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- JP2002249516A5 JP2002249516A5 JP2001386169A JP2001386169A JP2002249516A5 JP 2002249516 A5 JP2002249516 A5 JP 2002249516A5 JP 2001386169 A JP2001386169 A JP 2001386169A JP 2001386169 A JP2001386169 A JP 2001386169A JP 2002249516 A5 JP2002249516 A5 JP 2002249516A5
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【００４０】
本発明の方法で得られるエポキシ化重合体としては、例えばエポキシ化ポリブタジエン、エポキシ化ポリイソプレンなどのエポキシ化ポリジエン；シクロヘプテン、シクロオクテンなどのシクロアルケンを開環メタセシス重合して得られるポリアルケンのエポキシ化重合体；イソプレン−ブタジエンブロック共重合体、スチレン−ブタジエンブロック共重合体、スチレン−イソプレン共重合体、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−（イソプレン／ブタジエン）−スチレンブロック共重合体などのポリジエンブロックを含有するブロック共重合体のエポキシ化重合体；スチレン−ブタジエンランダム共重合体、スチレン−イソプレンランダム共重合体などのジエンと他の重合性単量体からなるランダム共重合体のエポキシ化重合体；スチレン−ブタジエンテーパー共重合体などのジエンと他の重合性単量体から得られるテーパー共重合体のエポキシ化重合体；これらの部分水素添加物などのエポキシ化重合体；テレフタル酸などの二塩基酸と２−ブテン−１，４−ジオールなどのジオール類または、テトラヒドロフタル酸などの二塩基酸と１，４−ブタンジオールなどのジオール類から得られる不飽和ポリエステル類のエポキシ化ポリエステル類；テレフタル酸などの二塩基酸と２−ブテン−１，４−ジアミンなどのジアミン類、または、テトラヒドロフタル酸などの二塩基酸と１，４−ブタンジアミンなどのジアミン類から得られる不飽和ポリアミド類のエポキシ化ポリアミド等が挙げられる。[0040]
The epoxidized polymer obtained by the method of the present invention includes, for example, epoxidized polydienes such as epoxidized polybutadiene and epoxidized polyisoprene; and epoxidation of polyalkene obtained by ring-opening metathesis polymerization of cycloalkene such as cycloheptene and cyclooctene. polymer; 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 styrene block copolymer; and die such as a styrene - butadiene random copolymer and a styrene-isoprene random copolymer. Random copolymer epoxidized polymer consisting of down and another polymerizable monomer; styrene - epoxidation weight of a diene and another polymerizable tapered copolymer obtained from monomers such as butadiene tapered copolymer Epoxidized polymers such as partially hydrogenated products thereof; 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 diacids such as tetrahydrophthalic acid. Epoxidized polyamides of unsaturated polyamides obtained from a basic acid and a diamine such as 1,4-butanediamine are exemplified.
【００４２】
実施例１
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム０．１５ｇ（０．０５ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．１である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液３７．４ｇ（０．３３ｍｏｌ）を３時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で４時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約３分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量：３０ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は８９％であり、エポキシ化率は８８％（選択率：９９％）であった。添加した過酸化水素の９８％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリイソプレン中のタングステン残存量を以下の方法で定量したところ、２１．１ｐｐｍであった。[0042]
Example 1
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and an aqueous solution having a pH of 3.1 prepared by dissolving 0.15 g (0.05 mmol) of ammonium tungstate and 0.33 g (3.3 mmol) of phosphoric acid in 20 g of water. After the addition, 37.4 g (0.33 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while vigorously stirring the resulting mixture at 70 ° C. After the completion of 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. The organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polyisoprene (yield: 30 g) was analyzed to at 1 H-NMR, the conversion of the double bonds is 89%, the epoxidation ratio of 88% (selectivity: 99%) Met. It was found that 98% of the added hydrogen peroxide contributed to the epoxidation reaction.
The amount of tungsten remaining in the obtained epoxidized polyisoprene was determined to be 21.1 ppm by the following method.
【００４４】
実施例２
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、リンタングステン酸０．１１ｇ（０．０４ｍｍｏｌ）およびリン酸０．０２ｇ（０．２０ｍｍｏｌ）を水１０ｇに溶解させて調製したｐＨが２．５である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液３７．４ｇ（０．３３ｍｏｌ）を３時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で４時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約１分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量３０ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は８８％、エポキシ化率は８７％（選択率９９％）であった。添加した過酸化水素の９７％がエポキシ化反応に寄与したことが分かった。
なお、得られたポリイソプレン中のタングステンの残存量を実施例１と同様の方法で分析したところ、１２．１ｐｐｍであった。[0044]
Example 2
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and an aqueous solution having a pH of 2.5 prepared by dissolving 0.11 g (0.04 mmol) of phosphotungstic acid and 0.02 g (0.20 mmol) of phosphoric acid in 10 g of water was added. After the addition, 37.4 g (0.33 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while vigorously stirring the resulting mixture at 70 ° C. After the completion of 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 1 minute. 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 solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
When obtained was analyzed by 1 H-NMR epoxidized polyisoprene (yield 30 g), the double bond conversion of 88%, the epoxidation rate was 87% (99% selectivity). 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.
【００４７】
比較例３
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム０．１５ｇ（０．０５ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させ、炭酸ナトリウム０．０７ｇ（０．６６ｍｍｏｌ）を加えて調製したｐＨが５．１である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液３７．４ｇ（０．３３ｍｏｌ）を３時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で９時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約５４分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量３０ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は９１％であり、エポキシ化率は７３％（選択率８０％）であった。添加した過酸化水素の７２％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリイソプレン中のタングステン残存量を実施例１と同様の方法で分析したところ、２９．１ｐｐｍであった。[0047]
Comparative Example 3
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride 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 0.33 g (3.3 mmol) of phosphoric acid were dissolved in 20 g of water, and 0.07 g (0.66 mmol) of sodium carbonate was added. After the addition of the prepared aqueous solution having a pH of 5.1, 37.4 g (0.33 mol) of a 30% aqueous hydrogen peroxide solution was added over 3 hours while vigorously stirring the resulting mixture at 70 ° C. It was dropped. 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. The organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
When obtained was analyzed by 1 H-NMR epoxidized polyisoprene (yield 30 g), the conversion of the double bonds is 91%, the epoxidation ratio of 73% (selectivity 80%) met Was. It was found that 72% 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 29.1 ppm.
【００４８】
比較例４
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム０．１５ｇ（０．０５ｍｍｏｌ）およびリン酸９．４ｍｇ（０．０１ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが４．２である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液３７．４ｇ（０．３３ｍｍｏｌ）を３時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で６時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約１２分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量３０ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は８３％であり、エポキシ化率は８０％（選択率９６％）であった。添加した過酸化水素の８１％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリイソプレン中のタングステン残存量を実施例１と同様の方法で分析したところ、２９．４ｐｐｍであった。[0048]
Comparative Example 4
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and an aqueous solution having a pH of 4.2 prepared by dissolving 0.15 g (0.05 mmol) of ammonium tungstate and 9.4 mg (0.01 mmol) of phosphoric acid in 20 g of water was added. After the addition, 37.4 g (0.33 mmol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while vigorously stirring the resulting mixture at 70 ° C. 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. The organic layer was washed with 100 ml of water, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polyisoprene (yield 30g) was analyzed by 1 H-NMR, the conversion of the double bonds is 83%, the epoxidation ratio of 80% (selectivity 96%) met Was. It was found that 81% of the added hydrogen peroxide contributed to the epoxidation reaction.
In addition, when the amount of tungsten remaining in the obtained epoxidized polyisoprene was analyzed by the same method as in Example 1, it was 29.4 ppm.
【００４９】
実施例３
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム・５水和物０．１２５ｇ（０．０４ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．１である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液２．２６ｇ（０．０２ｍｏｌ）を０．５時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で１時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約０．５分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量２５．５ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は５．３％であり、エポキシ化率は５．３％（選択率１００％）であった。添加した過酸化水素の９８％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリイソプレン中のタングステン残存量を実施例１と同様の方法で分析したところ、１．２ｐｐｍであった。[0049]
Example 3
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride 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. After adding the aqueous solution of No. 1, 2.26 g (0.02 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 0.5 hours while the resulting 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 1 hour, 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 0.5 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 solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
When obtained was analyzed by 1 H-NMR epoxidized polyisoprene (yield 25.5 g), the conversion of the double bond is 5.3%, the epoxidation ratio of 5.3% (Selection Rate of 100%). It was found that 98% 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 1.2 ppm.
【００５０】
実施例４
還流管、２つの滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム・５水和物０．１２５ｇ（０．０４ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．１である水溶液と、３０％過酸化水素水溶液３７．４ｇ（０．３３ｍｏｌ）を別々の滴下ロートから同時に滴下した（所要時間：３時間）。滴下終了後、反応混合液をさらに７０℃で４時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約１．５分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量３０ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は８８％であり、エポキシ化率は８８％（選択率１００％）であった。添加した過酸化水素の９９％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリイソプレン中のタングステン残存量を実施例１と同様の方法で分析したところ、１３．１ｐｐｍであった。[0050]
Example 4
In a 300 ml three-necked flask equipped with a reflux tube, two dropping funnels, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), toluene 100 g and 0.32 g of trioctylmethylammonium chloride were 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 37.4 g (0.33 mol) of a 30% aqueous hydrogen peroxide solution were simultaneously dropped from separate dropping funnels (time required: 3 hours). 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, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polyisoprene (yield 30g) was analyzed by 1 H-NMR, the conversion of the double bonds is 88%, the epoxidation ratio of 88% (selectivity 100%) met Was. 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.
【００５１】
比較例５
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリイソプレン（ＬＩＲ−１５、商品名、（株）クラレ製、数平均分子量：１５０００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させ、得られた溶液を７０℃に昇温した。タングステン酸アンモニウム・５水和物０．１２５ｇ（０．０４ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．１である水溶液に３０％過酸化水素水溶液３７．４ｇ（０．３３ｍｏｌ）を加え、添加液を調製した。この添加液を、上記で得られたポリイソプレンおよび塩化トリオクチルメチルアンモニウムを含有するトルエン溶液に、７０℃で３時間かけて滴下した。滴下中、該添加液からは酸素が発生し続けた。該添加液の滴下終了後、反応混合液をさらに７０℃で４時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約１．５分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリイソプレン（収量２８ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は７１％であり、エポキシ化率は６６％（選択率９３％）であった。添加した過酸化水素の４２％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリイソプレン中のタングステン残存量を実施例１と同様の方法で分析したところ、１１．４ｐｐｍであった。[0051]
Comparative Example 5
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyisoprene (LIR-15, trade name, manufactured by Kuraray Co., Ltd., number average molecular weight: 15000), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride was 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 solution 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, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polyisoprene (yield 28 g) was analyzed by 1 H-NMR, the conversion of the double bonds is 71%, the epoxidation ratio of 66% (selectivity 93%) met Was. 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.
【００５２】
実施例５
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、スチレン−イソプレン−スチレントリブロック共重合体（スチレン含有量：３２％、数平均分子量：３００００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．２０ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム・５水和物０．０９３ｇ（０．０３ｍｍｏｌ）およびリン酸０．２２ｇ（２．２ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．３である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液２６．９ｇ（０．２３ｍｏｌ）を３時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で８時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約１分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化スチレン−イソプレン−スチレントリブロック共重合体（収量２９ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は９２％であり、エポキシ化率は９１％（選択率９９％）であった。添加した過酸化水素の９６％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化スチレン−イソプレン−スチレントリブロック共重合体のタングステン残量を実施例１と同様の方法で分析したところ９ｐｐｍであった。[0052]
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 25 g of styrene-isoprene-styrene triblock copolymer (styrene content: 32%, number average molecular weight: 30,000), toluene 100 g and 0.20 g of trioctylmethylammonium chloride were added and completely dissolved with stirring at 60 ° C. The temperature of this solution was raised to 70 ° C., and 0.093 g (0.03 mmol) of ammonium tungstate pentahydrate and 0.22 g (2.2 mmol) of phosphoric acid were dissolved in 20 g of water. After adding the aqueous solution of No. 3, 26.9 g (0.23 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while vigorously stirring the resulting mixture at 70 ° C. 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 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 minute. 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 solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized styrene - isoprene - styrene tri-block copolymer was analyzed with (yield 29 g) in 1 H-NMR, the conversion of the double bonds is 92%, the epoxidation ratio of 91% (Selectivity 99%). It was found that 96% of the added hydrogen peroxide contributed to the epoxidation reaction.
The residual amount of tungsten in the obtained epoxidized styrene-isoprene-styrene triblock copolymer was analyzed by the same method as in Example 1 and found to be 9 ppm.
【００５３】
実施例６
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、ポリオクテニレン（ヒュルス・アメリカ製、数平均分子量：６００００）２５ｇ、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．１５ｇを加え、７０℃で攪拌しながら完全に溶解させた。この溶液を８０℃に昇温し、タングステン酸アンモニウム・５水和物０．０７８ｇ（０．０２５ｍｍｏｌ）およびリン酸０．１７ｇ（１．７ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．５である水溶液を加えた後、得られた混合液を８０℃で激しく攪拌しながら、３０％過酸化水素水溶液２６．２ｇ（０．２３ｍｏｌ）を３時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに８０℃で６時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約２分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄した後、活性炭〔ＹＰ−１７（商品名、クラレケミカル（株）社製）〕１２ｇを添加し、５０℃で１時間攪拌した。活性炭をフィルターによって除去し、得られた濾液からトルエンを減圧下に留去し、残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリオクテニレン（収量２８ｇ）を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は１００％であり、エポキシ化率は１００％（選択率１００％）であった。添加した過酸化水素の９９％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリオクテニレン中のタングステン残存量を実施例１と同様の方法で分析したところ、７．３ｐｐｍであった。[0053]
Example 6
In a 300 ml three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer, 25 g of polyoctenylene (manufactured by Huls America, number average molecular weight: 60000), 100 g of toluene and 0.15 g of trioctylmethyl ammonium chloride were placed. In addition, the mixture was completely dissolved with stirring at 70 ° C. The temperature of the solution was raised to 80 ° C., and 0.078 g (0.025 mmol) of ammonium tungstate pentahydrate and 0.17 g (1.7 mmol) of phosphoric acid were dissolved in 20 g of water to adjust the pH to 3. After adding the aqueous solution of No. 5, 26.2 g (0.23 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while vigorously stirring the resulting mixture at 80 ° C. After the completion of 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 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 2 minutes. The aqueous layer was separated and removed, and the organic layer was washed with 100 ml of water. Then, 12 g of activated carbon [YP-17 (trade name, manufactured by Kuraray Chemical Co., Ltd.)] was added, and the mixture was 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.
The obtained epoxidized polyoctenylene the (yield 28 g) was analyzed by 1 H-NMR, the conversion of the double bonds was 100%, the epoxidation rate was 100% (100% selectivity) . 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.
【００５４】
実施例７
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、シス−ポリブタジエン（Ｎｉｐｏｌ−ＢＲ、日本ゼオン製、数平均分子量：３００００）２５ｇ、シクロヘキサン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム０．１５ｇ（０．０５ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．１である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液５２．１ｇ（０．４６ｍｏｌ）を４時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに７０℃で２時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（シクロヘキサン層）と水層の界面が形成されるまでの時間は約２．５分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、シクロヘキサンを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリブタジエン（収量３３．２ｇ）を1Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は１００％であり、エポキシ化率は９８．５％（選択率９８％）であった。添加した過酸化水素の９８％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリブタジエン中のタングステン残存量を実施例１と同様の方法で分析したところ、１４．１ｐｐｍであった。[0054]
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 Nippon Zeon, number average molecular weight: 30000), 100 g of cyclohexane and trioctylmethyl chloride 0.32 g of ammonium was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and an aqueous solution having a pH of 3.1 prepared by dissolving 0.15 g (0.05 mmol) of ammonium tungstate and 0.33 g (3.3 mmol) of phosphoric acid in 20 g of water. After the addition, 52.1 g (0.46 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 4 hours while vigorously stirring the resulting mixture at 70 ° C. 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 until the interface between the organic layer (cyclohexane layer) and the aqueous layer was formed 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, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and further washed twice with 100 ml of water, and cyclohexane was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polybutadiene (yield 33.2 g) was analyzed by 1 H-NMR, the conversion of the double bonds was 100%, the epoxidation ratio of 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.
【００５７】
比較例７
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、シス−ポリブタジエン（Ｎｉｐｏｌ−ＢＲ、日本ゼオン製、数平均分子量：３００００）２５ｇ、クロロホルム１１４ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸ナトリウム０．１１ｇ（０．３３ｍｍｏｌ）およびリン酸０．０６ｇ（０．６ｍｍｏｌ）を水１０ｇに溶解させて調製したｐＨが３．３である水溶液を加えた後、得られた混合液を７０℃で激しく攪拌しながら、３０％過酸化水素水溶液１０．２ｇ（０．０９ｍｏｌ）を４時間かけて滴下した。過酸化水素水溶液の滴下終了後、反応混合液をさらに８０℃で１２時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（クロロホルム層）と水層の界面が形成されるまでの時間は約１８分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、クロロホルムを減圧下に留去し、得られた残留物を８０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリブタジエン（収量２５．８ｇ）を1Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は１９％であり、エポキシ化率は１７％（選択率８９％）であった。添加した過酸化水素の８８％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリブタジエン中のタングステン残存量を実施例１と同様の方法で分析したところ、３１．４ｐｐｍであった。[0057]
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 Nippon Zeon, number average molecular weight: 30000), 114 g of chloroform, and 114 g of trioctylmethyl chloride 0.32 g of ammonium was added and completely dissolved with stirring at 60 ° C. This solution was heated to 70 ° C., and an aqueous solution having a pH of 3.3 prepared by dissolving 0.11 g (0.33 mmol) of sodium tungstate and 0.06 g (0.6 mmol) of phosphoric acid in 10 g of water was added. After the addition, 10.2 g (0.09 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 4 hours while vigorously stirring the resulting mixture at 70 ° C. After the completion of 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, 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 chloroform was distilled off under reduced pressure. The residue was dried at 80 ° C. and 800 Pa for 8 hours.
The obtained epoxidized polybutadiene (yield 25.8 g) was analyzed by 1 H-NMR, the conversion of the double bonds is 19%, in the epoxidation ratio 17% (selectivity 89%) there were. It was found that 88% 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 31.4 ppm.
【００６０】
参考例１〔ポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステルの製造〕
滴下ロート、還流管、メカニカルスターラを装着した容量５００ｍｌの三つ口フラスコに１，４−シクロヘキサンジメタノール４１．２ｇ（０．２９ｍｏｌ）およびテトラヒドロフタル酸無水物８８．５ｇ（０．５８ｍｏｌ）を仕込み、トルエン１５０ｇを加えて溶解させた後、１２０℃で５時間加熱した。室温まで冷却した後、ベンジルトリメチルアンモニウムクロリド０．８ｇ（０．００４ｍｏｌ）を添加して溶解させ、次いで８５％水酸化ナトリウムパウダー４１ｇ（０．８５ｍｏｌ）を加えた後、エピクロロヒドリン６６．９ｇ（０．７ｍｏｌ）を４０℃で８時間かけて滴下し、さらに５時間加熱攪拌した。反応混合物を水洗した後、低沸点物を減圧にて除去して、ポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステルを１３５．２ｇ（収率８３％）得た。[0060]
Reference Example 1 [poly (cyclohexane dimethyl tetrahydrophthalate) Preparation of diglycidyl ester le]
A 500 ml three-necked flask equipped with a dropping funnel, a reflux tube and a mechanical stirrer was charged with 41.2 g (0.29 mol) of 1,4-cyclohexanedimethanol and 88.5 g (0.58 mol) of tetrahydrophthalic anhydride. Then, 150 g of toluene was added and dissolved, and the mixture was heated at 120 ° C. for 5 hours. After cooling to room temperature, 0.8 g (0.004 mol) of benzyltrimethylammonium chloride was added and dissolved, and then 41 g (0.85 mol) of 85% sodium hydroxide powder was added, followed by 66.9 g of epichlorohydrin. (0.7 mol) was added dropwise at 40 ° C. over 8 hours, and the mixture was further heated and stirred for 5 hours. The reaction mixture was washed with water to remove the low boilers in vacuo, poly (cyclohexane dimethyl tetrahydrophthalate) 135.2 g diglycidyl ester le (83% yield).
【００６１】
実施例８
還流管、２つの滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、参考例１で製造したポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステル２５ｇ（０．０１８ｍｏｌ）、トルエン１００ｇおよび塩化トリオクチルメチルアンモニウム０．３２ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液を７０℃に昇温し、タングステン酸アンモニウム・５水和物０．１２５ｇ（０．０４ｍｍｏｌ）およびリン酸０．３３ｇ（３．３ｍｍｏｌ）を水２０ｇに溶解させて調製したｐＨが３．１である水溶液と、３０％過酸化水素水溶液９．０６ｇ（０．０８ｍｏｌ）を別々の滴下ロートから同時に滴下した（所要時間：３時間）。滴下終了後、反応混合液をさらに７０℃で４時間攪拌し、攪拌を停止した。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約１．５分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を６０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステル〔収量：２６．０ｇ〕を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は１００％であり、エポキシ化率は９８％（選択率９８％）であった。添加した過酸化水素の９９％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステル中のタングステン残存量を実施例１と同様の方法で分析したところ、９．１ｐｐｍであった。[0061]
Example 8
Reflux condenser, two dropping funnels, a three-necked flask 300ml equipped with a thermometer and a mechanical stirrer, poly prepared in Reference Example 1 (cyclohexane dimethyl tetrahydrophthalate) diglycidyl ester le 2 5 g (0.018 mol), 100 g of toluene and 0.32 g of trioctylmethylammonium chloride were 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. The aqueous solution of No. 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 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, washed with 100 ml of a 5% aqueous solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 60 ° C. and 800 Pa for 8 hours.
The obtained epoxidized poly (cyclohexane dimethyl tetrahydrophthalate) diglycidyl ester le [Yield: 26.0 g] where was analyzed by 1 H-NMR, the conversion of the double bonds is 100% epoxidized The rate was 98% (selectivity 98%). It was found that 99% of the added hydrogen peroxide contributed to the epoxidation reaction.
Incidentally, when the tungsten remaining amount of the obtained epoxidized poly (cyclohexane dimethyl tetrahydrophthalate) diglycidyl during ester le was analyzed in the same manner as in Example 1, was 9.1 ppm.
【００６２】
比較例９
還流管、滴下ロート、温度計およびメカニカルスターラを装着した容量３００ｍｌの三つ口フラスコに、参考例１で製造したポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステル２５ｇ（０．０１８ｍｏｌ）、トルエン１００ｇおよび塩化セチルピリジニウム０．０９ｇを加え、６０℃で攪拌しながら完全に溶解させた。この溶液に、タングステン酸ナトリウム０．１７ｇ（０．５１ｍｍｏｌ）およびリン酸０．２７ｇ（０．２７ｍｍｏｌ）を水１．８ｇに溶解し、炭酸ナトリウム０．０５ｇ（０．４７ｍｍｏｌ）を用いてｐＨ３に調整した水溶液を加えた後、得られた混合液を激しく攪拌しながら、３０％過酸化水素水溶液９．０５ｇ（０．０８ｍｏｌ）を３時間かけて滴下し、さらに３時間反応させた。攪拌停止後、６０℃で有機層（トルエン層）と水層の界面が形成されるまでの時間は約３９．５分であった。水層を分液して除去し、有機層を水１００ｍｌで洗浄し、５％炭酸ナトリウム水溶液１００ｍｌで洗浄、さらに水１００ｍｌで２回洗浄した後、トルエンを減圧下に留去し、得られた残留物を６０℃、８００Ｐａの条件で８時間乾燥した。
得られたエポキシ化ポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステル〔収量：２５．６ｇ〕を１Ｈ−ＮＭＲにて分析したところ、二重結合の転化率は９５％であり、エポキシ化率は７１％（選択率７５％）であった。添加した過酸化水素の７０％がエポキシ化反応に寄与したことが分かった。
なお、得られたエポキシ化ポリ（シクロヘキサンジメチルテトラヒドロフタレート）ジグリシジルエステル中のタングステン残存量を実施例１と同様の方法で分析したところ、８９．３ｐｐｍであった。[0062]
Comparative Example 9
Reflux condenser, a dropping funnel, a three-necked flask 300ml equipped with a thermometer and a mechanical stirrer, poly prepared in Reference Example 1 (cyclohexane dimethyl tetrahydrophthalate) diglycidyl ester le 2 5 g (0.018 mol), toluene 100g And 0.09 g of cetylpyridinium chloride were added and completely dissolved with stirring at 60 ° C. In this solution, 0.17 g (0.51 mmol) of sodium tungstate and 0.27 g (0.27 mmol) of phosphoric acid are dissolved in 1.8 g of water, and the pH is adjusted to 3 with 0.05 g (0.47 mmol) of sodium carbonate. After adding the adjusted aqueous solution, 9.05 g (0.08 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 3 hours while vigorously stirring the resulting mixture, and the mixture was further reacted for 3 hours. 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 39.5 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 solution of sodium carbonate, and twice with 100 ml of water, and toluene was distilled off under reduced pressure. The residue was dried at 60 ° C. and 800 Pa for 8 hours.
The obtained epoxidized poly (cyclohexane dimethyl tetrahydrophthalate) diglycidyl ester le [Yield: 25.6 g] where was analyzed by 1 H-NMR, the conversion of the double bonds is 95%, the epoxidation The rate was 71% (selectivity 75%). It was found that 70% of the added hydrogen peroxide contributed to the epoxidation reaction.
Incidentally, when the tungsten remaining amount of the obtained epoxidized poly (cyclohexane dimethyl tetrahydrophthalate) diglycidyl during ester le was analyzed in the same manner as in Example 1, it was 89.3Ppm.
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| KR101640067B1 (en) * | 2014-10-15 | 2016-07-15 | 경상대학교산학협력단 | Method of preparing epoxidized natural rubber |
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