JP2014062057A - Method for producing acetylated sulfonium compound - Google Patents
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- JP2014062057A JP2014062057A JP2012206942A JP2012206942A JP2014062057A JP 2014062057 A JP2014062057 A JP 2014062057A JP 2012206942 A JP2012206942 A JP 2012206942A JP 2012206942 A JP2012206942 A JP 2012206942A JP 2014062057 A JP2014062057 A JP 2014062057A
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- -1 sulfonium compound Chemical class 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 72
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 19
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 239000003999 initiator Substances 0.000 abstract description 7
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 229910001415 sodium ion Inorganic materials 0.000 description 16
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- VCYVAWIVMROULW-UHFFFAOYSA-N [4-(2-phenylethylsulfanyl)phenyl] acetate Chemical compound C1=CC(OC(=O)C)=CC=C1SCCC1=CC=CC=C1 VCYVAWIVMROULW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZNCWTZBLEIZQEU-UHFFFAOYSA-N CC1=CC=CC=C1CSCC2=CC=C(C=C2)OC(=O)C Chemical compound CC1=CC=CC=C1CSCC2=CC=C(C=C2)OC(=O)C ZNCWTZBLEIZQEU-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- ZLDYRICIPMEJEK-UHFFFAOYSA-N (4-acetyloxyphenyl)-dimethylsulfanium Chemical compound C[S+](C)C1=CC=C(OC(C)=O)C=C1 ZLDYRICIPMEJEK-UHFFFAOYSA-N 0.000 description 1
- BGXFYNDXRSLDAH-UHFFFAOYSA-N (4-sulfanylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(S)C=C1 BGXFYNDXRSLDAH-UHFFFAOYSA-N 0.000 description 1
- JFNIDIDTWDBBFR-UHFFFAOYSA-N 4-(2-phenylethylsulfanyl)phenol Chemical compound C1=CC(O)=CC=C1SCCC1=CC=CC=C1 JFNIDIDTWDBBFR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- QBJQRXLQICGKAT-UHFFFAOYSA-N CC1=C(C=CC(=C1)SCCC2=CC=CC=C2)OC(=O)C Chemical compound CC1=C(C=CC(=C1)SCCC2=CC=CC=C2)OC(=O)C QBJQRXLQICGKAT-UHFFFAOYSA-N 0.000 description 1
- YLEWRFJFRUXPRI-UHFFFAOYSA-N CC1=CC=C(C=C1)CSCC2=CC=C(C=C2)OC(=O)C Chemical compound CC1=CC=C(C=C1)CSCC2=CC=C(C=C2)OC(=O)C YLEWRFJFRUXPRI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PNNUGSUFBQGJQV-UHFFFAOYSA-N [Cl-].C(C)(=O)OC1=CC=C(C=C1)[SH+]CCC1=CC=CC=C1 Chemical compound [Cl-].C(C)(=O)OC1=CC=C(C=C1)[SH+]CCC1=CC=CC=C1 PNNUGSUFBQGJQV-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
この発明は、アセチル化スルホニウム化合物の製造方法に関する。さらに詳しくは、熱硬化組成物の硬化開始剤として有用な4−アセトキシフェニルスルホニウム化合物の製造方法であり、特にエポキシ樹脂やスチレンなどのカチオン重合性ビニル化合物の重合硬化開始剤として有効である高純度の4−アセトキシフェニルスルホニウム化合物の製造方法に関する。 The present invention relates to a method for producing an acetylated sulfonium compound. More specifically, it is a method for producing a 4-acetoxyphenylsulfonium compound useful as a curing initiator for a thermosetting composition, and is particularly effective as a polymerization curing initiator for cationically polymerizable vinyl compounds such as epoxy resins and styrene. To a process for producing a 4-acetoxyphenylsulfonium compound.
従来から4−アセトキシフェニルスルホニウムをカチオン部とし、テトラキス(ペンタフルオロフェニル)ボレートやヘキサフルオロアンチモナートのような非求核性のアニオンを有するスルホニウム化合物は、重合硬化開始剤として使用されている。 Conventionally, sulfonium compounds having non-nucleophilic anions such as tetrakis (pentafluorophenyl) borate and hexafluoroantimonate having 4-acetoxyphenylsulfonium as the cation moiety have been used as polymerization curing initiators.
この重合開始剤は一般の工業製品と異なり、製造時に中和で生成する塩化ナトリウムのような無機塩、未反応の原料、副生物といった不純物によって重合速度に影響があるため、高純度品が要求されている。不純物の性質にもよるが一般的には純度95%程度では使用が困難とされ、98%以上、好ましくは99%以上であることが要求されている。また、無機塩はナトリウムイオン量に換算して通常10ppm以下、好ましくは2ppm以下を要求されている。 Unlike general industrial products, this polymerization initiator has an effect on the polymerization rate due to impurities such as inorganic salts such as sodium chloride, unreacted raw materials, and by-products generated by neutralization during production, so high purity products are required. Has been. Although it depends on the nature of impurities, it is generally difficult to use at a purity of about 95%, and it is required to be 98% or more, preferably 99% or more. Further, the inorganic salt is usually required to be 10 ppm or less, preferably 2 ppm or less in terms of sodium ion amount.
特許文献1によれば、この明細書に記載したアセトキシフェニルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート類が開示されている。この特許文献1では、酢酸4-(メチルチオ)フェニルエステルに塩化ベンジルを作用させ、次いで塩交換する方法で合成すると開示されている。 According to Patent Document 1, acetoxyphenylsulfonium tetrakis (pentafluorophenyl) borates described in this specification are disclosed. In this Patent Document 1, it is disclosed that benzyl chloride is allowed to act on acetic acid 4- (methylthio) phenyl ester followed by salt exchange.
同様に特許文献2には、アセトキシフェニルスルホニウム ヘキサフルオロアンチモナートの製造方法が開示されている。この請求項には、4−ヒドロキシフェニルジアルキルスルホニウム化合物と酸無水物をジシクロヘキシルアミンの存在下に反応させる記載があり、具体的にこの実施例1では、4−ヒドロキシフェニルジメチルスルホニウム
ヘキサフルオロアンチモナートを酢酸エチルに溶解させ、撹拌しながら、ジシクロヘキシルアミンを混合し、さらに無水酢酸を滴下することで4−アセトキシフェニルジメチルスルホニウム
ヘキサフルオロアンチモナートを得ている。この従来技術は先に酸捕獲剤としてジシクロヘキシルアミンを存在させた中に無水酢酸を滴下してアセチル化反応をさせている。
Similarly, Patent Document 2 discloses a method for producing acetoxyphenylsulfonium hexafluoroantimonate. In this claim, there is a description of reacting a 4-hydroxyphenyldialkylsulfonium compound with an acid anhydride in the presence of dicyclohexylamine. Specifically, in this Example 1, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate is reacted with 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate is obtained by dissolving in ethyl acetate, mixing dicyclohexylamine with stirring, and adding acetic anhydride dropwise. In this prior art, acetic anhydride is added dropwise in the presence of dicyclohexylamine as an acid scavenger to cause an acetylation reaction.
ところが、先行技術文献に記載の方法では生成物の純度に不満があった。つまり技術分野に記載のとおり、重合開始剤は不純物によって重合速度に影響があるため、高純度品が要求されており、具体的には純度99%以上であることが要求されている。本発明の課題は、従来の問題点である不純物の低減を目的とし、不純物の少ない重合開始剤を簡易な方法で得ることのできる製造方法を提示することにある。 However, the methods described in the prior art documents were unsatisfactory in the purity of the product. That is, as described in the technical field, since the polymerization initiator has an influence on the polymerization rate due to impurities, a high-purity product is required, and specifically, the purity is required to be 99% or more. An object of the present invention is to provide a production method capable of obtaining a polymerization initiator with few impurities by a simple method for the purpose of reducing impurities, which is a conventional problem.
本発明は、上記の課題を解決すべく検討された、化1で表わされるスルホニウム化合物の製造法に関するものであり、詳細には、化2で表されるスルホニウム化合物を無水酢酸でエステル化し、化1で表されるスルホニウム化合物を製造する反応において、反応溶媒を酢酸エチルおよび/またはアセトニトリルとした上で、先に化2のスルホニウム化合物に対して2〜4モル量の無水酢酸を投入し、その後化2のスルホニウム化合物に対して0.9〜1.05モル量のジシクロヘキシルアミンを反応させてなる化1で表されるアセチル化スルホニウム化合物の製造方法である。 The present invention relates to a process for producing a sulfonium compound represented by Chemical Formula 1 that has been studied to solve the above-mentioned problems. Specifically, the sulfonium compound represented by Chemical Formula 2 is esterified with acetic anhydride to form a chemical compound. In the reaction for producing the sulfonium compound represented by 1, the reaction solvent was changed to ethyl acetate and / or acetonitrile, and then 2 to 4 mol amount of acetic anhydride was added to the sulfonium compound of Chemical Formula 2, and then This is a method for producing an acetylated sulfonium compound represented by Chemical Formula 1 obtained by reacting 0.9 to 1.05 mole amount of dicyclohexylamine with the sulfonium compound of Chemical Formula 2.
(化1、化2に共通してR1は水素,C1〜C4のアルキル基のいずれかを、R2はC1〜C4のアルキル基,C1〜C4のアルキル基で置換されていてもよいベンジル基,2−ナフチルメチル基のいずれかを、R3はC1〜C4のアルキル基を、Xはテトラキス(ペンタフルオロフェニル)ボレート,ヘキサフルオロアンチモナート,ヘキサフルオロホスファートのいずれかを示す。) (Formula 1, common to reduction 2 R 1 represents hydrogen, substituted or an alkyl group of C 1 -C 4, alkyl group R 2 is C 1 -C 4, alkyl group of C 1 -C 4 R 3 is a C 1 -C 4 alkyl group, X is tetrakis (pentafluorophenyl) borate, hexafluoroantimonate, hexafluorophosphate Indicates one of these.)
本発明は、4−ヒドロキシフェニルスルホニウム化合物を無水酢酸でエステル化し、4−アセトキシフェニルスルホニウム化合物を製造する反応において、特定の溶媒中で先に無水酢酸を4−ヒドロキシフェニルスルホニウム化合物の2〜4モル量投入し、次いでスルホニウム化合物の0.9〜1.05モル量のジシクロヘキシルアミンを反応させてなる製造方法である。なお、塩化アセチルを適用するアセチル化の例も先行文献に見出されるが、副生するハロゲンアニオンが洗浄後もわずかに残存し、このアニオンが重合開始種を捕獲するなど重合時に阻害要因となるので好ましくない。 In the reaction for producing 4-acetoxyphenylsulfonium compound by esterifying 4-hydroxyphenylsulfonium compound with acetic anhydride, acetic anhydride is first converted to 2-4 mol of 4-hydroxyphenylsulfonium compound in a specific solvent. This is a production method in which 0.9 to 1.05 mol of dicyclohexylamine of the sulfonium compound is reacted. An example of acetylation using acetyl chloride is also found in the prior literature, but a slight amount of by-produced halogen anion remains after washing, and this anion becomes a hindrance during polymerization such as capturing the polymerization initiation species. It is not preferable.
ここで、無水酢酸の反応量は化2で表されるスルホニウム化合物の2〜4モルである。さらに好ましくは2.5〜3.5モルである。この過剰の無水酢酸を先に存在させると、溶媒や原料に残存する微量の水と反応することで、脱水剤として作用していると推定される。ジシクロヘキシルアミンの反応量は化2で表されるスルホニウム化合物の0.9〜1.05モルであり、好ましくは0.95〜1.00モル、さらに好ましくは0.98〜0.99モルである。また、この反応において、反応温度は20℃以下が好ましく、より好ましくは10℃以下である。 Here, the reaction amount of acetic anhydride is 2 to 4 mol of the sulfonium compound represented by Chemical Formula 2. More preferably, it is 2.5-3.5 mol. If this excess acetic anhydride is present first, it is presumed that it acts as a dehydrating agent by reacting with a trace amount of water remaining in the solvent or raw material. The reaction amount of dicyclohexylamine is 0.9 to 1.05 mol of the sulfonium compound represented by Chemical Formula 2, preferably 0.95 to 1.00 mol, and more preferably 0.98 to 0.99 mol. . In this reaction, the reaction temperature is preferably 20 ° C. or lower, more preferably 10 ° C. or lower.
本発明の製造方法を適用できるアセチル化スルホニウム化合物を具体的に例示すれば、4−アセトキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、4−アセトキシ−3−メチルフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、4−アセトキシフェニルメチル(2−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレート、4−アセトキシフェニルメチル(4−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレート、4−アセトキシフェニルベンジルメチルスルホニウム ヘキサフルオロアンチモナート、4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナート、4−アセトキシフェニル(メチル)2−ナフチルメチルスルホニウム ヘキサフルオロアンチモナート、4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロホスファート等である。 Specific examples of acetylated sulfonium compounds to which the production method of the present invention can be applied include 4-acetoxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate, 4-acetoxy-3-methylphenylbenzylmethylsulfonium tetrakis (pentafluoro). Phenyl) borate, 4-acetoxyphenylmethyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate, 4-acetoxyphenylmethyl (4-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate, 4-acetoxyphenylbenzylmethyl Sulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxy Eniru (methyl) 2-naphthylmethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium hexafluorophosphate or the like.
先の特許文献1の問題点として、生成した開始剤の純度が99%と記載されており、開始剤として有効に作用するものの、不純物が重合を阻害しているようであり、生成する重合物の物性に不満があった。本発明によるスルホニウム化合物の製造方法の要件は、従来技術に比べて、特定の溶媒中、無水酢酸とジシクロヘキシルアミンの反応順を前後させること、また、無水酢酸とジシクロヘキシルアミンの量を原料のスルホニウム化合物に対して特定モルとすることであるが、このことによって、簡易な方法で高純度の重合開始剤が得られるという有利な点が生じる。 As a problem of the above-mentioned Patent Document 1, although the purity of the produced initiator is described as 99%, it acts effectively as an initiator, but it seems that impurities are inhibiting the polymerization, and the produced polymer I was dissatisfied with the physical properties. The requirements for the method for producing a sulfonium compound according to the present invention are that the reaction order of acetic anhydride and dicyclohexylamine is changed in a specific solvent as compared with the prior art, and the amount of acetic anhydride and dicyclohexylamine is the raw material sulfonium compound. However, this has the advantage that a highly pure polymerization initiator can be obtained by a simple method.
ここで、無水酢酸の量は、原料のスルホニウム化合物に対して2〜4モルと小過剰である。この理由として、過剰の無水酢酸が、0013に記載したように反応の初期で脱水剤として作用することで、水にわずかに溶解している無機塩を有機溶媒から押し出して無機イオンも除去していると推定している。この作用効果により、無機イオンを含んだ原料を使用しても、製品に無機塩が夾雑することはない。そしてジシクロヘキシルアミンの量もスルホニウム化合物の0.9〜1.05モル量と規定することにより、副反応が抑制された製造方法が提供される。 Here, the amount of acetic anhydride is a small excess of 2 to 4 moles relative to the raw material sulfonium compound. The reason for this is that excess acetic anhydride acts as a dehydrating agent at the beginning of the reaction as described in 0013, so that inorganic salts slightly dissolved in water are pushed out of the organic solvent to remove inorganic ions. It is estimated that Due to this action and effect, inorganic salts are not contaminated in the product even if raw materials containing inorganic ions are used. And the manufacturing method with which the side reaction was suppressed is provided by prescribing | regulating the quantity of a dicyclohexylamine as 0.9-1.05 molar quantity of a sulfonium compound.
さらにこの発明によれば、装置の簡易性など製造方法が容易で経済的であり、本発明の製造方法で製造したものは、収量が増加し、また、融点が有意に上昇しており、融点幅が小さくなるなど、不純物の生成を防止した高純度の重合開始剤を得ることができる。 Furthermore, according to the present invention, the manufacturing method such as simplicity of the apparatus is easy and economical, and those manufactured by the manufacturing method of the present invention have an increased yield and a significantly increased melting point. It is possible to obtain a high-purity polymerization initiator that prevents generation of impurities, such as a reduced width.
以下に本発明の実施例を示すが、本発明の範囲はこれに限定されるものではない。ここで、Naイオン量はサンプルを灰化処理後、ICP発光分析装置(日立ハイテク製 P-4010)で測定した。 Examples of the present invention are shown below, but the scope of the present invention is not limited thereto. Here, the amount of Na ions was measured with an ICP emission analyzer (P-4010 manufactured by Hitachi High-Tech) after ashing the sample.
4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナートの合成
Naイオンを50ppm含む4−ヒドロキシフェニルジメチルスルホニウム
ヘキサフルオロアンチモナート 83.3g(0.213モル)を酢酸エチル250mlに溶解させ、撹拌しながら10℃以下で無水酢酸 50.0g(0.490モル)を5分で滴下する。1時間撹拌後、ジシクロヘキシルアミン
37.5g(0.207モル)を15分で滴下する。滴下後、更に20時間撹拌する。生成した酢酸ジシクロヘキシルアミン塩をろ別し、溶媒を濃縮し、n-ヘキサンで洗浄することで、白色結晶の4−アセトキシフェニルジメチルスルホニウム
ヘキサフルオロアンチモナートを得る。収量80.6g(収率90.0%)、融点 156.0〜157.3℃、高速液体クロマトグラフィー(HPLC)による純度は99.9%、Naイオンは1ppmであった。
Synthesis of 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate 83.3 g (0.213 mol) of 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate containing 50 ppm of Na ion was dissolved in 250 ml of ethyl acetate and stirred at 10 ° C. or lower. Then, 50.0 g (0.490 mol) of acetic anhydride is added dropwise over 5 minutes. After stirring for 1 hour, 37.5 g (0.207 mol) of dicyclohexylamine is added dropwise over 15 minutes. After the addition, the mixture is further stirred for 20 hours. The formed dicyclohexylamine salt is filtered off, the solvent is concentrated, and washed with n-hexane to obtain 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate as white crystals. The yield was 80.6 g (90.0% yield), the melting point was 156.0-157.3 ° C., the purity by high performance liquid chromatography (HPLC) was 99.9%, and the Na ion was 1 ppm.
4−アセトキシフェニル(ベンジル)メチルスルホニウム ヘキサフルオロアンチモナートの合成
Naイオンを30ppm含む4−ヒドロキシフェニル(ベンジル)メチルスルホニウム
ヘキサフルオロアンチモナート57.2g(0.122モル)を酢酸エチル250mlに溶解させ、撹拌しながら10℃以下で無水酢酸37.7g(0.369モル)を5分で滴下する。1時間撹拌後、ジシクロヘキシルアミン
21.8g(0.120モル)を30分で滴下する。滴下後、更に1時間撹拌する。生成した酢酸ジシクロヘキシルアミン塩をろ別し、溶媒を濃縮し、ヘキサンで洗浄することで、白色結晶性粉末の4−アセトキシフェニル(ベンジル)メチルスルホニウム ヘキサフルオロアンチモナートを得る。収量54.4g(収率89.0%)、融点116.0〜117.4℃、高速液体クロマトグラフィー(HPLC)による純度は99.8%、Naイオンは1ppmであった。
Synthesis of 4-acetoxyphenyl (benzyl) methylsulfonium hexafluoroantimonate 57.2 g (0.122 mol) of 4-hydroxyphenyl (benzyl) methylsulfonium hexafluoroantimonate containing 30 ppm of Na ions was dissolved in 250 ml of ethyl acetate. While stirring, 37.7 g (0.369 mol) of acetic anhydride is added dropwise over 5 minutes at 10 ° C. or lower. After stirring for 1 hour, 21.8 g (0.120 mol) of dicyclohexylamine is added dropwise over 30 minutes. After the addition, the mixture is further stirred for 1 hour. The produced dicyclohexylamine salt is filtered off, the solvent is concentrated, and washed with hexane to give 4-acetoxyphenyl (benzyl) methylsulfonium hexafluoroantimonate as white crystalline powder. The yield was 54.4 g (yield 89.0%), the melting point was 116.0 to 117.4 ° C., the purity by high performance liquid chromatography (HPLC) was 99.8%, and the Na ion was 1 ppm.
4−アセトキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレートの合成
Naイオンを40ppm含む4−ヒドロキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート71.8g(0.079モル)をアセトニトリル500mlに溶解させ、撹拌しながら10℃以下で無水酢酸24.0g(0.235モル)を5分で滴下する。10分撹拌後、ジシクロヘキシルアミン14.0g(0.077モル)を15分で滴下する。滴下後、更に2時間攪拌する。生成した酢酸ジシクロヘキシルアミン塩をろ別し、溶媒を濃縮し、ヘキサンで洗浄することで、白色結晶の4−アセトキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレートを得る。収量65.8g(収率90.0%)、融点 148.1〜149.3℃、高速液体クロマトグラフィー(HPLC)による純度は99.5%、Naイオンは1ppmであった。
Synthesis of 4-acetoxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate 71.8 g (0.079 mol) of 4-hydroxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate containing 40 ppm of Na ion was dissolved in 500 ml of acetonitrile. While stirring, 24.0 g (0.235 mol) of acetic anhydride is added dropwise over 5 minutes at 10 ° C. or lower. After stirring for 10 minutes, 14.0 g (0.077 mol) of dicyclohexylamine is added dropwise over 15 minutes. After the addition, the mixture is further stirred for 2 hours. The produced dicyclohexylamine salt is filtered off, the solvent is concentrated, and washed with hexane to obtain 4-acetoxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate as white crystals. The yield was 65.8 g (yield 90.0%), the melting point was 148.1 to 149.3 ° C., the purity by high performance liquid chromatography (HPLC) was 99.5%, and the Na ion was 1 ppm.
4−アセトキシフェニルメチル(2−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレートの合成
Naイオンを40ppm含む4−ヒドロキシフェニルメチル(2−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレート72.0g(0.078モル)をアセニトニトリル500mlに溶解させ、攪拌しながら10℃以下で無水酢酸25.0g(0.245モル)を5分で滴下する。10分撹拌後、ジシクロヘキシルアミン14.0g(0.077モル)を30分で滴下する。滴下後、更に1時間攪拌する。以下、実施例3と同様に処理して、白色結晶の4−アセトキシフェニルメチル(2−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレートを得る。収量63.6g(収率85.0%)、融点141.7〜142.9℃、高速液体クロマトグラフィー(HPLC)による純度は99.0%、Naイオンは1ppmであった。
Synthesis of 4-acetoxyphenylmethyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate 4-hydroxyphenylmethyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate 72.0 g (0 0.078 mol) is dissolved in 500 ml of acetononitrile, and 25.0 g (0.245 mol) of acetic anhydride is added dropwise over 5 minutes at 10 ° C. or lower with stirring. After stirring for 10 minutes, 14.0 g (0.077 mol) of dicyclohexylamine is added dropwise over 30 minutes. After the addition, the mixture is further stirred for 1 hour. Thereafter, the same treatment as in Example 3 is carried out to obtain 4-acetoxyphenylmethyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate as white crystals. The yield was 63.6 g (yield 85.0%), the melting point was 141.7-142.9 ° C., the purity by high performance liquid chromatography (HPLC) was 99.0%, and the Na ion was 1 ppm.
以下、比較例を記載する。
[比較例1]
特許文献1として記載の、公開特許公報2012年第153642号に従って、この出願の実施例3と同一の化合物を合成した。手法を記載する。
Hereinafter, comparative examples will be described.
[Comparative Example 1]
The same compound as Example 3 of this application was synthesized according to Japanese Patent Laid-Open No. 2012-153642 described as Patent Document 1. Describe the technique.
酢酸4-(メチルチオ)フェニルエステル9.1g(0.05モル)、塩化ベンジル
6.65g(0.0525モル)を水中で反応させて、4−アセトキシフェニルベンジルメチルスルホニウム クロライドの水溶液を得た。これに酢酸エチルを加え、テトラキス(ペンタフルオロフェニル)ほう酸ナトリウム塩の10%水溶液350g(0.05モル)を滴下し、塩交換反応を行った。反応後、有機層を脱水し、溶媒を除き、残渣をn-ヘキサン
100mlで処理することで、白色の4−アセトキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート41.0g(収率 86.1%)を得る。融点
132〜138℃、Naイオンは10ppmであった。
Acetic acid 4- (methylthio) phenyl ester (9.1 g, 0.05 mol) and benzyl chloride (6.65 g, 0.0525 mol) were reacted in water to obtain an aqueous solution of 4-acetoxyphenylbenzylmethylsulfonium chloride. Ethyl acetate was added thereto, and 350 g (0.05 mol) of a 10% aqueous solution of sodium tetrakis (pentafluorophenyl) borate was added dropwise to carry out a salt exchange reaction. After the reaction, the organic layer was dehydrated, the solvent was removed, and the residue was treated with 100 ml of n-hexane to give 41.0 g of white 4-acetoxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate (yield 86.1). %). Melting point was 132 to 138 ° C. and Na ion was 10 ppm.
[比較例2]
特許文献2として記載の、公開特許公報2006年第131612号の実施例1に従って、この出願の実施例1と同一の化合物を合成した。手法を記載する。
[Comparative Example 2]
The same compound as Example 1 of this application was synthesized according to Example 1 of Published Patent Publication No. 2006131612 described as Patent Document 2. Describe the technique.
Naイオンを50ppm含む4−ヒドロキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナート 11.73g(0.030モル)を酢酸エチルに溶解させ、撹拌しながら、ジシクロヘキシルアミン 5.44g(0.030モル)を混合し、さらに無水酢酸
3.06g(0.030モル)を3分で滴下する。滴下時から沈殿が生じる。滴下後、更に1時間撹拌する。生成した酢酸ジシクロヘキシルアミン塩をろ別し、溶媒を濃縮することで白色結晶の4−アセトキシフェニルジメチルスルホニウム
ヘキサフルオロアンチモナートを得る。収量11.52g(収率88.7%)であった。融点 152.5〜156.0℃、高速液体クロマトグラフィー(HPLC)による純度は99.3%、Naイオンは7ppmであった。
11.73 g (0.030 mol) of 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate containing 50 ppm of Na ion is dissolved in ethyl acetate, and while stirring, 5.44 g (0.030 mol) of dicyclohexylamine is mixed. Further, 3.06 g (0.030 mol) of acetic anhydride is added dropwise over 3 minutes. Precipitation occurs from the time of dropping. After the addition, the mixture is further stirred for 1 hour. The produced dicyclohexylamine salt is filtered off and the solvent is concentrated to obtain white crystalline 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate. The yield was 11.52 g (yield 88.7%). Melting point: 152.5 to 156.0 ° C., purity by high performance liquid chromatography (HPLC) was 99.3%, and Na ion was 7 ppm.
[比較例3]
4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナートの合成
無水酢酸を塩化アセチルに代えて、塩化アセチルの使用量を17.6g(0.224モル)とした以外は実施例1に準じて実施し、白色結晶の4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナートを24.2g(収率28.1%)を得る。融点 151.0〜156.5℃、高速液体クロマトグラフィー(HPLC)による純度は98.1%、Naイオンは10ppmであった。
[Comparative Example 3]
Synthesis of 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate The same procedure as in Example 1 was carried out except that acetic anhydride was replaced with acetyl chloride and the amount of acetyl chloride was changed to 17.6 g (0.224 mol). 24.2 g (yield 28.1%) of crystalline 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate are obtained. Melting point: 151.0 to 156.5 ° C., purity by high performance liquid chromatography (HPLC) was 98.1%, and Na ion was 10 ppm.
[比較例4]
4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナートの合成
溶媒をイソプロピルアルコールに代えた以外は実施例1に準じて実施し、反応後、溶媒を濃縮することで白色結晶の白色結晶の4−アセトキシフェニルジメチルスルホニウム ヘキサフルオロアンチモナートを得る。収量31.3g(収率35.0%)であった。融点151.5〜156.3℃、高速液体クロマトグラフィー(HPLC)による純度は98.5%、Naイオンは10ppmであった。
[Comparative Example 4]
4-acetoxyphenyldimethylsulfonium Synthesis of hexafluoroantimonate was performed according to Example 1 except that isopropyl alcohol was used. After the reaction, the solvent was concentrated to give white crystals of 4-acetoxyphenyldimethyl as white crystals. Sulfonium hexafluoroantimonate is obtained. The yield was 31.3 g (yield 35.0%). Melting point was 151.5 to 156.3 ° C., purity by high performance liquid chromatography (HPLC) was 98.5%, and Na ion was 10 ppm.
[比較例5]
4−アセトキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレートの合成
実施例3の無水酢酸の滴下をジシクロヘキシルアミンの滴下後に実施した以外は、実施例3と同様の仕込み量で反応、後処理し、白色結晶の4−アセトキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレートを得る。収量47.5g(収率65.4%)、融点 145.6〜147.9℃、高速液体クロマトグラフィー(HPLC)による純度は98.5%、Naイオンは6ppmであった。
[Comparative Example 5]
Synthesis of 4-acetoxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate The reaction and post-treatment were performed in the same amount as in Example 3, except that the dropwise addition of acetic anhydride in Example 3 was performed after the dropwise addition of dicyclohexylamine. White crystalline 4-acetoxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate is obtained. The yield was 47.5 g (yield 65.4%), the melting point was 145.6 to 147.9 ° C., the purity by high performance liquid chromatography (HPLC) was 98.5%, and the Na ion was 6 ppm.
[比較例6]
4−アセトキシフェニルメチル(2−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレートの合成
実施例4の無水酢酸の滴下をジシクロヘキシルアミンの滴下後に実施した以外は、実施例4と同様の仕込み量で反応、後処理し、白色結晶の4−アセトキシフェニルメチル(2−メチルベンジル)スルホニウム テトラキス(ペンタフルオロフェニル)ボレートを得る。収量41.1g(収率55.0%)、融点136.2〜140.5℃、高速液体クロマトグラフィー(HPLC)による純度は97.3%、Naイオンは8ppmであった。
[Comparative Example 6]
Synthesis of 4-acetoxyphenylmethyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate Reaction was carried out in the same amount as in Example 4 except that the dropwise addition of acetic anhydride in Example 4 was performed after the dropwise addition of dicyclohexylamine. After-treatment, white crystalline 4-acetoxyphenylmethyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate is obtained. The yield was 41.1 g (yield 55.0%), the melting point was 136.2-140.5 ° C., the purity by high performance liquid chromatography (HPLC) was 97.3%, and the Na ion was 8 ppm.
試験例
本発明の化合物を重合開始剤として使用した例を記載する。実施例1で得られた化合物0.1gをエピコート828(ジャパンエポキシレジン株式会社製 エポキシ樹脂の商品名)10gを混合してJISK7071(1988)の手法に準じてゲル化時間を測定した。加熱温度180℃でのゲル化時間は、5分25秒であった。比較として、比較例3で得られた同じ化合物のゲル化時間は、6分30秒であった。またこの実施例1で得られた化合物をメタノールで再結晶を2回繰り返して得られた純品のゲル化時間は、5分30秒であった。
Test Example An example in which the compound of the present invention was used as a polymerization initiator will be described. 0.1 g of the compound obtained in Example 1 was mixed with 10 g of Epicoat 828 (trade name of epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.), and the gelation time was measured according to the method of JIS K7071 (1988). The gelation time at a heating temperature of 180 ° C. was 5 minutes and 25 seconds. As a comparison, the gelation time of the same compound obtained in Comparative Example 3 was 6 minutes 30 seconds. Further, the gelation time of a pure product obtained by repeating recrystallization of the compound obtained in Example 1 twice with methanol was 5 minutes 30 seconds.
本発明は重合開始剤として使用されるアセチル化スルホニウム化合物の製造方法であり、本発明のスルホニウム化合物の製造方法によれば、高純度を必要とするエポキシ樹脂の重合硬化開始剤として有用に作用する化合物が収率よく、簡易な方法で得られる。
The present invention is a method for producing an acetylated sulfonium compound used as a polymerization initiator, and according to the method for producing a sulfonium compound of the present invention, it usefully acts as a polymerization curing initiator for epoxy resins that require high purity. The compound is obtained in a simple manner with good yield.
Claims (1)
(化1、化2に共通してR1は水素,C1〜C4のアルキル基のいずれかを、R2はC1〜C4のアルキル基,C1〜C4のアルキル基で置換されていてもよいベンジル基,2−ナフチルメチル基のいずれかを、R3はC1〜C4のアルキル基を、Xはテトラキス(ペンタフルオロフェニル)ボレート,ヘキサフルオロアンチモナート,ヘキサフルオロホスファートのいずれかを示す。)
In the reaction of esterifying the sulfonium compound represented by Chemical Formula 2 with acetic anhydride in the presence of dicyclohexylamine to produce the sulfonium compound represented by Chemical Formula 1, the reaction solvent is ethyl acetate and / or acetonitrile, and A method for producing an acetylated sulfonium compound represented by Chemical Formula 1, wherein 2 to 4 mol of acetic anhydride of a sulfonium compound is added and then 0.9 to 1.05 mol of dicyclohexylamine of the sulfonium compound is reacted.
(Formula 1, common to reduction 2 R 1 represents hydrogen, substituted or an alkyl group of C 1 -C 4, alkyl group R 2 is C 1 -C 4, alkyl group of C 1 -C 4 R 3 is a C 1 -C 4 alkyl group, X is tetrakis (pentafluorophenyl) borate, hexafluoroantimonate, hexafluorophosphate Indicates one of these.)
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003055301A (en) * | 2001-06-07 | 2003-02-26 | Tokuyama Corp | Method for 2-alkyl-2-adamanthyl (meth)acrylate production |
JP2003238481A (en) * | 2002-02-13 | 2003-08-27 | Tokuyama Corp | Method for producing alkyladamanthyl (meth)acrylate |
JP2006131612A (en) * | 2004-10-08 | 2006-05-25 | Sanshin Chem Ind Co Ltd | Method for producing sulfonium compound |
-
2012
- 2012-09-20 JP JP2012206942A patent/JP5918670B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003055301A (en) * | 2001-06-07 | 2003-02-26 | Tokuyama Corp | Method for 2-alkyl-2-adamanthyl (meth)acrylate production |
JP2003238481A (en) * | 2002-02-13 | 2003-08-27 | Tokuyama Corp | Method for producing alkyladamanthyl (meth)acrylate |
JP2006131612A (en) * | 2004-10-08 | 2006-05-25 | Sanshin Chem Ind Co Ltd | Method for producing sulfonium compound |
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