably in the range of 2 to 4 from the viewpoint of reaction rate and operability. If the pH during the reaction is too low, the epoxidation reaction proceeds violently and is difficult to control, and the stability of the target epoxidized polymer may be reduced. Also, if the pH during the reaction is too high, the stability of hydrogen peroxide is impaired, and the epoxidation selectivity per hydrogen peroxide may be significantly reduced.

  In the production method of the present invention, the reaction pressure is not particularly limited, but it is usually preferably in the range of 80 kPa to 1 MPa from the viewpoint of preventing volatilization of the solvent. Moreover, it is preferable to perform the manufacturing method of this invention in the atmosphere of inert gas, such as nitrogen and argon, from a safety viewpoint.

  In the production method of the present invention, the reaction temperature is not particularly limited, but is usually in the range of 0 to 140 ° C, preferably in the range of 40 to 100 ° C, from the viewpoint of reaction rate and safety, A range of 100 ° C. is more preferable. When the reaction temperature is high, the decomposition reaction of hydrogen peroxide may be accelerated and the selectivity of the epoxidation reaction may be reduced. If the reaction temperature is low, the reaction rate may decrease, and the productivity may decrease.

  Separation of the epoxidized polymer from the reaction mixture after completion of the reaction can be performed by a normal isolation and purification operation. For example, the reaction mixture is allowed to stand to separate into an organic layer and an aqueous layer, then the aqueous layer is removed, and the resulting organic layer is washed with water, an aqueous sodium bisulfite solution, an aqueous sodium sulfite solution, etc. It can be carried out by performing known operations for isolating the polymer from the solution, such as precipitation, removal of the solvent under heating, removal of the solvent under reduced pressure, and removal of the solvent with steam (steam stripping).

  Efficient removal of the catalyst should be performed by contacting the organic layer after separation from the aqueous layer and washing with water, aqueous sodium bisulfite, aqueous sodium sulfite, etc. with activated carbon or a basic substance. Can do.

<Epoxidized polymer>
The epoxidized polymer obtained by the method of the present invention has an epoxy group content of 0.01 to 100 mol%, preferably 1 to 70 mol%, more preferably based on the total monomer units constituting the polymer. It is 3 to 50 mol%, most preferably 5 to 30 mol%. When the content of the epoxy group is small, the functions such as the reaction point of the epoxy group, polarity, compatibility and the like are difficult to exhibit, and when the content is too large, the thermal stability, PH stability and the like may be insufficient. In addition, there is no restriction | limiting in particular in the distribution of the epoxy group contained in the epoxidized polymer obtained by the method of this invention, For example, regular distribution, block-shaped distribution, random distribution, tapered distribution, these Some distributions are mixed. The epoxy group may be contained in either the main chain or the side chain of the epoxidized polymer, but from the viewpoint of the stability of the epoxidized polymer, 70 mol% or more of all the epoxy groups of the epoxidized polymer are the main chain. Is preferably contained in the main chain, and more preferably 80 mol% or more 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 epoxidized polyalkene obtained by ring-opening metathesis polymerization of cycloalkene such as cycloheptene and cyclooctene. 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 block copolymer containing polydiene block such as polymer on styrene block; diene such as styrene-butadiene random copolymer, styrene-isoprene random copolymer Random copolymer epoxidized polymer consisting of styrene and other polysynthetic monomers; taper copolymer epoxidized polymers obtained from dienes such as styrene-butadiene taper copolymer and other polymer monomers Epoxidized polymers such as these partially hydrogenated products; dibasic acids such as terephthalic acid and diols such as 2-butene-1,4-diol or dibasic acids such as tetrahydrophthalic acid and 1,4- Epoxidized polyesters of unsaturated polyesters obtained from diols such as butanediol; dibasic acids such as terephthalic acid and diamines such as 2-butene-1,4-diamine, or dibasic such as tetrahydrophthalic acid Epoxidized polyamides of unsaturated polyamides obtained from acids and diamines such as 1,4-butanediamine; acrylic acid esters And epoxides such as ethylene acrylate, butyl acrylate and isoprene, epoxidized butadiene copolymer, ethylene-propylene-diene rubber, isoprene rubber, chloroprene rubber, etc. Can do.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

<Measurement method>
The data shown below was measured according to the following method.

(1) Epoxidation rate The epoxidation rate was determined by a proton nuclear magnetic resonance ( ¹ H-NMR) method.
Equipment: JEOL-LA500 (resolution 500MHz)
Solvent: deuterated chloroform reference: TMS or chloroform temperature: 20 ° C

  In addition, although the shift position of the signal required for quantification and the signal used as a reference is as follows, it can assign and quantify easily compared with well-known literature etc. Note that the shift position may move depending on the solvent, temperature measurement conditions, and polymer structure. At that time, the entire monomer unit composition contained in the polymer is assigned and assigned appropriately.

[Signals used for quantification]
(A) 2.6-3.0 ppm
Epoxy group (—CH—). Contains 2H per unit of epoxy group.

(B) 4.8-5.0 ppm
Butadiene 1,2-bond (= CH2). It contains 2H per unit of 1,2-vinyl group by 1,2-bond.

(C) 5.0-5.6 ppm
1,2-vinyl group (-CH =) and butadiene 1,4-bond (double bond in the main chain) (-CH =) by butadiene 1,2-bond. Contains 1H per 1,2-vinyl group by 1,2-bond and 2H per 1,4-bond

(D) 6.3 to 7.3 ppm
Benzene ring H in styrene. Contains 5H per unit of styrene. When chloroform is used as a standard, this range (7.2 ppm) includes H1 in chloroform.

[Quantitative method]
(I) Molar ratio of epoxy group The value obtained by dividing the integrated value in the range of (a) by 2 indicates the molar ratio of epoxy group.

(Ii) 1,2-bond (1,2-vinyl) molar ratio The value obtained by dividing the integrated value in the range of (b) by 2 is the mole of 1,2-bond (1,2-vinyl) of the butadiene component. Indicates the ratio.

(Iii3) Molar ratio of 1,4-bond The value obtained by subtracting the molar ratio of butadiene 1,2-bond calculated in (2) from the integral value in the range of (c) and then dividing by 2 is butadiene 1,4- The molar ratio of bonds is shown.

(Iv) Molar ratio of styrene The value obtained by subtracting the chloroform content from the integral value in the range of (d) and then dividing by 5 shows the molar ratio of styrene.

  A value obtained by dividing each of the molar ratios (i) to (iv) by the total value of (i) to (iv) and then multiplying by 100 is the mol% of each component.

  The value obtained by multiplying the mol% of each component by the respective molecular weight, dividing by the total, and multiplying by 100 is the weight% of each component.

  Hereinafter, the butadiene 1,2-bond ratio represents the molar ratio of 1,2-bond to the total of 1,4-bond and 1,2-bond for butadiene in the polymer.

  In the following examples using butadiene, the butadiene 1,2-bond was confirmed to be inert to the oxidation reaction under the conditions shown, so that the epoxidation rate was determined as butadiene 1,4- Of the bonds, the ratio (molar ratio) converted to epoxy groups is shown.

  In addition, the amount of epoxy groups corresponded with the value calculated | required separately by the following titration methods (HCl-dioxane method).

[Titration method (HCl-dioxane method)]
0.1 g of the polymer after the reaction is precisely weighed and made up to 50 mL with a solution obtained by mixing 1 mL of 12N-hydrochloric acid with 100 mL of purified dioxane. Add a small amount of 1% phenolphthalein in ethanol and titrate with 0.1N NaOH.

(2) Molecular weight The molecular weight was measured by GPC.
Equipment: Tosoh HLC-8220
Column: Showa Denko Shodex GPC KF-400HQ × 4 series connection temperature: 40 ° C.
Detection: RI (differential refractive index)
Solvent: Tetrahydrofuran Concentration: 2 wt%
Calibration curve: Standard polystyrene (manufactured by Tosoh)

(3) Glass transition point The glass transition point was calculated | required by DSC measurement.
Device name: DSC6200 (Seiko Instruments Inc.)
Measurement temperature range: -120 ° C to 200 ° C
Temperature increase rate: 10 ° C / min

In addition, the sample was extract | collected by heat-pressing on condition of the following before a measurement.
Temperature: 220 ° C
Pressure: 300kg, 3 minutes Thickness: 0.5mm

(4) Observation of rubber particle shape and particle size The shape and particle size of rubber particles were observed with a transmission electron microscope (TEM).
Device name: H-7500 (Hitachi)
Acceleration voltage: 80KV

  Samples were cut to a thickness of 1000 angstroms after osmic acid staining.

<Polymer containing carbon-carbon double bond>
The following polymer was used as a polymer containing a carbon-carbon double bond as a raw material.

(1) Sample A
Styrene-butadiene block copolymer ("Clearen 760M", Denki Kagaku Kogyo Co., Ltd.)
Styrene / butadiene ratio in polymer = 24/76 (mass ratio)
Butadiene 1,2-bond ratio = 13%
Mw 121,000, Mn 952,000, Mw / Mn 1.27
Glass transition point: -55 ° C, 97 ° C

(2) Sample B
Styrene-butadiene block copolymer ("TR2003" JSR)
Styrene / butadiene ratio in polymer = 40/60 (mass ratio)
Butadiene 1,2-bond ratio 16%
Mw 103,000, Mn 87770, Mw / Mn 1.18
Glass transition point: -78 ° C, 102 ° C

(3) Sample C
Rubber-reinforced styrene-butadiene-methyl methacrylate copolymer (grafted rubber particles with an average particle size of 0.5 μm (styrene-methyl methacrylate copolymer grafted with styrene-butadiene rubber) are uniform in styrene / methyl methacrylate copolymer Distributed)
Styrene / butadiene / methyl methacrylate ratio in polymer = 59/3/38 (mass ratio)
Butadiene 1,2-bond ratio = 17%
Mw 1290,000, Mn 6250,000, Mw / Mn 2.06
Glass transition point: -56 ° C, 86 ° C

(4) Sample D
Polystyrene-polybutadiene diblock copolymer Mw / Mn 1.04
Peak top molecular weight of polystyrene block chain 6,200
Polybutadiene block chain peak top molecular weight 16,300
Butadiene 1,2-bond ratio 11%

  Sample D was synthesized as follows.

  A stainless steel polymerization tank with an internal volume of 3 L and a stirrer was washed with cyclohexane, replaced with nitrogen gas, and charged with 1,260 g of cyclohexane (dehydrated to a water content of 10 ppm or less and containing 150 ppm of tetrahydrofuran) in a nitrogen gas atmosphere. 62.9 g of styrene dehydrated to a water content of 5 ppm or less was added. After raising the internal temperature to 50 ° C., 13.9 ml of a 10% cyclohexane solution of n-butyllithium was added and polymerized for 20 minutes in a range where the maximum temperature did not exceed 120 ° C. (polystyrene block chain synthesis).

  Further, after raising the internal temperature to 80 ° C., 251.6 g of butadiene dehydrated by passing through a molecular sieve was added and polymerized for 30 minutes in a range where the maximum temperature did not exceed 120 ° C. (synthesis of polybutadiene block chain).

  Finally, the active terminal was deactivated with methanol, and this solution was added little by little in a large amount of methanol containing a hindered phenol stabilizer, followed by vacuum drying.

(5) Sample E
Polystyrene-polybutadiene diblock copolymer Mw / Mn 1.04
Peak top molecular weight of polystyrene block chain 4,500
Polybutadiene block chain peak top molecular weight 16,700
Butadiene 1,2-bond ratio 27%

  Sample E was synthesized as follows.

  A stainless steel polymerization tank with an internal volume of 3 L and a stirrer was washed with cyclohexane, and after replacement with nitrogen gas, 1,260 g of cyclohexane (dehydrated to 10 ppm or less of water and containing 2,000 ppm of tetrahydrofuran) was charged in a nitrogen gas atmosphere. Next, 62.9 g of styrene dehydrated to a water content of 5 ppm or less was added. After raising the internal temperature to 50 ° C., 13.9 ml of a 10% cyclohexane solution of n-butyllithium was added and polymerized for 20 minutes in a range where the maximum temperature did not exceed 120 ° C. (polystyrene block chain synthesis).

  Further, after raising the internal temperature to 80 ° C., 251.6 g of butadiene dehydrated by passing through a molecular sieve was added and polymerized for 30 minutes in a range where the maximum temperature did not exceed 120 ° C. (synthesis of polybutadiene block chain).

  Finally, the active terminal was deactivated with methanol, and this solution was added little by little in a large amount of methanol containing a hindered phenol stabilizer, followed by vacuum drying.

(6) Sample F
Ethyl acrylate / normal butyl acrylate / isoprene ratio in the emulsion polymer of ethyl acrylate / normal butyl acrylate / isoprene copolymer = 70/29/1 (mass ratio)
37% solids in emulsion
Emulsion average particle size is 100 nm (light diffraction method)
pH = 2.3

  Sample F was synthesized under the nitrogen atmosphere as follows.

  Distilled water 2,400 g, alkylbenzene sulfonic acid 96 g, and sodium acetate 3 g were added to a stainless steel reactor with an internal volume of 5 L to prepare an emulsifier solution, and 2.6 g of isoprene was added. After adding a redox-type radical reaction initiator in the reactor, the temperature was raised to 55 ° C., and 480 g of normal butyl acrylate, 1,120 g of ethyl acrylate, 27 g of isoprene, and 0.4 g of t-dodecyl mercaptan were added over 6 hours. Added continuously. On the other hand, after raising the temperature to 55 ° C., an aqueous solution comprising 42 g of tertiary butyl hydroperoxide and an emulsifier was continuously added over 6.5 hours.

  After completion of the reaction, the temperature was lowered and the produced emulsion was taken out.

<(C) Surfactant>
As (C) surfactant which is one component of the catalyst, trioctylmethylammonium hydrogen sulfate was synthesized as follows.

  To a 1 L eggplant-shaped flask equipped with a magnetic stirrer was added 4.2 g of methyl trioctylammonium chloride, 150 ml of 50% sulfuric acid and 200 ml of toluene. After stirring at room temperature for 12 hours, the toluene layer was separated from the aqueous layer and anhydrous sodium sulfate. After dehydration, toluene was distilled off to precipitate as a white solid, followed by vacuum drying.

<Example 1 (Sample A)>
To a 3000 ml three-necked separable flask equipped with a magnetic stirrer, a reflux tube, and a dropping funnel, 150 g of polymer (sample A) and 1000 ml of toluene were added and dissolved.

  On the other hand, in a 200 ml eggplant-shaped flask, (A) 1.17 g of sodium tungstate, (B) 0.39 g of aminomethylphosphonic acid, (C) 1.65 g of trioctylmethylammonium hydrogen sulfate, and an aqueous hydrogen peroxide solution (30%, 96 g) was weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

This was added to the previous polymer solution and stirred vigorously at 70 ° C. for 2 hours. The reaction solution was cooled to room temperature, and the aqueous layer and the organic layer were separated. The organic layer was washed 3 times with 100 g of water to remove the aqueous layer. A part was dropped into methanol, dried and analyzed by ¹ H-NMR. The epoxidation rate was 9.3%.

  The epoxidation rate was calculated based on the carbon-carbon double bond in the polymer main chain (1,4-vinyl structure). In all the following examples, the 1,2-vinyl structure was unreacted.

  As a result of GPC measurement, Mw was 169,000, Mn was 884,000, and Mw / Mn was 1.91, and gelation, molecular chain breakage, and coloring were suppressed. Moreover, the glass transition point was -47 degreeC and 94 degreeC.

<Example 2 (Sample B)>
To a 3000 ml three-necked separable flask equipped with a magnetic stirrer, a reflux tube, and a dropping funnel, 100 g of polymer (sample B) and 2000 ml of toluene were added and dissolved.

  On the other hand, in a 200 ml eggplant-shaped flask, (A) 1.74 g of sodium tungstate, (B) 0.585 g of aminomethylphosphonic acid, (C) 2.45 g of trioctylmethylammonium hydrogen sulfate, and an aqueous hydrogen peroxide solution (30%, 118 g) was weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

This was added to the previous polymer solution and stirred vigorously at 70 ° C. for 2 hours. The reaction solution was cooled to room temperature, and the aqueous layer and the organic layer were separated. The organic layer was washed 3 times with 100 g of water to remove the aqueous layer. A part of the solution was dropped into methanol to be solidified, dried and analyzed by ¹ H-NMR. The epoxidation rate was 29%.

  As a result of GPC measurement, Mw was 142,000, Mn was 663,000, and Mw / Mn was 2.15, and gelation, molecular chain breakage, and coloring were suppressed. Moreover, the glass transition point was -53 degreeC and 100 degreeC.

<Example 3 (Sample C)>
To a 3000 ml three-necked separable flask equipped with a magnetic stirrer, reflux tube, and dropping funnel, 100 g of polymer (sample C) pellets and 2000 ml of toluene were added. The polymer pellets did not dissolve completely, but the swollen components coexisted, but the oxidation reaction was carried out as it was.

  On the other hand, in a 200 ml eggplant-shaped flask, (A) 3.30 g of sodium tungstate, (B) 1.11 g of aminomethylphosphonic acid, (C) 4.66 g of trioctylmethylammonium hydrogen sulfate, and an aqueous hydrogen peroxide solution (30%, 123 g) was weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

This was added to the previous polymer solution and stirred vigorously at 70 ° C. for 2 hours. The reaction solution was cooled to room temperature, and the aqueous layer and the organic layer were separated. The organic layer was washed 3 times with 100 g of water to remove the aqueous layer. A part was dropped into methanol, dried and analyzed by ¹ H-NMR. The epoxidation rate was 37%.

  As a result of the GPC measurement, Mw was 124,000, Mn was 5250,000, and Mw / Mn was 2.36, and gelation, molecular chain breakage, and coloring were suppressed.

  As a result of TEM observation, there was no significant change in the rubber particle shape (single cell and salami shape coexisted) and particle size before and after the reaction.

<Example 4 (Sample D)>
In a beaker, 678.9 mg of polymer (sample D) and 5 ml of toluene were added and dissolved.

  On the other hand, in a 30 ml eggplant type flask equipped with a magnetic stirrer and a reflux tube, (A) 16.5 mg of sodium tungstate, (B) 5.55 mg of aminomethylphosphonic acid, (C) 23.3 mg of trioctylmethylammonium hydrogen sulfate. And an aqueous hydrogen peroxide solution (30%, 1.2 g) were weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

The previous polymer solution was added thereto, and the mixture was vigorously stirred at 70 ° C. for 2.5 hours. The consumption of hydrogen peroxide was confirmed with a peroxide test paper, the reaction solution was cooled to room temperature, and the aqueous layer and the organic layer were separated. When manganese dioxide was added to the organic layer and hydrogen peroxide was completely consumed, it was dried over anhydrous sodium sulfate, isolated on a silica gel column using ethyl acetate, and analyzed by ¹ H-NMR. The epoxidation rate was 26%.

<Example 5 (Sample D)>
In a beaker, 678.9 mg of polymer (sample D) and 4 ml of cyclohexane were added and dissolved.

  On the other hand, in a 50 ml eggplant type flask equipped with a magnetic stirrer and a reflux tube, (A) 16.5 mg of sodium tungstate, (B) 5.55 mg of aminomethylphosphonic acid, (C) 23.3 mg of trioctylmethylammonium hydrogen sulfate. And an aqueous hydrogen peroxide solution (30%, 1.2 g) were weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

The previous polymer solution was added thereto, and the mixture was vigorously stirred at 70 ° C. for 1.5 hours. The consumption of hydrogen peroxide was confirmed with a peroxide test paper, the reaction solution was cooled to room temperature, and the aqueous layer and the organic layer were separated. When manganese dioxide was added to the organic layer and hydrogen peroxide was completely consumed, it was dried over anhydrous sodium sulfate, isolated on a silica gel column using ethyl acetate, and analyzed by ¹ H-NMR. The epoxidation rate was 2%.

<Example 6 (Sample E)>
In a beaker, 3.44 g of polymer (sample E) and 25 ml of toluene were added and dissolved.

  On the other hand, in a 100 ml eggplant type flask equipped with a magnetic stirrer and a reflux tube, (A) 82.4 mg of sodium tungstate, (B) 27.8 mg of aminomethylphosphonic acid, (C) 116.4 mg of trioctylmethylammonium hydrogen sulfate. And an aqueous hydrogen peroxide solution (30%, 6.0 g) were weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

The previous polymer solution was added thereto, and the mixture was vigorously stirred at 70 ° C. for 1.5 hours. The consumption of hydrogen peroxide was confirmed with a peroxide test paper, the reaction solution was cooled to room temperature, and the aqueous layer and the organic layer were separated. When manganese dioxide was added to the organic layer and hydrogen peroxide was completely consumed, it was dried over anhydrous sodium sulfate, isolated on a silica gel column using ethyl acetate, and analyzed by ¹ H-NMR. The epoxidation rate was 54%.

<Example 7 (Sample F)>
1.65 g (of which 0.614 g of polymer) of Sample F was collected in a beaker.

  On the other hand, in a 30 ml eggplant type flask equipped with a magnetic stirrer and a reflux tube, (A) 16.5 mg of sodium tungstate, (B) 5.55 mg of aminomethylphosphonic acid, (C) 23.3 mg of trioctylmethylammonium hydrogen sulfate. And an aqueous hydrogen peroxide solution (30%, 3.3 g) were weighed, the internal temperature was gradually raised to 60 ° C., and the mixture was vigorously stirred for 30 minutes to prepare a catalyst.

The previous emulsion was added thereto, and the mixture was vigorously stirred at 70 ° C. for 2 hours. The consumption of hydrogen peroxide was confirmed with a peroxide test paper, and the reaction solution was cooled to room temperature and analyzed by ¹ H-NMR. Signals were observed at 3.04 and 3.21 ppm attributed to the epoxy group, confirming the formation of the epoxy group.

<Comparative Example 1>
In Example 1, the reaction was carried out without adding (A) sodium tungstate. Almost no epoxy groups were observed in 2 hours.

<Comparative example 2>
In Example 1, the reaction was carried out without adding (B) aminomethylphosphonic acid, and almost no epoxy group was observed in 2 hours.

<Comparative Example 3>
In Example 1, when the reaction was carried out without adding (C) trioctylmethylammonium hydrogensulfate, almost no epoxy group was observed in 2 hours.

Claims (9)

  Using a catalyst comprising hydrogen peroxide as an oxidizing agent, (A) a group VI metal oxide salt, (B) a phosphonic acid compound and (C) a surfactant, a polymer containing a carbon-carbon double bond is oxidized. And a method for producing an epoxidized polymer, comprising the step of introducing an epoxy group.   2. The method for producing an epoxidized polymer according to claim 1, wherein the salt of the (A) Group VI metal oxide is a tungstate.   The method for producing an epoxidized polymer according to claim 1 or 2, wherein the surfactant (C) is a quaternary ammonium salt or a quaternary phosphonium salt.   The method for producing an epoxidized polymer according to claim 3, wherein the quaternary ammonium salt or quaternary phosphonium salt is a quaternary ammonium hydrogen sulfate or a quaternary phosphonium hydrogen sulfate.   The method for producing an epoxidized polymer according to any one of claims 1 to 4, wherein the (B) phosphonic acid compound is a phosphonic acid compound containing an amino group.   6. The epoxidized polymer according to claim 1, wherein the carbon-carbon double bond of the polymer containing the carbon-carbon double bond is formed by a polymerization reaction of a diene monomer. Production method.   The epoxidized polymer according to any one of claims 1 to 6, wherein the step is performed in an epoxidation reaction inert solvent in which a polymer containing a carbon-carbon double bond is dissolved at 30 ° C by 1% by mass or more. Manufacturing method.   The method for producing an epoxidized polymer according to any one of claims 1 to 6, wherein the step is performed in a dispersion state in which a polymer containing a carbon-carbon double bond has an average particle diameter of 10 µm or less.   The method for producing an epoxidized polymer according to any one of claims 1 to 8, wherein the step is performed in an acidic state having a pH of 2 or more and less than 7.