JP2980514B2 - Method for stabilizing acrylic-functional organosilicon compounds during distillation - Google Patents
Method for stabilizing acrylic-functional organosilicon compounds during distillationInfo
- Publication number
- JP2980514B2 JP2980514B2 JP6098625A JP9862594A JP2980514B2 JP 2980514 B2 JP2980514 B2 JP 2980514B2 JP 6098625 A JP6098625 A JP 6098625A JP 9862594 A JP9862594 A JP 9862594A JP 2980514 B2 JP2980514 B2 JP 2980514B2
- Authority
- JP
- Japan
- Prior art keywords
- functional organosilicon
- distillation
- organosilicon compound
- acrylic
- cupric oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004821 distillation Methods 0.000 title claims description 32
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 18
- 230000000087 stabilizing effect Effects 0.000 title claims description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 62
- 229960004643 cupric oxide Drugs 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 239000003112 inhibitor Substances 0.000 claims description 27
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 21
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 9
- -1 acryloxy group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 3
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 3
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 description 3
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 2
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 239000005048 methyldichlorosilane Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- IAJDMVQJWLFQBX-UHFFFAOYSA-N 1-n,2-n-dinaphthalen-1-ylbenzene-1,2-diamine Chemical compound C1=CC=C2C(NC=3C(=CC=CC=3)NC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 IAJDMVQJWLFQBX-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- CSBJCQMIXISILC-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl prop-2-enoate Chemical compound C[Si](C)(Cl)CCCOC(=O)C=C CSBJCQMIXISILC-UHFFFAOYSA-N 0.000 description 1
- QXKMQBOTKLTKOE-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(Cl)Cl QXKMQBOTKLTKOE-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- VZHMDLWQMMQGOY-UHFFFAOYSA-N 4-(2,2-dimethyl-1-phenylpropyl)phenol Chemical compound C=1C=C(O)C=CC=1C(C(C)(C)C)C1=CC=CC=C1 VZHMDLWQMMQGOY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明はアクリル官能性有機ケイ
素化合物を蒸留時に安定化する方法に関するもので、ア
クリロキシ基とかメタクリロキシ基を有するアクリル官
能性有機ケイ素化合物を蒸留により精製しようとする時
の安定化に広く適用できる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stabilizing an acryl-functional organosilicon compound at the time of distillation. Can be widely applied to
【０００２】[0002]
【従来の技術】アクリル官能性有機ケイ素化合物は、一
般的には、不飽和結合含有アルコールのアクリル酸エス
テルまたはメタクリル酸エステルとケイ素原子−水素原
子結合を含有する有機ケイ素化合物とを白金化合物を触
媒としてヒドロシリル化反応させること、あるいはアク
リル酸カリウムまたはメタクリル酸カリウムとハロアル
キル基含有有機ケイ素化合物とを脱塩反応させることな
どによって得られる。しかし、反応終了後に反応混合物
から蒸留によって目的物を収率よく取得することは極め
て困難であった。その理由は、アクリロキシ基とかメタ
クリロキシ基を有するアクリル官能性有機ケイ素化合物
が熱などにより重合を起こし易いためである。また、蒸
留塔や配管がゲル生成により閉塞するという問題もあっ
た。このように重合を起こし易いことから、前記反応混
合物の蒸留のみならずアクリル官能性有機ケイ素化合物
を取得しようとする蒸留は低収率の問題を抱えていた。BACKGROUND OF THE INVENTION Acrylic-functional organosilicon compounds are generally prepared by catalyzing a platinum compound with an acrylate or methacrylate of an alcohol containing an unsaturated bond and an organosilicon compound containing a silicon-hydrogen bond. Or a desalting reaction between potassium acrylate or potassium methacrylate and a haloalkyl group-containing organosilicon compound. However, it has been extremely difficult to obtain the desired product in good yield from the reaction mixture by distillation after completion of the reaction. The reason is that an acrylic functional organosilicon compound having an acryloxy group or a methacryloxy group is liable to be polymerized by heat or the like. Further, there is a problem that the distillation column and the piping are clogged due to gel formation. Because of the susceptibility to polymerization, not only distillation of the reaction mixture but also distillation for obtaining an acryl-functional organosilicon compound has a problem of low yield.
【０００３】この低収率や閉塞の問題の対策として、蒸
留精製時の目的物の安定化のために種々の重合禁止剤を
添加することが従来周知である。この種の重合禁止剤と
しては下記のようなものが提案されている。 ヒンダードフェノール化合物；2,6-ジ-tert-ブチル−4-
メチルフェノール、2,6-ジ-tert-ブチルフェノール、2,
4-ジメチル−6-tert−ブチルフェノール、2,2'−メチレ
ン−ビス（4-メチル−6-tert−ブチルフェノール）など
（特開昭63-188689 号公報参照）、 アミン化合物；p-フェニレンジアミン、N-イソプロピル
-N'-フェニル−p-フェニレンジアミン、N,N'−ジフェニ
ル−p-フェニレンジアミン、ジフェニルアミンなど、 ハイドロキノン類；ハイドロキノン、2,5-ジ-tert-アミ
ルハイドロキノン、2,5-ジ-tert-ブチルハイドロキノン
など（米国特許第3258477 号明細書参照）、 金属ハロゲン化物；塩化ニッケル、塩化銅、塩化鉄など
（特開平5-271248号公報参照）。As a countermeasure against the problems of low yield and blockage, it is conventionally well known to add various polymerization inhibitors to stabilize the target product during distillation purification. The following are proposed as this type of polymerization inhibitor. Hindered phenol compound; 2,6-di-tert-butyl-4-
Methylphenol, 2,6-di-tert-butylphenol, 2,
4-dimethyl-6-tert-butylphenol, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) and the like (see JP-A-63-188689), amine compounds; p-phenylenediamine, N-isopropyl
-N'-phenyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, diphenylamine, and the like; hydroquinones; hydroquinone, 2,5-di-tert-amylhydroquinone, 2,5-di-tert- Butyl hydroquinone and the like (see U.S. Pat. No. 3,258,477); metal halides; nickel chloride, copper chloride, iron chloride and the like (see JP-A-5-271248).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
重合禁止剤をアクリル官能性有機ケイ素化合物を含む混
合物に添加して蒸留しても必ずしも十分な効果を示さな
いため、熱安定化効果の高い重合禁止剤が求め続けられ
ていた。上述のような状況に鑑み、本発明は、アクリル
官能性有機ケイ素化合物を蒸留によって精製しようとす
る際に有効な、優れた重合防止効果を有する新規な添加
剤を使用した安定化方法を提供しようとしてなされたも
のである。However, even if these polymerization inhibitors are added to a mixture containing an acryl-functional organosilicon compound and then distilled, they do not always show a sufficient effect, and therefore, a polymerization inhibitor having a high heat stabilizing effect is obtained. Drugs were being sought. In view of the above situation, the present invention is to provide a stabilizing method using a novel additive having an excellent anti-polymerization effect, which is effective in purifying an acrylic functional organosilicon compound by distillation. It was done as.
【０００５】[0005]
【課題を解決するための手段】本発明者らは前記の課題
を解決するため鋭意努力を重ねた結果、前記反応混合物
をはじめとするアクリル官能性有機ケイ素化合物の混合
物を、従来の常識からは予想できなかったことである
が、酸化第二銅または硫酸銅の存在下に蒸留することに
より意外にもアクリル官能性有機ケイ素化合物の重合が
極めて有効に防止されること、さらにヒンダードフェノ
ール系などの重合禁止剤を併用すると相乗効果が得られ
ることを見出し、本発明をなすに到った。本発明は、第
一に、アクリル官能性有機ケイ素化合物を蒸留精製する
方法において、酸化第二銅または硫酸銅を存在させるこ
とを特徴とする該アクリル官能性有機ケイ素化合物の蒸
留時の安定化方法に関し、第二に、アクリル官能性有機
ケイ素化合物を蒸留精製する方法において、酸化第二銅
または硫酸銅のほかに、ヒンダードフェノール系重合禁
止剤、アミン系重合禁止剤及びハイドロキノン系重合禁
止剤から選ばれた重合禁止剤をも同時に存在させること
を特徴とする該アクリル官能性有機ケイ素化合物の蒸留
時の安定化方法に関するものである。以下に本発明につ
いて詳しく説明する。The inventors of the present invention have made intensive efforts to solve the above-mentioned problems, and as a result, have found that a mixture of the acryl-functional organosilicon compounds including the above-mentioned reaction mixture can be obtained from conventional common sense. Unexpectedly, the distillation in the presence of cupric oxide or copper sulfate unexpectedly and extremely effectively prevents the polymerization of acrylic-functional organosilicon compounds, and furthermore, hindered phenols, etc. It has been found that a synergistic effect can be obtained when the polymerization inhibitor is used in combination, and the present invention has been accomplished. The present invention firstly provides a method for purifying an acrylic-functional organosilicon compound by distillation, wherein a method of stabilizing the acrylic-functional organosilicon compound at the time of distillation, characterized in that cupric oxide or copper sulfate is present. Secondly, in a method for purifying an acrylic-functional organosilicon compound by distillation, in addition to cupric oxide or copper sulfate, from a hindered phenol polymerization inhibitor, an amine polymerization inhibitor and a hydroquinone polymerization inhibitor. The present invention relates to a method for stabilizing the acrylic-functional organosilicon compound during distillation, wherein a selected polymerization inhibitor is also present at the same time. Hereinafter, the present invention will be described in detail.
【０００６】本発明の安定化方法が適用されるアクリル
官能性有機ケイ素化合物にはアクリル官能とメタクリル
官能の両者が包含され、このような有機ケイ素化合物は
前述のとおり、一般的には、不飽和結合含有アルコール
のアクリル酸エステルまたはメタクリル酸エステルとケ
イ素原子−水素原子結合を含有する有機ケイ素化合物と
を白金化合物を触媒としてヒドロシリル化反応させるこ
と、あるいはアクリル酸カリウムまたはメタクリル酸カ
リウムとハロアルキル基含有有機ケイ素化合物とを脱塩
反応させることなどによって得られる。The acrylic-functional organosilicon compound to which the stabilization method of the present invention is applied includes both an acryl function and a methacryl function, and as described above, such an organosilicon compound is generally unsaturated. Hydrosilylation reaction of an acrylate or methacrylate of a bond-containing alcohol with an organosilicon compound having a silicon-hydrogen atom bond using a platinum compound as a catalyst, or potassium acrylate or potassium methacrylate and a haloalkyl group-containing organic compound. It can be obtained by desalting with a silicon compound.
【０００７】上述の反応によって得られるアクリル官能
性有機ケイ素化合物は下記一般式（Ｉ）で示される。The acrylic functional organosilicon compound obtained by the above reaction is represented by the following general formula (I).
【化２】 （式中、R1は水素原子またはメチル基、R2は加水分解性
基、R3は１価炭化水素基、ｎは０、１、２、３を表
す。）Embedded image (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrolyzable group, R 3 represents a monovalent hydrocarbon group, and n represents 0, 1, 2 , or 3. )
【０００８】前記一般式（Ｉ）で示される化合物の具体
例としては、（3-メタクリロキシプロピル）ジメチルク
ロロシラン、（3-メタクリロキシプロピル）メチルジク
ロロシラン、（3-メタクリロキシプロピル）トリクロロ
シラン、（3-メタクリロキシプロピル）メチルジメトキ
シシラン、（3-メタクリロキシプロピル）トリメトキシ
シラン、（3-メタクリロキシプロピル）トリエトキシシ
ラン、（3-アクリロキシプロピル）ジメチルクロロシラ
ン、（3-アクリロキシプロピル）メチルジクロロシラ
ン、（3-アクリロキシプロピル）トリクロロシラン、
（3-アクリロキシプロピル）メチルジメトキシシラン、
（3-アクリロキシプロピル）トリエトキシシランなどが
挙げられる。Specific examples of the compound represented by the general formula (I) include (3-methacryloxypropyl) dimethylchlorosilane, (3-methacryloxypropyl) methyldichlorosilane, (3-methacryloxypropyl) trichlorosilane, (3-methacryloxypropyl) methyldimethoxysilane, (3-methacryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) triethoxysilane, (3-acryloxypropyl) dimethylchlorosilane, (3-acryloxypropyl) Methyldichlorosilane, (3-acryloxypropyl) trichlorosilane,
(3-acryloxypropyl) methyldimethoxysilane,
(3-acryloxypropyl) triethoxysilane and the like.
【０００９】本発明の安定化方法は、前述のごとき反応
を行った後の反応混合物をはじめとするアクリル官能性
有機ケイ素化合物の混合物からこのものを蒸留精製する
際に酸化第二銅または硫酸銅を存在させることを特徴と
するが、酸化第二銅または硫酸銅としては市販品を使用
することができ、また、その使用量については特に制限
はないが、アクリル官能性有機ケイ素化合物に対して
0.001〜10重量％、特には0.01〜１重量％とすることが
好ましい。[0009] The stabilization method of the present invention relates to a method for purifying a mixture of an acrylic functional organosilicon compound including a reaction mixture after the above-described reaction by distillation, from cupric oxide or copper sulfate. However, a commercially available product can be used as cupric oxide or copper sulfate, and its use amount is not particularly limited, but is based on the acryl-functional organosilicon compound.
It is preferably 0.001 to 10% by weight, particularly preferably 0.01 to 1% by weight.
【００１０】さらに、酸化第二銅または硫酸銅に、ヒン
ダードフェノール系重合禁止剤、アミン系重合禁止剤及
びハイドロキノン系重合禁止剤から選ばれた重合禁止剤
を併用すると、予想し得なかった相乗効果により、アク
リル官能性有機ケイ素化合物の蒸留時の熱安定性がより
向上することがわかった。このような重合禁止剤の例と
しては従来公知のもの、例えば2,6-ジ-tert-ブチル−4-
メチルフェノール、2,2'−メチレン−ビス（6-tert−ブ
チル−4-メチルフェノール）等のヒンダードフェノール
化合物；フェノチアジン、ジフェニルアミン、N,N'−ジ
ナフチルフェニレンジアミン等のアミン化合物；メトキ
シフェノール、ハイドロキノン、2,5-ジ-tert-アミルハ
イドロキノン、2,5-ジ-tert-ブチルハイドロキノン等の
ハイドロキノン化合物などを挙げることができる。酸化
第二銅または硫酸銅と併用する重合禁止剤の量について
は特に制限はなく、任意の量を用いることができる。Further, when a polymerization inhibitor selected from a hindered phenol-based polymerization inhibitor, an amine-based polymerization inhibitor and a hydroquinone-based polymerization inhibitor is used in combination with cupric oxide or copper sulfate, unexpected synergism can be expected. It was found that the effect further improved the thermal stability during distillation of the acrylic-functional organosilicon compound. Examples of such polymerization inhibitors include conventionally known ones such as 2,6-di-tert-butyl-4-.
Hindered phenol compounds such as methylphenol and 2,2'-methylene-bis (6-tert-butyl-4-methylphenol); amine compounds such as phenothiazine, diphenylamine, N, N'-dinaphthylphenylenediamine; methoxyphenol And hydroquinone compounds such as hydroquinone, 2,5-di-tert-amylhydroquinone and 2,5-di-tert-butylhydroquinone. The amount of the polymerization inhibitor used in combination with cupric oxide or copper sulfate is not particularly limited, and any amount can be used.
【００１１】本発明の安定化方法は従来周知のいずれの
蒸留手段においても実施することができ蒸留手段に特に
制限はないが、アクリル官能性有機ケイ素化合物は一般
に沸点が高く熱に不安定な性質を有するので、減圧下で
蒸留することが好ましい。The stabilization method of the present invention can be carried out by any conventional distillation means and there is no particular limitation on the distillation means. However, acrylic-functional organosilicon compounds generally have a high boiling point and a heat-labile property. Therefore, it is preferable to perform distillation under reduced pressure.
【００１２】[0012]
【実施例】つぎに本発明の実施例及び比較例を挙げる。 ［実施例１］（３−メタクリロキシプロピル）トリメト
キシシラン10g と酸化第二銅0.03gを試験管に入れ、試
験管空間部を窒素ガスで置換した後、十分に栓をして密
閉状態とした。次いでこの試験管を 150℃の油浴につけ
て加熱し酸化第二銅の安定化効果を調べたところ、30時
間経過後も増粘は見られなかった。Next, examples and comparative examples of the present invention will be described. [Example 1] 10 g of (3-methacryloxypropyl) trimethoxysilane and 0.03 g of cupric oxide were put into a test tube, and the test tube space was replaced with nitrogen gas. did. Then, the test tube was placed in an oil bath at 150 ° C. and heated to examine the stabilizing effect of cupric oxide. As a result, no increase in viscosity was observed even after 30 hours.
【００１３】［実施例２］実施例１において、酸化第二
銅の代わりに硫酸銅0.03g を使用した以外は実施例１と
同様にして硫酸銅の安定化効果を調べたところ、30時間
経過後も増粘は見られなかった。Example 2 The stabilizing effect of copper sulfate was examined in the same manner as in Example 1 except that 0.03 g of copper sulfate was used instead of cupric oxide. No thickening was seen afterwards.
【００１４】［比較例１］酸化第二銅、硫酸銅のいずれ
をも添加せず、（３−メタクリロキシプロピル）トリメ
トキシシラン単独で実施例１と同様にして加熱したとこ
ろ、５時間でゲル化してしまった。[Comparative Example 1] When neither of cupric oxide nor copper sulfate was added and (3-methacryloxypropyl) trimethoxysilane was heated in the same manner as in Example 1, the gel was obtained in 5 hours. It has become.
【００１５】［実施例３］実施例１において、（３−メ
タクリロキシプロピル）トリメトキシシランの代わり
に、トリクロロシランとメタクリル酸アリルを原料とし
公知の反応方法により得られた（３−メタクリロキシプ
ロピル）トリクロロシランを95重量％含む反応液10g を
使用した以外は、実施例１と同様にして酸化第二銅の安
定化効果を調べたところ、20時間経過後も増粘は見られ
なかった。Example 3 In Example 1, trichlorosilane and allyl methacrylate were used as starting materials instead of (3-methacryloxypropyl) trimethoxysilane to obtain (3-methacryloxypropyl). ) The stabilizing effect of cupric oxide was examined in the same manner as in Example 1 except that 10 g of a reaction solution containing 95% by weight of trichlorosilane was used. As a result, no increase in viscosity was observed even after 20 hours.
【００１６】［実施例４］実施例３において、酸化第二
銅の代わりに硫酸銅0.03g を使用した以外は実施例３と
同様にして硫酸銅の安定化効果を調べたところ、24時間
経過後も増粘は見られなかった。Example 4 The stabilizing effect of copper sulfate was examined in the same manner as in Example 3 except that 0.03 g of copper sulfate was used instead of cupric oxide. No thickening was seen afterwards.
【００１７】［比較例２］実施例３において酸化第二銅
を添加しないこと以外は実施例３と同様な操作を行った
ところ、４時間でゲル化してしまった。Comparative Example 2 The same operation as in Example 3 was carried out except that cupric oxide was not added, and gelation occurred in 4 hours.
【００１８】［実施例５］実施例１において、（３−メ
タクリロキシプロピル）トリメトキシシランの代わり
に、メチルジクロロシランとメタクリル酸アリルを原料
とし公知の反応方法により得られた（３−メタクリロキ
シプロピル）メチルジクロロシランを95重量％含む反応
液10g を使用した以外は、実施例１と同様にして酸化第
二銅の安定化効果を調べたところ、24時間経過後も増粘
は見られなかった。Example 5 In Example 1, methyldichlorosilane and allyl methacrylate were used as raw materials in place of (3-methacryloxypropyl) trimethoxysilane to obtain (3-methacryloxy). When the stabilizing effect of cupric oxide was examined in the same manner as in Example 1 except that 10 g of a reaction solution containing 95% by weight of propyl) methyldichlorosilane was used, no thickening was observed even after 24 hours. Was.
【００１９】［実施例６］実施例５において、酸化第二
銅の代わりに硫酸銅0.03g を使用した以外は実施例５と
同様にして硫酸銅の安定化効果を調べたところ、24時間
経過後も増粘は見られなかった。Example 6 The stabilizing effect of copper sulfate was examined in the same manner as in Example 5 except that 0.03 g of copper sulfate was used instead of cupric oxide. No thickening was seen afterwards.
【００２０】［比較例３］実施例５において酸化第二銅
を添加しないこと以外は実施例５と同様な操作を行った
ところ、５時間でゲル化してしまった。Comparative Example 3 The same operation as in Example 5 was carried out except that cupric oxide was not added, and gelation occurred in 5 hours.
【００２１】［実施例７、比較例４］ジメチルクロロシ
ラン及びメタクリル酸アリルを原料とし公知の反応方法
により（３−メタクリロキシプロピル）ジメチルクロロ
シランを76重量％含む反応液を得た。この反応液各10g
に各種添加物0.05g をそれぞれ加え、実施例１と同様に
して安定化効果を調べた。結果は次のとおりであった。
反応液単独では２時間でゲル化、酸化第二銅または硫酸
銅では40時間経過後増粘が見られ、酸化第二銅(0.05g)
と2,6-ジ-tert-ブチルフェノール(0.05g) の併用、酸化
第二銅(0.05g)と2,2'−メチレン−ビス（6-tert−ブチ
ル−4-メチルフェノール）(0.05g) の併用、酸化第二銅
(0.05g) とp-フェニレンジアミン(0.05g) の併用及び酸
化第二銅(0.05g) と2,5-ジ-tert-ブチルハイドロキノン
(0.05g) の併用では40時間経過後増粘なく、上記の重合
禁止剤との併用において酸化第二銅を硫酸銅に代えた場
合も40時間経過後増粘はなかった。一方、CuClでは６時
間、CuBrでは６時間、CuIでは５時間、CuCl2 では10時
間、CuBr2 では８時間、Cu2Oでは５時間、NiCl2 では７
時間、FeCl3 では８時間、2,6-ジ-tert-ブチルフェノー
ルのみでは５時間、p-フェニレンジアミンのみでは４時
間、2,2'−メチレン−ビス（6-tert−ブチル−4-メチル
フェノール）のみでは５時間でそれぞれゲル化した。Example 7, Comparative Example 4 Using dimethylchlorosilane and allyl methacrylate as raw materials, a reaction solution containing 76% by weight of (3-methacryloxypropyl) dimethylchlorosilane was obtained by a known reaction method. 10 g each of this reaction solution
, And the stabilizing effect was examined in the same manner as in Example 1. The results were as follows:
The reaction solution gelled in 2 hours, cupric oxide or copper sulfate increased in viscosity after 40 hours, and cupric oxide (0.05 g)
And 2,6-di-tert-butylphenol (0.05 g), cupric oxide (0.05 g) and 2,2′-methylene-bis (6-tert-butyl-4-methylphenol) (0.05 g) , Cupric oxide
(0.05g) and p-phenylenediamine (0.05g) and cupric oxide (0.05g) and 2,5-di-tert-butylhydroquinone
(0.05 g), there was no thickening after 40 hours, and when the cupric oxide was replaced with copper sulfate in combination with the above polymerization inhibitor, there was no thickening after 40 hours. On the other hand, the CuCl 6 hours, the CuBr 6 hours, the CuI 5 hours, the CuCl 2 10 hours, CuBr 2 in 8 hours, Cu 2 O in 5 hours, the NiCl 2 7
Time, 8 hours for FeCl 3 , 5 hours for 2,6-di-tert-butylphenol alone, 4 hours for p-phenylenediamine alone, 2,2′-methylene-bis (6-tert-butyl-4-methylphenol ) Alone gelled in 5 hours.
【００２２】以上の例から明らかなように、酸化第二銅
あるいは硫酸銅は熱に不安定なアクリル官能性有機ケイ
素化合物を熱に対して著しく安定化させる効果を有す
る。この効果は公知の重合禁止剤の効果よりもはるかに
大きいものである。また、酸化第二銅または硫酸銅と共
に、ヒンダードフェノール系重合禁止剤、アミン系重合
禁止剤及びハイドロキノン系重合禁止剤から選ばれる重
合禁止剤を使用すると相乗効果があり、さらに熱安定性
が高まることが明らかとなった。As is clear from the above examples, cupric oxide or copper sulfate has the effect of remarkably stabilizing a thermally unstable acrylic-functional organosilicon compound against heat. This effect is much greater than that of known polymerization inhibitors. Further, when a polymerization inhibitor selected from a hindered phenol-based polymerization inhibitor, an amine-based polymerization inhibitor and a hydroquinone-based polymerization inhibitor is used together with cupric oxide or copper sulfate, a synergistic effect is obtained, and the thermal stability is further increased. It became clear.
【００２３】［実施例８］ジメチルクロロシラン及びメ
タクリル酸アリルを原料とし公知の反応方法により（３
−メタクリロキシプロピル）ジメチルクロロシランを76
重量％含む反応液を得た。この反応液185.6gに2,2'−メ
チレン−ビス（6-tert−ブチル−4-メチルフェノール）
1.86g 、1,3,5-トリメチル−2,4,6-トリス（3,5-ジ-ter
t-ブチル−4-ヒドロキシベンジル）ベンゼン0.48g 及び
酸化第二銅0.93g を添加し、蒸留を行った。まず、この
反応液を40mmHgに減圧し、昇温して62℃までの留分15.5
g を低沸点物として取った。次いで、冷却して室温に戻
してから10mmHgに減圧し、再び昇温して 105℃までの留
分7.0gを前留とし、 105〜 107℃の留分135.6gを主留と
して取った。この主留分は（３−メタクリロキシプロピ
ル）ジメチルクロロシランであり、ガスクロマトグラフ
ィーによる純度は94％であった。なお、蒸留にはガラス
製の単蒸留装置を用いた。上述の蒸留操作において装置
内にはゲルの発生が全く見られず、高い蒸留収率（95
％）で目的物を得ることができた。Example 8 Using dimethylchlorosilane and allyl methacrylate as raw materials, a known reaction method (3)
-Methacryloxypropyl) dimethylchlorosilane to 76
A reaction solution containing a weight% was obtained. In 185.6 g of this reaction solution, 2,2'-methylene-bis (6-tert-butyl-4-methylphenol)
1.86 g, 1,3,5-trimethyl-2,4,6-tris (3,5-di-ter
0.48 g of (t-butyl-4-hydroxybenzyl) benzene and 0.93 g of cupric oxide were added and distilled. First, the pressure of the reaction solution was reduced to 40 mmHg, and the temperature was increased to a fraction 15.5 to 62 ° C.
g was taken as low boiler. Then, after cooling to room temperature, the pressure was reduced to 10 mmHg, and the temperature was raised again to take a 7.0 g fraction up to 105 ° C as a forerunner and a 135.6 g fraction at 105 to 107 ° C as a main fraction. This main fraction was (3-methacryloxypropyl) dimethylchlorosilane, and the purity by gas chromatography was 94%. Note that a simple distillation apparatus made of glass was used for the distillation. In the distillation operation described above, no gel was generated in the apparatus, and a high distillation yield (95%) was obtained.
%) To obtain the desired product.
【００２４】［実施例９］実施例８において酸化第二銅
の代わりに硫酸銅0.093gを添加した以外は実施例８と同
様にして蒸留を行った。まず、この反応液を40mmHgに減
圧し、昇温して62℃までの留分16.3g を低沸点物として
取った。次いで、冷却して室温に戻してから10mmHgに減
圧し、再び昇温して 104℃までの留分3.6gを前留とし、
104〜 108℃の留分134.2gを主留として取った。主留分
のガスクロマトグラフィーによる純度は95％であった。
上述の蒸留操作において装置内にはゲルの発生が全く見
られず、高い蒸留収率（95％）で目的物を得ることがで
きた。Example 9 Distillation was carried out in the same manner as in Example 8, except that 0.093 g of copper sulfate was added instead of cupric oxide. First, the pressure of the reaction solution was reduced to 40 mmHg, the temperature was raised, and 16.3 g of a fraction up to 62 ° C was taken as a low-boiling substance. Then, after cooling and returning to room temperature, the pressure was reduced to 10 mmHg, and the temperature was raised again, and 3.6 g of a fraction up to 104 ° C was taken as a forerunner,
134.2 g of a 104-108 ° C distillate was taken as the main distillate. The purity of the main fraction by gas chromatography was 95%.
In the distillation operation described above, no gel was generated in the apparatus, and the desired product could be obtained with a high distillation yield (95%).
【００２５】［比較例５］実施例８において酸化第二銅
0.93g の代わりに o-tert-ブチルフェノール1.19g を使
用した以外は、実施例８と同じ装置、反応液および重合
禁止剤を用いて蒸留を行った。まず、40mmHgに減圧し、
昇温して61℃までの留分15.1g を低沸点物として取っ
た。次いで、冷却して室温に戻してから8mmHg に減圧
し、再び昇温して 101℃までの留分6.2gを前留とし、 1
01℃からの留分を主留として取り続けていたところ、 1
04℃で蒸気上昇管においてポップコーン状のゲル物が大
量に発生し、蒸気上昇管がほとんど閉塞して蒸留不可能
になった。Comparative Example 5 Cupric oxide of Example 8
Distillation was carried out using the same apparatus, reaction solution and polymerization inhibitor as in Example 8, except that 1.19 g of o-tert-butylphenol was used instead of 0.93 g. First, reduce the pressure to 40 mmHg,
The temperature was raised, and 15.1 g of a fraction up to 61 ° C was taken as a low-boiling substance. Then, after cooling and returning to room temperature, the pressure was reduced to 8 mmHg, and the temperature was raised again to 6.2 g of a fraction up to 101 ° C as a forerunner.
While the fraction from 01 ° C was taken as the main fraction, 1
At 04 ° C., a large amount of popcorn-like gel was generated in the vapor riser, and the vapor riser was almost blocked, making distillation impossible.
【００２６】［比較例６］実施例８において酸化第二銅
0.93g の代わりに塩化第二鉄0.19g を使用した以外は、
実施例８と同じ装置、反応液および重合禁止剤を用いて
蒸留を行った。まず、41mmHgに減圧し、昇温して59℃ま
での留分13.1g を低沸点物として取った。次いで、冷却
して室温に戻してから10mmHgに減圧し、再び昇温して 1
11℃までの留分6.1gを前留とし、 111℃からの留分を主
留分として取り続けていたところ、112℃で蒸気上昇管
においてポップコーン状のゲル物が発生し、蒸気上昇管
がほとんど閉塞してしまった。Comparative Example 6 Cupric oxide of Example 8
Except that 0.19 g of ferric chloride was used instead of 0.93 g
Distillation was carried out using the same apparatus, reaction solution and polymerization inhibitor as in Example 8. First, the pressure was reduced to 41 mmHg, the temperature was raised, and 13.1 g of a fraction up to 59 ° C was taken as a low-boiling substance. Then, after cooling to room temperature, the pressure was reduced to 10 mmHg, and the temperature was raised again to 1
A 6.1 g distillate up to 11 ° C was taken as a forerunner, and a fraction from 111 ° C was continuously taken as the main fraction.At 112 ° C, popcorn-like gel material was generated in the steam riser, and almost no steam riser was formed. It has been blocked.
【００２７】[0027]
【発明の効果】本発明によれば、アクリル官能性有機ケ
イ素化合物の蒸留による精製が容易にかつ収率よく行え
るので、本発明の実用的な効果は極めて大きい。According to the present invention, the acryl-functional organosilicon compound can be easily purified by distillation at a high yield, so that the practical effect of the present invention is extremely large.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 昭 新潟県中頸城郡頸城村大字西福島28番地 １ 信越化学工業株式会社 合成技術研 究所内 (72)発明者 遠藤 幹夫 新潟県中頸城郡頸城村大字西福島28番地 １ 信越化学工業株式会社 合成技術研 究所内 (56)参考文献 特開 平５−271248（ＪＰ，Ａ) 特開 平４−77489（ＪＰ，Ａ) 特開 昭60−16996（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07F 7/18 C07F 7/20 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Yamamoto 28, Nishifukushima, Oaza, Kushiro-mura, Nakakushiro-gun, Niigata Prefecture 1 Within Shin-Etsu Chemical Co., Ltd., Synthetic Technology Research Institute (72) Inventor Mikio Endo, Kushiro, Nakakushiro-gun, Niigata Prefecture 28, Nishifukushima, Village Daiichi 1 Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) References JP-A-5-271248 (JP, A) JP-A-4-77489 (JP, A) JP-A-60-16996 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) C07F 7/18 C07F 7/20
Claims (3)
精製する方法において、酸化第二銅または硫酸銅を存在
させることを特徴とする該アクリル官能性有機ケイ素化
合物の蒸留時の安定化方法。1. A method for distilling and purifying an acryl-functional organosilicon compound, the method comprising stabilizing the acryl-functional organosilicon compound during distillation, wherein cupric oxide or copper sulfate is present.
精製する方法において、酸化第二銅または硫酸銅のほか
に、ヒンダードフェノール系重合禁止剤、アミン系重合
禁止剤及びハイドロキノン系重合禁止剤から選ばれた重
合禁止剤をも同時に存在させることを特徴とするアクリ
ル官能性有機ケイ素化合物の蒸留時の安定化方法。2. A method for purifying an acrylic-functional organosilicon compound by distillation, wherein in addition to cupric oxide or copper sulfate, a hindered phenol-based polymerization inhibitor, an amine-based polymerization inhibitor and a hydroquinone-based polymerization inhibitor are selected. A method for stabilizing an acrylic-functional organosilicon compound at the time of distillation, wherein a polymerization inhibitor is also present at the same time.
一般式（Ｉ）で示されるものである請求項１または２に
記載のアクリル官能性有機ケイ素化合物の蒸留時の安定
化方法。 【化１】 （式中、R1は水素原子またはメチル基、R2は加水分解性
基、R3は１価炭化水素基、ｎは０、１、２、３を表
す。）3. The method for stabilizing an acrylic functional organosilicon compound during distillation according to claim 1 or 2, wherein the acrylic functional organosilicon compound is represented by the following general formula (I). Embedded image (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrolyzable group, R 3 represents a monovalent hydrocarbon group, and n represents 0, 1, 2 , or 3. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6098625A JP2980514B2 (en) | 1994-03-31 | 1994-05-12 | Method for stabilizing acrylic-functional organosilicon compounds during distillation |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-62726 | 1994-03-31 | ||
| JP6272694 | 1994-03-31 | ||
| JP6098625A JP2980514B2 (en) | 1994-03-31 | 1994-05-12 | Method for stabilizing acrylic-functional organosilicon compounds during distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07316164A JPH07316164A (en) | 1995-12-05 |
| JP2980514B2 true JP2980514B2 (en) | 1999-11-22 |
Family
ID=26403775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6098625A Expired - Fee Related JP2980514B2 (en) | 1994-03-31 | 1994-05-12 | Method for stabilizing acrylic-functional organosilicon compounds during distillation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2980514B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4025384B2 (en) * | 1996-12-02 | 2007-12-19 | 東レ・ダウコーニング株式会社 | Method for purifying 3-methacryloxypropyldimethylhalosilane or 3-methacryloxypropylmethyldihalosilane |
| DE69920329T3 (en) * | 1998-06-19 | 2009-07-09 | Shin-Etsu Chemical Co., Ltd. | Distillation process for (meth) acryloxysilanes |
| US20080119627A1 (en) * | 2006-11-22 | 2008-05-22 | Masataka Nakamura | Methods for purifying siloxanyl monomers |
| JP6489275B1 (en) | 2018-08-14 | 2019-03-27 | セントラル硝子株式会社 | Distillation purification method of fluorine-containing polymerizable monomer |
-
1994
- 1994-05-12 JP JP6098625A patent/JP2980514B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07316164A (en) | 1995-12-05 |
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