JP2004026660A - Method of manufacturing compound of silyl (meth)acrylate - Google Patents
Method of manufacturing compound of silyl (meth)acrylate Download PDFInfo
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- JP2004026660A JP2004026660A JP2002180859A JP2002180859A JP2004026660A JP 2004026660 A JP2004026660 A JP 2004026660A JP 2002180859 A JP2002180859 A JP 2002180859A JP 2002180859 A JP2002180859 A JP 2002180859A JP 2004026660 A JP2004026660 A JP 2004026660A
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- Prior art keywords
- acrylate
- silyl
- meth
- general formula
- ammonia
- Prior art date
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- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 title description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 acrylate compound Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 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 5
- 238000009835 boiling Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KNNOZYMZRGTZQM-UHFFFAOYSA-N tri(propan-2-yl)silyl 2-methylprop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C(C)=C KNNOZYMZRGTZQM-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- CVHFFPVHUPXZBP-UHFFFAOYSA-N tert-butyl-chloro-di(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)(C)C CVHFFPVHUPXZBP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XMNMAKAFOUTNNM-UHFFFAOYSA-N C=CC(=O)O[Si](C1CCCC1)(C2CCCC2)C3CCCC3 Chemical compound C=CC(=O)O[Si](C1CCCC1)(C2CCCC2)C3CCCC3 XMNMAKAFOUTNNM-UHFFFAOYSA-N 0.000 description 1
- ZZOJDLOASRLIJG-UHFFFAOYSA-N C=CC(=O)O[Si](C1CCCCC1)(C2CCCCC2)C3CCCCC3 Chemical compound C=CC(=O)O[Si](C1CCCCC1)(C2CCCCC2)C3CCCCC3 ZZOJDLOASRLIJG-UHFFFAOYSA-N 0.000 description 1
- YNLXQIYGXPUJMX-UHFFFAOYSA-N CC(=C)C(=O)O[Si](C1CCCC1)(C2CCCC2)C3CCCC3 Chemical compound CC(=C)C(=O)O[Si](C1CCCC1)(C2CCCC2)C3CCCC3 YNLXQIYGXPUJMX-UHFFFAOYSA-N 0.000 description 1
- ATNOWXJMJJZTBP-UHFFFAOYSA-N CC(=C)C(=O)O[Si](C1CCCCC1)(C1CCCCC1)C1CCCCC1 Chemical compound CC(=C)C(=O)O[Si](C1CCCCC1)(C1CCCCC1)C1CCCCC1 ATNOWXJMJJZTBP-UHFFFAOYSA-N 0.000 description 1
- LPNLASIEYTWMBC-UHFFFAOYSA-N [tert-butyl(dimethyl)silyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[Si](C)(C)C(C)(C)C LPNLASIEYTWMBC-UHFFFAOYSA-N 0.000 description 1
- XDWFDZKNUBWRDD-UHFFFAOYSA-N [tert-butyl(dimethyl)silyl] prop-2-enoate Chemical compound CC(C)(C)[Si](C)(C)OC(=O)C=C XDWFDZKNUBWRDD-UHFFFAOYSA-N 0.000 description 1
- AVJGFXADJHXBLW-UHFFFAOYSA-N [tert-butyl(diphenyl)silyl] 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)(OC(=O)C(=C)C)C1=CC=CC=C1 AVJGFXADJHXBLW-UHFFFAOYSA-N 0.000 description 1
- ZBVUYILTDMIBQT-UHFFFAOYSA-N [tert-butyl(diphenyl)silyl] prop-2-enoate Chemical compound C=1C=CC=CC=1[Si](OC(=O)C=C)(C(C)(C)C)C1=CC=CC=C1 ZBVUYILTDMIBQT-UHFFFAOYSA-N 0.000 description 1
- VSIDCUZXWQHDOI-UHFFFAOYSA-N [tert-butyl-di(propan-2-yl)silyl] 2-methylprop-2-enoate Chemical compound CC(C)[Si](C(C)(C)C)(C(C)C)OC(=O)C(C)=C VSIDCUZXWQHDOI-UHFFFAOYSA-N 0.000 description 1
- ALKDAKOWKWZIMT-UHFFFAOYSA-N [tert-butyl-di(propan-2-yl)silyl] prop-2-enoate Chemical compound CC(C)[Si](C(C)(C)C)(C(C)C)OC(=O)C=C ALKDAKOWKWZIMT-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 1
- UANDAQWXKUOGLV-UHFFFAOYSA-N chloro(tricyclohexyl)silane Chemical compound C1CCCCC1[Si](C1CCCCC1)(Cl)C1CCCCC1 UANDAQWXKUOGLV-UHFFFAOYSA-N 0.000 description 1
- HOOMRPALMNVKFZ-UHFFFAOYSA-N chloro(tricyclopentyl)silane Chemical compound C1CCCC1[Si](C1CCCC1)(Cl)C1CCCC1 HOOMRPALMNVKFZ-UHFFFAOYSA-N 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- ACTAPAGNZPZLEF-UHFFFAOYSA-N chloro(tripropyl)silane Chemical compound CCC[Si](Cl)(CCC)CCC ACTAPAGNZPZLEF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JWQYRTCIGFYTOK-UHFFFAOYSA-N di(propan-2-yl)silyl prop-2-enoate Chemical compound C(C=C)(=O)O[SiH](C(C)C)C(C)C JWQYRTCIGFYTOK-UHFFFAOYSA-N 0.000 description 1
- JEJQTXYAGBHWHV-UHFFFAOYSA-N dimethylsilyl 2-methylprop-2-enoate Chemical compound C[SiH](C)OC(=O)C(C)=C JEJQTXYAGBHWHV-UHFFFAOYSA-N 0.000 description 1
- KUXKETZHDPDMHZ-UHFFFAOYSA-N dimethylsilyl prop-2-enoate Chemical compound C[SiH](C)OC(=O)C=C KUXKETZHDPDMHZ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical compound [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- DOVSWWRKFANNHT-UHFFFAOYSA-N tri(butan-2-yl)-chlorosilane Chemical compound CCC(C)[Si](Cl)(C(C)CC)C(C)CC DOVSWWRKFANNHT-UHFFFAOYSA-N 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- WEAZWKYSTGLBSQ-UHFFFAOYSA-N tributylsilyl 2-methylprop-2-enoate Chemical compound CCCC[Si](CCCC)(CCCC)OC(=O)C(C)=C WEAZWKYSTGLBSQ-UHFFFAOYSA-N 0.000 description 1
- NIBPEHGZRFSWSY-UHFFFAOYSA-N tributylsilyl prop-2-enoate Chemical compound CCCC[Si](CCCC)(CCCC)OC(=O)C=C NIBPEHGZRFSWSY-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- PWVJTRQTFFVDEU-UHFFFAOYSA-N triethylsilyl 2-methylprop-2-enoate Chemical compound CC[Si](CC)(CC)OC(=O)C(C)=C PWVJTRQTFFVDEU-UHFFFAOYSA-N 0.000 description 1
- UGKLJUIMKCCNGS-UHFFFAOYSA-N triethylsilyl prop-2-enoate Chemical compound CC[Si](CC)(CC)OC(=O)C=C UGKLJUIMKCCNGS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- PGQNYIRJCLTTOJ-UHFFFAOYSA-N trimethylsilyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[Si](C)(C)C PGQNYIRJCLTTOJ-UHFFFAOYSA-N 0.000 description 1
- OTYBJBJYBGWBHB-UHFFFAOYSA-N trimethylsilyl prop-2-enoate Chemical compound C[Si](C)(C)OC(=O)C=C OTYBJBJYBGWBHB-UHFFFAOYSA-N 0.000 description 1
- PIQIWPDMOYYEBV-UHFFFAOYSA-N triphenylsilyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PIQIWPDMOYYEBV-UHFFFAOYSA-N 0.000 description 1
- HVMNIRCQQXUXRP-UHFFFAOYSA-N triphenylsilyl prop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C=C)C1=CC=CC=C1 HVMNIRCQQXUXRP-UHFFFAOYSA-N 0.000 description 1
- SDTUJUAYRASPMK-UHFFFAOYSA-N tripropylsilyl 2-methylprop-2-enoate Chemical compound CCC[Si](CCC)(CCC)OC(=O)C(C)=C SDTUJUAYRASPMK-UHFFFAOYSA-N 0.000 description 1
- ZYPHHWVSWUHVGF-UHFFFAOYSA-N tripropylsilyl prop-2-enoate Chemical compound CCC[Si](CCC)(CCC)OC(=O)C=C ZYPHHWVSWUHVGF-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、下記一般式（２）で示されるシリル（メタ）アクリレート化合物の製造方法に関する。この化合物は、船底塗料などの加水分解性自己研磨型ポリマーの原料等として有用である。
【化２】
【０００２】
【従来の技術及び発明が解決しようとする課題】
上記一般式（２）のシリル（メタ）アクリレート化合物は、一般的にクロロシラン化合物とアクリル酸又はメタクリル酸とを反応させる方法で製造され、その製造例としては特許第３０５２４３０号公報、同第３０５２４３１号公報、特開平４−３４２５９５号公報等が例示される。特許第３０５２４３１号公報、特開平４−３４２５９５号公報では、塩酸捕捉剤を反応系中に加えずに脱塩酸をおこなっているが、反応を進行させるためには高温に加熱する必要があり、シリル（メタ）アクリレート化合物、又は原料のアクリル酸、メタクリル酸の重合の危険性が伴うため、工業的製造は困難である。また、特許第３０５２４３０号公報においては、反応の際に生成する塩酸をトラップするために用いる塩酸捕捉剤として３級アミン化合物を用いている。３級アミンを用いることにより、反応性が向上し、反応を定量的に進行させるために高温に加熱する必要はなくなるが、３級アミンは高価であり、また分子量が大きいため、反応で生成する３級アミン塩酸塩の量が多く、撹拌のために大量の溶媒を必要とするので工業的に製造するには有利ではない。また、この特許明細書には３級アミンの代わりに、１級アミンや２級アミンを用いると副反応が生じるため、３級アミンを用いなければならないとの記載もある。
【０００３】
本発明は上記事情に鑑みなされたもので、より安価に効率的かつ安全に行うことのできる上記一般式（２）のシリル（メタ）アクリレート化合物の製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段及び発明の実施の形態】
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、安価で工業的に入手容易でかつ３級アミンに比べて著しく分子量の小さなアンモニアを塩酸捕捉剤として用いると、生じる塩酸塩（塩化アンモニウム）の量が少なくなるため、溶媒を実質的に用いる必要がなくなり、また意外にも１級アミンや２級アミンを用いた時に起こる副反応も起こらず、効率的に収率よく安全にシリル（メタ）アクリレート化合物が製造できることを知見し、本発明を完成するに至ったものである。
【０００５】
従って、本発明は、下記一般式（１）
Ｒ１Ｒ２Ｒ３ＳｉＣｌ （１）
（式中、Ｒ１、Ｒ２、Ｒ３は、互いに同一又は異なる炭素数１〜１０の１価炭化水素基を示す。）
で示されるクロロシラン化合物と、アクリル酸又はメタクリル酸とを反応させ、下記一般式（２）
【化３】
で示されるシリル（メタ）アクリレート化合物を製造する方法において、上記反応をアンモニアの存在下で行うことを特徴とする、上記一般式（２）で示されるシリル（メタ）アクリレート化合物の製造方法を提供するものである。
【０００６】
以下、本発明につき更に詳しく説明する。
本発明のシリル（メタ）アクリレート化合物の製造方法において、原料として用いられるクロロシラン化合物は、下記一般式（１）
Ｒ１Ｒ２Ｒ３ＳｉＣｌ （１）
（式中、Ｒ１、Ｒ２、Ｒ３は、互いに同一又は異なる炭素数１〜１０の１価炭化水素基を示す。）
で示されるものである。
【０００７】
ここで、上記一般式（１）で示されるクロロシラン化合物としては、具体的にはトリメチルクロロシラン、トリエチルクロロシラン、トリプロピルクロロシラン、トリブチルクロロシラン、トリイソプロピルクロロシラン、トリ（ｓｅｃ−ブチル）クロロシラン、トリシクロペンチルクロロシラン、トリシクロヘキシルクロロシラン、トリフェニルクロロシラン、ｔｅｒｔ−ブチルジメチルクロロシラン、ｔｅｒｔ−ブチルジフェニルクロロシラン、ｔｅｒｔ−ブチルジイソプロピルクロロシラン、テキシルジメチルクロロシラン、テキシルジイソプロピルクロロシラン等が例示されるが、シリル（メタ）アクリレート化合物及びシリル（メタ）アクリレート化合物をポリマーに導いた時の加水分解性に対する適度な安定性の点から、上記一般式（１）で示されるクロロシラン化合物のＲ１、Ｒ２、Ｒ３置換基が、互いに同一又は異なるα位に炭化水素基を有する炭素数３〜１０の１価の分岐状炭化水素基又は炭素数３〜１０の１価の環状炭化水素基であるものが好ましく、具体的にはトリイソプロピルクロロシラン、ｔｅｒｔ−ブチルジイソプロピルクロロシラン、テキシルジイソプロピルクロロシランが例示される。
【０００８】
アクリル酸又はメタクリル酸と上記一般式（１）で示されるクロロシラン化合物との配合比は特に限定されないが、反応性、生産性の点から、アクリル酸又はメタクリル酸１モルに対し、クロロシラン化合物０．５〜２．０モル、特に０．８〜１．２モルの範囲が好ましい。
【０００９】
本発明では、反応中に生じる塩酸をアンモニアを用いて脱塩酸するものである。アンモニアの量は特に限定されないが、反応性、生産性の点から、アクリル酸又はメタクリル酸１モルに対し、０．５〜５モル、特に１．０〜３．０モルの範囲が好ましい。アンモニアが０．５モル未満だと充分に脱塩酸が行われず反応が未達になる可能性があり、５モルを超えると、アンモニアの量に見合うだけの反応促進効果がみられない可能性がある。
【００１０】
また、反応温度は特に限定されないが、常圧又は加圧下で−２０℃〜１５０℃、特に０℃〜１００℃が好ましい。
【００１１】
なお、本反応は生成する塩化アンモニウムによる撹拌の負荷上昇が起こらず、反応性も良好であるので、実質的に溶媒を使用しなくてもよい。
【００１２】
上記の反応は、アクリル酸又はメタクリル酸にアンモニアをフィードしながらクロロシラン化合物を加える方法、アクリル酸又はメタクリル酸にアンモニアをフィードし、（メタ）アクリル酸アンモニウムとした後、クロロシラン化合物を加える方法、クロロシラン化合物にアンモニアをフィードしながらアクリル酸又はメタクリル酸を加える方法、クロロシラン化合物にアンモニアをフィードし、シラザンとした後、アクリル酸又はメタクリル酸を加える方法、アクリル酸又はメタクリル酸とクロロシラン化合物との混合液にアンモニアをフィードする方法のいずれの方法を採用してもよいが、操作の簡便性の点から、アクリル酸又はメタクリル酸とクロロシラン化合物との混合液にアンモニアをフィードする方法が好ましい。
【００１３】
また、上記の反応において、重合を防止するために、ヒドロキノン、ｐ−メトキシフェノール、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール等の重合禁止剤を添加してもよい。
【００１４】
反応終了後には塩化アンモニウムが生じるが、これは反応液を濾過、又は水を加えて塩化アンモニウムを溶解、分離することにより除去できる。以上のようにして塩を除去した反応液からは、通常の方法で目的物を回収することができる。
【００１５】
このような本発明の製造法では、下記一般式（２）
【化４】
で示されるシリル（メタ）アクリレート化合物を得ることができる。
【００１６】
上記一般式（２）で示されるシリル（メタ）アクリレート化合物として具体的には、トリメチルシリルアクリレート、トリエチルシリルアクリレート、トリプロピルシリルアクリレート、トリブチルシリルアクリレート、トリイソプロピルシリルアクリレート、トリ（ｎ−ブチル）シリルアクリレート、トリ（ｓｅｃ−ブチル）アクリレート、トリシクロペンチルシリルアクリレート、トリシクロヘキシルシリルアクリレート、トリフェニルシリルアクリレート、ｔｅｒｔ−ブチルジメチルシリルアクリレート、ｔｅｒｔ−ブチルジフェニルシリルアクリレート、ｔｅｒｔ−ブチルジイソプロピルシリルアクリレート、テキシルジメチルシリルアクリレート、テキシルジイソプロピルシリルアクリレート、トリメチルシリルメタクリレート、トリエチルシリルメタクリレート、トリプロピルシリルメタクリレート、トリブチルシリルメタクリレート、トリイソプロピルシリルメタクリレート、トリ（ｓｅｃ−ブチル）シリルメタクリレート、トリシクロペンチルシリルメタクリレート、トリシクロヘキシルシリルメタクリレート、トリフェニルシリルメタクリレート、ｔｅｒｔ−ブチルジメチルシリルメタクリレート、ｔｅｒｔ−ブチルジフェニルシリルメタクリレート、ｔｅｒｔ−ブチルジイソプロピルシリルメタクリレート、テキシルジメチルシリルメタクリレート、テキシルジイソプロピルシリルメタクリレート等が例示される。
【００１７】
【実施例】
以下、実施例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００１８】
［実施例１］
撹拌機、還流冷却器、滴下ロート及び温度計を備えたフラスコに、アクリル酸（３６．８ｇ、０．５１ｍｏｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（０．１１ｇ）を仕込み、２５℃にてアンモニア（９．４ｇ、０．５５ｍｏｌ）とトリイソプロピルクロロシラン（９６．４ｇ、０．５０ｍｏｌ）とを１時間かけて同時にフィードした。フィード終了後、反応液を５０℃で５時間撹拌した。その後反応液を室温まで冷却し、生じた塩化アンモニウムを濾別し蒸留した。トリイソプロピルシリルアクリレートを沸点８９−９０℃／０．６７ｋＰａの留分として１０２．０ｇ得た（収率８９％）。
【００１９】
［実施例２］
撹拌機、還流冷却器、滴下ロート及び温度計を備えたフラスコに、メタクリル酸（４３．９ｇ、０．５１ｍｏｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（０．１１ｇ）を仕込み、２５℃にてアンモニア（９．４ｇ、０．５５ｍｏｌ）とトリイソプロピルクロロシラン（９６．４ｇ、０．５０ｍｏｌ）とを１時間かけて同時にフィードした。フィード終了後、反応液を５０℃で５時間撹拌した。その後反応液を室温まで冷却し、生じた塩化アンモニウムを濾別し蒸留した。トリイソプロピルシリルメタクリレートを沸点８９−９０℃／０．６７ｋＰａの留分として１０９．５ｇ得た（収率９０％）。
【００２０】
［実施例３］
撹拌機、還流冷却器、滴下ロート及び温度計を備えたフラスコに、アクリル酸（３６．８ｇ、０．５１ｍｏｌ）、トリイソプロピルクロロシラン（９６．４ｇ、０．５０ｍｏｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（０．１１ｇ）を仕込み、２５℃にてアンモニア（９．４ｇ、０．５５ｍｏｌ）を１時間かけてフィードした。フィード終了後、反応液を５０℃で５時間撹拌した。その後反応液を室温まで冷却し、反応液に水（７５ｇ）を加え、生じた塩酸塩を溶解し、水層を除いた後、有機層を蒸留した。トリイソプロピルシリルアクリレートを沸点８９−９０℃／０．６７ｋＰａの留分として１０８．３ｇ得た（収率９５％）。
【００２１】
［実施例４］
撹拌機、還流冷却器、滴下ロート及び温度計を備えたフラスコに、メタクリル酸（４３．９ｇ、０．５１ｍｏｌ）、トリイソプロピルクロロシラン（９６．４ｇ、０．５０ｍｏｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（０．１１ｇ）を仕込み、２５℃にてアンモニア（９．４ｇ、０．５５ｍｏｌ）を１時間かけてフィードした。フィード終了後、反応液を５０℃で５時間撹拌した。その後反応液を室温まで冷却し、反応液に水（７５ｇ）を加え、生じた塩酸塩を溶解し、水層を除いた後、有機層を蒸留した。トリイソプロピルシリルメタクリレートを沸点１１０−１１１℃／１．３ｋＰａの留分として１１５．３ｇ得た（収率９５％）。
【００２２】
［比較例１］
トリエチルアミンを用いたトリイソプロピルシリルアクリレートの製造法
撹拌機、還流冷却器、滴下ロート及び温度計を備えたフラスコに、アクリル酸（３６．８ｇ、０．５１ｍｏｌ）、トルエン（５０ｍｌ）、２，６−ジ−ｔ−ブチル−４−メチルフェノール（０．１１ｇ）を仕込み、２５℃にてトリエチルアミン（５５．７ｇ、０．５５ｍｏｌ）を１時間かけて滴下した。滴下終了後、トリイソプロピルクロロシラン（９６．４ｇ、０．５０ｍｏｌ）を２５℃で１時間かけて滴下した。滴下中に生じた塩により撹拌が困難になったため、トルエンを１２０ｍｌ追加しなければならなかった。滴下終了後、反応液を５０℃で５時間撹拌した。その後反応液を室温まで冷却し、生じたトリエチルアミン塩酸塩を濾別し蒸留した。トリイソプロピルシリルアクリレートを沸点１１０−１１１℃／１．３ｋＰａの留分として１０１．８ｇ得た（収率８９％）。
【００２３】
【発明の効果】
本発明によれば、安価で工業的に入手容易なアンモニアを塩酸捕捉剤として用いることにより、溶媒を実質的に用いることなく、効率的に収率よく安全にシリル（メタ）アクリレートを製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a silyl (meth) acrylate compound represented by the following general formula (2). This compound is useful as a raw material of a hydrolyzable self-polishing polymer such as a ship bottom paint.
Embedded image
[0002]
Problems to be solved by the prior art and the invention
The silyl (meth) acrylate compound represented by the general formula (2) is generally produced by a method of reacting a chlorosilane compound with acrylic acid or methacrylic acid. Examples of the production are described in Japanese Patent Nos. 3052430 and 3052431. And Japanese Patent Application Laid-Open No. 4-342595. In Japanese Patent No. 3052431 and JP-A-4-342595, dehydrochlorination is carried out without adding a hydrochloric acid scavenger into the reaction system. However, in order to advance the reaction, it is necessary to heat the mixture to a high temperature. Since there is a risk of polymerization of the (meth) acrylate compound or acrylic acid or methacrylic acid as raw materials, industrial production is difficult. In Japanese Patent No. 3052430, a tertiary amine compound is used as a hydrochloric acid scavenger used to trap hydrochloric acid generated during the reaction. By using a tertiary amine, the reactivity is improved, and it is not necessary to heat to a high temperature in order to progress the reaction quantitatively. However, the tertiary amine is expensive and has a large molecular weight, so that it is formed by the reaction. Since the amount of the tertiary amine hydrochloride is large and a large amount of solvent is required for stirring, it is not advantageous for industrial production. This patent also states that if a primary amine or a secondary amine is used instead of a tertiary amine, a side reaction occurs, so that a tertiary amine must be used.
[0003]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a silyl (meth) acrylate compound of the above general formula (2), which can be carried out more efficiently and safely at lower cost.
[0004]
Means for Solving the Problems and Embodiments of the Invention
The inventor of the present invention has conducted intensive studies to achieve the above object. As a result, when ammonia is used as a hydrochloric acid scavenger, it is inexpensive, industrially available, and has a significantly smaller molecular weight than a tertiary amine. (Ammonium chloride) is reduced, so that it is not necessary to use a solvent substantially, and surprisingly, no side reaction occurs when a primary amine or a secondary amine is used. The inventors have found that silyl (meth) acrylate compounds can be produced, and have completed the present invention.
[0005]
Therefore, the present invention provides the following general formula (1)
R 1 R 2 R 3 SiCl (1)
(In the formula, R 1 , R 2 , and R 3 represent the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms.)
Is reacted with acrylic acid or methacrylic acid to obtain a compound represented by the following general formula (2)
Embedded image
A method for producing a silyl (meth) acrylate compound represented by the general formula (2), wherein the reaction is carried out in the presence of ammonia. Is what you do.
[0006]
Hereinafter, the present invention will be described in more detail.
In the method for producing a silyl (meth) acrylate compound of the present invention, the chlorosilane compound used as a raw material is represented by the following general formula (1)
R 1 R 2 R 3 SiCl (1)
(In the formula, R 1 , R 2 , and R 3 represent the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms.)
It is shown by.
[0007]
Here, as the chlorosilane compound represented by the general formula (1), specifically, trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, tributylchlorosilane, triisopropylchlorosilane, tri (sec-butyl) chlorosilane, tricyclopentylchlorosilane, Examples include tricyclohexylchlorosilane, triphenylchlorosilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, tert-butyldiisopropylchlorosilane, texyldimethylchlorosilane, texyldiisopropylchlorosilane, and the like. Examples thereof include a silyl (meth) acrylate compound and silyl. From the viewpoint of appropriate stability against hydrolysis when the (meth) acrylate compound is introduced into the polymer, R 1, R 2 of the chlorosilane compound represented by formula (1), R 3 substituent is a monovalent branched hydrocarbon group or a C 3 to 10 carbon atoms having a hydrocarbon group at the same or different α-position to each other Those which are monovalent cyclic hydrocarbon groups of several to 10 are preferable, and specific examples include triisopropylchlorosilane, tert-butyldiisopropylchlorosilane, and texyldiisopropylchlorosilane.
[0008]
The mixing ratio of acrylic acid or methacrylic acid to the chlorosilane compound represented by the above general formula (1) is not particularly limited. However, from the viewpoint of reactivity and productivity, the chlorosilane compound is added in an amount of 0.1 mol to 1 mol of acrylic acid or methacrylic acid. The range of 5 to 2.0 mol, particularly 0.8 to 1.2 mol is preferable.
[0009]
In the present invention, hydrochloric acid generated during the reaction is dehydrochlorinated using ammonia. The amount of ammonia is not particularly limited, but is preferably from 0.5 to 5 mol, particularly preferably from 1.0 to 3.0 mol, per 1 mol of acrylic acid or methacrylic acid from the viewpoint of reactivity and productivity. If the amount of ammonia is less than 0.5 mol, the reaction may not be achieved due to insufficient dehydrochlorination, and if the amount exceeds 5 mol, there is a possibility that the effect of promoting the reaction corresponding to the amount of ammonia may not be obtained. is there.
[0010]
The reaction temperature is not particularly limited, but is preferably -20 ° C to 150 ° C, particularly preferably 0 ° C to 100 ° C under normal pressure or under pressure.
[0011]
This reaction does not cause an increase in stirring load due to the generated ammonium chloride and has good reactivity, so that it is not necessary to substantially use a solvent.
[0012]
The above-mentioned reaction is a method of adding a chlorosilane compound while feeding ammonia to acrylic acid or methacrylic acid, a method of feeding ammonia to acrylic acid or methacrylic acid to obtain ammonium (meth) acrylate, and then adding a chlorosilane compound. A method of adding acrylic acid or methacrylic acid while feeding ammonia to the compound, a method of feeding ammonia to the chlorosilane compound to form silazane, and then adding acrylic acid or methacrylic acid, a mixed solution of acrylic acid or methacrylic acid and a chlorosilane compound Any method of feeding ammonia to the mixture may be employed, but from the viewpoint of easy operation, a method of feeding ammonia to a mixture of acrylic acid or methacrylic acid and a chlorosilane compound is preferable.
[0013]
In the above reaction, polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, and 2,6-di-tert-butyl-4-methylphenol are used to prevent polymerization. May be added.
[0014]
After the completion of the reaction, ammonium chloride is produced, which can be removed by filtering the reaction solution or adding water to dissolve and separate ammonium chloride. From the reaction solution from which the salt has been removed as described above, the target substance can be recovered by an ordinary method.
[0015]
In such a production method of the present invention, the following general formula (2)
Embedded image
Can be obtained.
[0016]
Specific examples of the silyl (meth) acrylate compound represented by the general formula (2) include trimethylsilyl acrylate, triethylsilyl acrylate, tripropylsilyl acrylate, tributylsilyl acrylate, triisopropylsilyl acrylate, and tri (n-butyl) silyl acrylate. , Tri (sec-butyl) acrylate, tricyclopentylsilyl acrylate, tricyclohexylsilyl acrylate, triphenylsilyl acrylate, tert-butyldimethylsilyl acrylate, tert-butyldiphenylsilyl acrylate, tert-butyldiisopropylsilyl acrylate, texyl dimethylsilyl acrylate , Texyl diisopropylsilyl acrylate, trimethylsilyl methacrylate, Triethylsilyl methacrylate, tripropylsilyl methacrylate, tributylsilyl methacrylate, triisopropylsilyl methacrylate, tri (sec-butyl) silyl methacrylate, tricyclopentylsilyl methacrylate, tricyclohexylsilyl methacrylate, triphenylsilyl methacrylate, tert-butyldimethylsilyl methacrylate, Examples thereof include tert-butyldiphenylsilyl methacrylate, tert-butyldiisopropylsilyl methacrylate, texyl dimethylsilyl methacrylate, texyl diisopropylsilyl methacrylate, and the like.
[0017]
【Example】
EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.
[0018]
[Example 1]
Acrylic acid (36.8 g, 0.51 mol) and 2,6-di-tert-butyl-4-methylphenol (0.11 g) were placed in a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. Ammonia (9.4 g, 0.55 mol) and triisopropylchlorosilane (96.4 g, 0.50 mol) were fed simultaneously at 25 ° C. over 1 hour. After the feed was completed, the reaction solution was stirred at 50 ° C. for 5 hours. Thereafter, the reaction solution was cooled to room temperature, and the resulting ammonium chloride was filtered off and distilled. 102.0 g of triisopropylsilyl acrylate was obtained as a fraction having a boiling point of 89-90 ° C./0.67 kPa (yield 89%).
[0019]
[Example 2]
In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, methacrylic acid (43.9 g, 0.51 mol) and 2,6-di-tert-butyl-4-methylphenol (0.11 g) were added. Ammonia (9.4 g, 0.55 mol) and triisopropylchlorosilane (96.4 g, 0.50 mol) were fed simultaneously at 25 ° C. over 1 hour. After the feed was completed, the reaction solution was stirred at 50 ° C. for 5 hours. Thereafter, the reaction solution was cooled to room temperature, and the resulting ammonium chloride was filtered off and distilled. 109.5 g of triisopropylsilyl methacrylate was obtained as a fraction having a boiling point of 89-90 ° C./0.67 kPa (yield 90%).
[0020]
[Example 3]
Acrylic acid (36.8 g, 0.51 mol), triisopropylchlorosilane (96.4 g, 0.50 mol), 2,6-di-tert were placed in a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. -Butyl-4-methylphenol (0.11 g) was charged, and ammonia (9.4 g, 0.55 mol) was fed at 25 ° C. over 1 hour. After the feed was completed, the reaction solution was stirred at 50 ° C. for 5 hours. Thereafter, the reaction solution was cooled to room temperature, water (75 g) was added to the reaction solution, the resulting hydrochloride was dissolved, and after removing the aqueous layer, the organic layer was distilled. 108.3 g of triisopropylsilyl acrylate was obtained as a fraction having a boiling point of 89-90 ° C./0.67 kPa (yield 95%).
[0021]
[Example 4]
In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, methacrylic acid (43.9 g, 0.51 mol), triisopropylchlorosilane (96.4 g, 0.50 mol), 2,6-di-tert -Butyl-4-methylphenol (0.11 g) was charged, and ammonia (9.4 g, 0.55 mol) was fed at 25 ° C. over 1 hour. After the feed was completed, the reaction solution was stirred at 50 ° C. for 5 hours. Thereafter, the reaction solution was cooled to room temperature, water (75 g) was added to the reaction solution, the resulting hydrochloride was dissolved, and after removing the aqueous layer, the organic layer was distilled. 115.3 g of triisopropylsilyl methacrylate was obtained as a fraction having a boiling point of 110 to 111 ° C./1.3 kPa (yield: 95%).
[0022]
[Comparative Example 1]
Production method of triisopropylsilyl acrylate using triethylamine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, acrylic acid (36.8 g, 0.51 mol), toluene (50 ml), 2,6- Di-t-butyl-4-methylphenol (0.11 g) was charged, and triethylamine (55.7 g, 0.55 mol) was added dropwise at 25 ° C. over 1 hour. After completion of the dropwise addition, triisopropylchlorosilane (96.4 g, 0.50 mol) was added dropwise at 25 ° C. over 1 hour. 120 ml of toluene had to be added because the salt formed during the addition made stirring difficult. After the addition was completed, the reaction solution was stirred at 50 ° C. for 5 hours. Thereafter, the reaction solution was cooled to room temperature, and the resulting triethylamine hydrochloride was separated by filtration and distilled. 101.8 g of triisopropylsilyl acrylate was obtained as a fraction having a boiling point of 110-111 ° C./1.3 kPa (89% yield).
[0023]
【The invention's effect】
Advantageous Effects of Invention According to the present invention, by using inexpensive and industrially available ammonia as a hydrochloric acid scavenger, it is possible to efficiently and efficiently produce silyl (meth) acrylate without substantially using a solvent and with good yield. Can be.
Claims (4)
Ｒ１Ｒ２Ｒ３ＳｉＣｌ （１）
（式中、Ｒ１、Ｒ２、Ｒ３は、互いに同一又は異なる炭素数１〜１０の１価炭化水素基を示す。）
で示されるクロロシラン化合物と、アクリル酸又はメタクリル酸とを反応させ、下記一般式（２）
で示されるシリル（メタ）アクリレート化合物を製造する方法において、上記反応をアンモニアの存在下で行うことを特徴とする、上記一般式（２）で示されるシリル（メタ）アクリレート化合物の製造方法。The following general formula (1)
R 1 R 2 R 3 SiCl (1)
(In the formula, R 1 , R 2 , and R 3 represent the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms.)
Is reacted with acrylic acid or methacrylic acid to obtain the following general formula (2)
A method for producing a silyl (meth) acrylate compound represented by the general formula (2), wherein the reaction is carried out in the presence of ammonia.
Ｒ１Ｒ２Ｒ３ＳｉＣｌ （１）
で示されるクロロシラン化合物のＲ１、Ｒ２、Ｒ３置換基が、互いに同一又は異なるα位に炭化水素基を有する炭素数３〜１０の１価の分岐状炭化水素基又は炭素数３〜１０の１価の環状炭化水素基である、請求項１又は２記載のシリル（メタ）アクリレート化合物の製造方法。The following general formula (1)
R 1 R 2 R 3 SiCl (1)
Wherein the R 1 , R 2 , and R 3 substituents of the chlorosilane compound represented by the formula ( 1) are the same or different, and each have a hydrocarbon group at the α-position. The method for producing a silyl (meth) acrylate compound according to claim 1, wherein the monovalent cyclic hydrocarbon group is a monovalent cyclic hydrocarbon group.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012512219A (en) * | 2008-12-16 | 2012-05-31 | ビーエーエスエフ ソシエタス・ヨーロピア | Silylation of monocarboxylic acids |
| JP2013520452A (en) * | 2010-02-25 | 2013-06-06 | エボニック デグサ ゲーエムベーハー | Carboxy-functionalized silicon-containing precursor compounds of various organic carboxylic acids |
| JP5434913B2 (en) * | 2008-05-16 | 2014-03-05 | 旭硝子株式会社 | Polymerizable compound, photocurable composition, optical element and optical head device |
| CN103709190A (en) * | 2014-01-08 | 2014-04-09 | 浙江胡涂硅有限公司 | Method for preparing triisopropyl silicon acrylate |
| JP2016501951A (en) * | 2012-12-19 | 2016-01-21 | ヨトゥン アーエス | Silyl ester copolymer |
-
2002
- 2002-06-21 JP JP2002180859A patent/JP4178369B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5434913B2 (en) * | 2008-05-16 | 2014-03-05 | 旭硝子株式会社 | Polymerizable compound, photocurable composition, optical element and optical head device |
| JP2012512219A (en) * | 2008-12-16 | 2012-05-31 | ビーエーエスエフ ソシエタス・ヨーロピア | Silylation of monocarboxylic acids |
| JP2013520452A (en) * | 2010-02-25 | 2013-06-06 | エボニック デグサ ゲーエムベーハー | Carboxy-functionalized silicon-containing precursor compounds of various organic carboxylic acids |
| JP2016501951A (en) * | 2012-12-19 | 2016-01-21 | ヨトゥン アーエス | Silyl ester copolymer |
| CN103709190A (en) * | 2014-01-08 | 2014-04-09 | 浙江胡涂硅有限公司 | Method for preparing triisopropyl silicon acrylate |
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