JP3009327B2 - Method for producing 2-alkoxysilylpropionate - Google Patents
Method for producing 2-alkoxysilylpropionateInfo
- Publication number
- JP3009327B2 JP3009327B2 JP6088420A JP8842094A JP3009327B2 JP 3009327 B2 JP3009327 B2 JP 3009327B2 JP 6088420 A JP6088420 A JP 6088420A JP 8842094 A JP8842094 A JP 8842094A JP 3009327 B2 JP3009327 B2 JP 3009327B2
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- butyl
- mol
- reaction
- alkoxysilylpropionate
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 7
- -1 acrylate ester Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 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 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- WTCRPVQWYABJEI-UHFFFAOYSA-N [Pt+] Chemical compound [Pt+] WTCRPVQWYABJEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- MAWLKRJXJGHDRD-UHFFFAOYSA-N ethene;platinum Chemical compound [Pt].C=C MAWLKRJXJGHDRD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 claims 1
- ADCFFIGZZVYRNB-UHFFFAOYSA-N silyl propanoate Chemical compound CCC(=O)O[SiH3] ADCFFIGZZVYRNB-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 13
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 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 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- QLUSTQCLSFYRMI-UHFFFAOYSA-N 2-ethylhexyl 2-trimethoxysilylpropanoate Chemical compound CCCCC(CC)COC(=O)C(C)[Si](OC)(OC)OC QLUSTQCLSFYRMI-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
- 239000007983 Tris buffer Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WGDQJBLQZYDQMH-UHFFFAOYSA-N ethyl 2-trimethoxysilylpropanoate Chemical compound CCOC(=O)C(C)[Si](OC)(OC)OC WGDQJBLQZYDQMH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はアクリル酸エステルとア
ルコキシシランとの反応により２−アルコキシシリルプ
ロピオン酸エステルを高収率で製造する方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a 2-alkoxysilylpropionate in a high yield by reacting an acrylate with an alkoxysilane.
【０００２】[0002]
【従来の技術】２−アルコキシシリルプロピオン酸エス
テルは、分子中のケイ素原子−炭素原子結合部分がシラ
ノール類やアルコール類と容易に反応するのでα，ω−
ジヒドロキシポリジメチルシロキサン等のオルガノポリ
シロキサンの末端アルコキシシリル化剤や脱アルコール
タイプＲＴＶ（常温加流性）ゴムの保存安定剤に利用さ
れている。2. Description of the Related Art 2-alkoxysilylpropionic acid esters have α, ω-, since the silicon-carbon atom bond in the molecule easily reacts with silanols or alcohols.
It is used as a terminal alkoxysilylating agent for organopolysiloxanes such as dihydroxypolydimethylsiloxane and as a storage stabilizer for dealcohol-type RTV (room temperature flowable) rubber.
【０００３】２−アルコキシシリルプロピオン酸エステ
ルはアクリル酸エステルとアルコキシシランとを反応さ
せて製造することができる。従来の製造方法は、下記反
応式(1)[0003] 2-Alkoxysilylpropionates can be prepared by reacting acrylic esters with alkoxysilanes. The conventional production method uses the following reaction formula (1)
【０００４】[0004]
【化１】 Embedded image
【０００５】に示されるようにハイドロシリル化触媒で
ある白金系触媒の存在下で、温度を６０℃〜１２０℃に
保ちながらアクリル酸エステルにメトキシシランを滴下
するというものである。As shown in the above, in the presence of a platinum-based catalyst which is a hydrosilylation catalyst, methoxysilane is added dropwise to an acrylate ester while maintaining the temperature at 60 ° C to 120 ° C.
【０００６】特開平5-155891号公報には２−アルコキシ
シリルプロピオン酸エステルの一種である２−トリメト
キシシリルプロピオン酸２−エチルヘキシルの製造方法
が記載されている。具体的には白金系触媒の存在下、温
度を８０℃〜９０℃に保ちながらアクリル酸２−エチル
ヘキシルにトリメトキシシランを滴下する方法である。
しかしながらこの方法ではアクリル酸２−エチルヘキシ
ルとトリメトキシシランとの反応が遅く、滴下したトリ
メトキシシランが未反応のまま残って蓄積されることが
ある。その後、未反応のトリメトキシシランとアクリル
酸２−エチルヘキシルとが一挙に反応して反応温度が急
に上昇しアクリル酸２−エチルヘキシルの重合や種々の
副反応が生じるという問題があった。このため製造上安
全性が高く、２−アルコキシシリルプロピオン酸エステ
ルを高収率で製造できる方法が望まれていた。Japanese Patent Application Laid-Open No. 5-155891 discloses a process for producing 2-ethylhexyl 2-trimethoxysilylpropionate which is a kind of 2-alkoxysilylpropionate. Specifically, it is a method in which trimethoxysilane is added dropwise to 2-ethylhexyl acrylate while maintaining the temperature at 80 ° C to 90 ° C in the presence of a platinum-based catalyst.
However, in this method, the reaction between 2-ethylhexyl acrylate and trimethoxysilane is slow, and the dropped trimethoxysilane may remain unreacted and accumulate. Thereafter, unreacted trimethoxysilane and 2-ethylhexyl acrylate react at once, causing a problem that the reaction temperature rises rapidly and polymerization of 2-ethylhexyl acrylate and various side reactions occur. Therefore, there has been a demand for a method which is highly safe in production and can produce 2-alkoxysilylpropionate in high yield.
【０００７】[0007]
【発明が解決しようとする課題】本発明は前記の課題を
解決するためなされたもので、反応が円滑に進行して副
反応が発生せず、収率がよい２−アルコキシシリルプロ
ピオン酸エステルの製造方法を提供することを目的とす
る。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the reaction proceeds smoothly without causing any side reaction and the yield of 2-alkoxysilylpropionate is high. It is intended to provide a manufacturing method.
【０００８】[0008]
【課題を解決するための手段】前記の目的を達成するた
めになされた本発明の２−アルコキシシリルプロピオン
酸エステルの製造方法は、白金系触媒および重合禁止剤
の存在下で、ＨＳｉＲ1 n（ＯＲ2 )3-nで示されるアルコ
キシシランに、ＣＨ2 ＣＨＣＯＯＲ3 で示されるアクリ
ル酸エステルを滴下して反応させ、反応温度を３０〜６
０℃に制御して、下記反応式(2) に示されるように２−
アルコキシシリルプロピオン酸エステルを製造する方法
である。The process for producing 2-alkoxysilylpropionate of the present invention, which has been made to achieve the above-mentioned object, comprises a process for preparing HSiR 1 n (HSiR 1 n ) in the presence of a platinum-based catalyst and a polymerization inhibitor. OR 2 ) 3-n , an acrylate ester represented by CH 2 CHCOOR 3 is dropped and reacted with the alkoxysilane represented by 3-n.
The temperature was controlled at 0 ° C., and as shown in the following reaction formula (2), 2-
This is a method for producing an alkoxysilylpropionate.
【０００９】[0009]
【化２】 Embedded image
【００１０】Ｒ1 およびＲ2 は炭素数１〜４の一価炭化
水素基であり、ｎは０〜２の整数である。炭素数１〜４
の一価炭化水素基はメチル基、エチル基、ｎ−プロピル
基、ｎ−ブチル基である。R 1 and R 2 are monovalent hydrocarbon groups having 1 to 4 carbon atoms, and n is an integer of 0 to 2. C 1-4
Are a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
【００１１】Ｒ3 は炭素数１〜１２の一価炭化水素基で
ある。炭素数１〜１２の一価炭化水素基は直鎖状、枝わ
かれ状、環状のいずれの構造でもよい。直鎖状の一価炭
化水素基には、例えばメチル基、エチル基、ｎ−プロピ
ル基、ｎ−ブチル基が挙げられる。枝わかれした鎖状の
一価炭化水素基にはｉ−プロピル基、ｉ−ブチル基、２
−エチルヘキシル基が挙げられる。環状の一価炭化水素
基にはシクロペンチル基、シクロヘキシル基が挙げられ
る。R 3 is a monovalent hydrocarbon group having 1 to 12 carbon atoms. The monovalent hydrocarbon group having 1 to 12 carbon atoms may have a linear, branched or cyclic structure. Examples of the linear monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Branched chain monovalent hydrocarbon groups include i-propyl group, i-butyl group,
-Ethylhexyl group. Examples of the cyclic monovalent hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
【００１２】白金系触媒は白金、その塩あるいはその錯
体である。白金塩には、例えば塩化白金酸、塩化白金酸
アルカリが挙げられる。白金錯体には、例えばビス（エ
チレン白金）クロライド、白金（Ｉ）アセチルアセトネ
ート、白金−ビニルシロキサン錯体が挙げられる。これ
らは単独で使用されても、混合して使用されてもよい。
白金系触媒の使用量については特に制限はないが、通常
はアクリル酸エステル１ｍｏｌに対して白金金属換算で
１μｍｏｌ〜１０００μｍｏｌが好ましい。１μｍｏｌ
以下の場合にはアルコキシシランとアクリル酸エステル
とが反応しにくくなる。１０００μｍｏｌ以上の場合に
は経済的に好ましくないばかりかそれだけの効果も認め
られない。The platinum-based catalyst is platinum, a salt thereof or a complex thereof. Examples of the platinum salt include chloroplatinic acid and alkali chloroplatinate. Examples of the platinum complex include bis (ethylene platinum) chloride, platinum (I) acetylacetonate, and platinum-vinylsiloxane complex. These may be used alone or as a mixture.
The amount of the platinum-based catalyst used is not particularly limited, but is usually preferably 1 μmol to 1000 μmol in terms of platinum metal per 1 mol of the acrylate ester. 1 μmol
In the following cases, it is difficult for the alkoxysilane and the acrylate to react. When the amount is 1000 μmol or more, not only is it economically undesirable, but no significant effect is observed.
【００１３】重合禁止剤にはフェノール類が使用され
る。フェノール類には、例えば２，６−ジ−ｔｅｒｔ−
ブチル−４−メチルフェノ−ル、２，６−ジ−ｔｅｒｔ
−ブチル−４−エチルフェノ−ル、２，６−ジ−ｔｅｒ
ｔ−ブチルフェノ−ル、２，２´−メチレン−ビス（６
−ｔｅｒｔ−ブチル−４−メチルフェノ−ル）、１，
３，５−トリメチル−２，４，６−トリス（３，５−ジ
−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼ
ン、モノメトキシハイドロキノンが挙げられる。これら
は単独で使用されても、混合して使用されてもよい。重
合禁止剤の使用量は特に制限はないが、通常はアクリル
酸エステル１ｍｏｌに対して０．０００１〜０．０１ｍ
ｏｌが好ましい。０．０００１ｍｏｌ以下の場合には、
アクリル酸エステルが重合する場合があり、２−アルコ
キシシリルプロピオン酸エステルの収率が低下してしま
う。０．０１ｍｏｌ以上の場合には、重合禁止剤を多量
に添加しただけの効果は発揮されない。Phenols are used as polymerization inhibitors. Phenols include, for example, 2,6-di-tert-
Butyl-4-methylphenol, 2,6-di-tert
-Butyl-4-ethylphenol, 2,6-di-ter
t-butylphenol, 2,2'-methylene-bis (6
-Tert-butyl-4-methylphenol), 1,
3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and monomethoxyhydroquinone. These may be used alone or as a mixture. The amount of the polymerization inhibitor used is not particularly limited, but is usually 0.0001 to 0.01 m per 1 mol of the acrylate ester.
ol is preferred. In the case of 0.0001 mol or less,
The acrylate may be polymerized, and the yield of 2-alkoxysilylpropionate decreases. When the amount is 0.01 mol or more, the effect of simply adding a large amount of the polymerization inhibitor is not exhibited.
【００１４】反応温度は３０〜６０℃、特に４０〜５０
℃が好ましい。反応温度が６０℃以上の場合には、種々
の副反応が増加して２−アルコキシシリルプロピオン酸
エステルの収率が低下し、原料のアルコキシシランの発
散、アクリル酸エステルの重合が生じることがある。反
応温度が３０℃以下の場合には、２−アルコキシシリル
プロピオン酸エステルの生成反応がおこりにくくなる。
しかしながら２０〜３０℃でアルコキシシランにアクリ
ル酸エステルを滴下すると、反応熱により反応系が４０
〜５０℃に上昇するので、この温度範囲を保ちつつアク
リル酸エステルの滴下を続け、２−アルコキシシリルプ
ロピオン酸エステルを生成することは可能である。[0014] The reaction temperature is 30 to 60 ° C, especially 40 to 50 ° C.
C is preferred. When the reaction temperature is 60 ° C. or higher, various side reactions increase, the yield of 2-alkoxysilylpropionate decreases, and emission of raw material alkoxysilane and polymerization of acrylic acid ester may occur. . When the reaction temperature is 30 ° C. or lower, the formation reaction of 2-alkoxysilylpropionic acid ester hardly occurs.
However, when the acrylic acid ester is dropped onto the alkoxysilane at 20 to 30 ° C., the reaction system becomes 40
Since the temperature rises to ５０50 ° C., it is possible to keep dropping the acrylate while maintaining this temperature range to produce 2-alkoxysilylpropionate.
【００１５】２−アルコキシシリルプロピオン酸エステ
ルの具体的な製造方法は以下の通りである。先ず、不活
性ガス、例えば窒素、アルゴンが充填されており空気や
水分が存在しない容器にアルコキシシラン、白金系触媒
およびフェノール類重合禁止剤を加える。容器中に窒素
を存在させたままアクリル酸エステルをアルコキシシラ
ンに滴下し、反応温度を３０〜６０℃に保ちながら反応
させる。得られた反応液を減圧蒸留して２−アルコキシ
シリルプロピオン酸エステルを製造する。A specific method for producing a 2-alkoxysilylpropionic acid ester is as follows. First, an alkoxysilane, a platinum-based catalyst, and a phenolic polymerization inhibitor are added to a container filled with an inert gas such as nitrogen or argon and free of air or moisture. Acrylic ester is added dropwise to alkoxysilane while nitrogen is present in the vessel, and the reaction is carried out while maintaining the reaction temperature at 30 to 60 ° C. The obtained reaction solution is distilled under reduced pressure to produce 2-alkoxysilylpropionate.
【００１６】[0016]
【発明の効果】本発明の２−アルコキシシリルプロピオ
ン酸エステルの製造方法ではアクリル酸エステルとアル
コキシシランとが円滑に反応するので、反応温度が突然
上昇したりすることがない。円滑な反応によって未反応
のアクリル酸エステルが減少しアクリル酸エステルの重
合および副反応が抑制され、目的物質である２−アルコ
キシシリルプロピオン酸エステルの収率が向上する。According to the method for producing 2-alkoxysilylpropionate of the present invention, the acrylate and alkoxysilane react smoothly, so that the reaction temperature does not suddenly rise. The unreacted acrylate decreases due to the smooth reaction, the polymerization and side reaction of the acrylate are suppressed, and the yield of the target substance, 2-alkoxysilylpropionate, is improved.
【００１７】[0017]
【実施例】以下、本発明の実施例を詳細に説明する。Embodiments of the present invention will be described below in detail.
【００１８】実施例１ 撹拌機、還流冷却管、温度計および滴下ロートを備えて
おり、窒素ガスで置換された２００ｍｌの四口フラスコ
に５８．２ｇ（０．４７６ｍｏｌ）のトリメトキシシラ
ン、０．９０ｇ（２３μｍｏｌ）の白金−１，３−ジビ
ニルテトラメチルジシロキサン錯体のトルエン溶液、
０．６３ｇ（０．８２ｍｍｏｌ）の１，３，５−トリメ
チル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）ベンゼン、０．６３ｇ
（２．９ｍｍｏｌ）の２，６−ジ−ｔｅｒｔ−ブチル−
４−メチルフェノールを入れ、窒素ガス存在下、撹拌加
熱しながら温度を４０℃に上昇させた。次いで、窒素ガ
ス存在下のまま温度を４０℃〜５０℃に保ち４５．０ｇ
（０．４４９ｍｏｌ）のアクリル酸エチルをトリメトキ
シシランに滴下した。滴下終了後、この反応系を４０℃
〜５０℃で２時間保持して反応を終了させ合成液の減圧
蒸留を行なうと、沸点９０〜９４℃／２０ｍｍＨｇの留
分が８７．７ｇ（アクリル酸エチルに対して収率８８
％）得られた。ガスクロマトグラフィー分析によれば、
この留分は主に下記式(3)、(4)、(5) に示される構造を有
する成分が含まれていた。Example 1 A 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel and purged with nitrogen gas was charged with 58.2 g (0.476 mol) of trimethoxysilane. 90 g (23 μmol) of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex,
0.63 g (0.82 mmol) of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 0.63 g
(2.9 mmol) of 2,6-di-tert-butyl-
4-Methylphenol was added, and the temperature was increased to 40 ° C. while stirring and heating in the presence of nitrogen gas. Next, the temperature was maintained at 40 ° C. to 50 ° C. in the presence of nitrogen gas and 45.0 g.
(0.449 mol) of ethyl acrylate was added dropwise to trimethoxysilane. After completion of the dropwise addition, the reaction system was heated to 40 ° C.
When the reaction was terminated by holding the mixture at ℃ 50 ° C. for 2 hours and the synthesis solution was distilled under reduced pressure, 87.7 g of a fraction having a boiling point of 90-94 ° C./20 mmHg (88% yield based on ethyl acrylate)
%) Obtained. According to gas chromatography analysis,
This fraction mainly contained components having the structures represented by the following formulas (3), (4) and (5).
【００１９】[0019]
【化３】 Embedded image
【００２０】[0020]
【化４】 Embedded image
【００２１】[0021]
【化５】 Embedded image
【００２２】クロマトグラムの面積比は(3) : (4) :
(5) = 93 : 4 : 3であった。The area ratio of the chromatogram is (3) :( 4):
(5) = 93: 4: 3.
【００２３】比較例１ 撹拌機、還流冷却管、温度計および滴下ロートを備えて
おり、窒素ガスで置換された２００ｍｌの四口フラスコ
に４５．０ｇ（０．４４９ｍｏｌ）のアクリル酸エチ
ル、０．９０ｇ（２３μｍｏｌ）の白金−１，３−ジビ
ニルテトラメチルジシロキサン錯体のトルエン溶液、
０．６３ｇ（０．８２ｍｍｏｌ）の１，３，５−トリメ
チル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブ
チル−４−ヒドロキシベンジル）ベンゼン、０．６３ｇ
（２．９ｍｍｏｌ）の２，６−ジ−ｔｅｒｔ−ブチル−
４−メチルフェノールを入れ、窒素ガス存在下、撹拌加
熱しながら温度を８０℃に上昇させた。次いで、窒素ガ
ス存在下のまま温度を８０℃〜９０℃に保ち５８．２ｇ
（０．４７６ｍｏｌ）のトリメトキシシランをアクリル
酸エチルに滴下した。トリメトキシシラン滴下中に、急
激に温度が１１０℃に上昇するという現象が見られた。
反応終了後、この合成液の減圧蒸留を行なうと、沸点９
０〜９９℃／２２ｍｍＨｇの留分が６３．３ｇ（アクリ
ル酸エチルに対して収率６３％）得られた。ガスクロマ
トグラフィー分析によれば、この留分は主に前記式(3)、
(4)、(5) に示される構造を有する成分が含まれていた。
クロマトグラムの面積比は(3) : (4) : (5) = 88 : 10
: 2 であった。Comparative Example 1 45.0 g (0.449 mol) of ethyl acrylate was placed in a 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. 90 g (23 μmol) of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex,
0.63 g (0.82 mmol) of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 0.63 g
(2.9 mmol) of 2,6-di-tert-butyl-
4-Methylphenol was added, and the temperature was increased to 80 ° C. while stirring and heating in the presence of nitrogen gas. Next, the temperature was maintained at 80 ° C. to 90 ° C. in the presence of nitrogen gas, and 58.2 g.
(0.476 mol) of trimethoxysilane was added dropwise to ethyl acrylate. During the dropping of trimethoxysilane, a phenomenon was observed in which the temperature rapidly increased to 110 ° C.
After completion of the reaction, the synthesis solution was subjected to distillation under reduced pressure to obtain a boiling point of 9%.
63.3 g (63% yield based on ethyl acrylate) of a fraction of 0 to 99 ° C / 22 mmHg was obtained. According to gas chromatography analysis, this fraction is mainly represented by the formula (3),
Components having the structures shown in (4) and (5) were included.
The area ratio of the chromatogram is (3): (4): (5) = 88: 10
: 2
【００２４】比較例２ 反応温度を８０〜９０℃に設定したことを除いて実施例
１と同様にして、合成液を調製した。反応温度が４０〜
５０℃で得られた実施例１の合成液と比較すると、反応
温度が８０〜９０℃で得られた比較例２の合成液のほう
が、明らかに２−トリメトキシシリルプロピオン酸エチ
ルの含有量が少なく、副生成物の含有量が多いことが確
認された。この合成液の減圧蒸留を行なうと沸点９０〜
１０６℃／１９ｍｍＨｇの留分が５７．８ｇ（アクリル
酸エチルに対しての収率５８％）得られた。Comparative Example 2 A synthetic solution was prepared in the same manner as in Example 1 except that the reaction temperature was set at 80 to 90 ° C. Reaction temperature 40 ~
Compared with the synthesis solution of Example 1 obtained at 50 ° C., the synthesis solution of Comparative Example 2 obtained at a reaction temperature of 80 to 90 ° C. has a clearly higher content of ethyl 2-trimethoxysilylpropionate. It was confirmed that the content was small and the content of by-products was large. When the synthesis liquid is subjected to distillation under reduced pressure, the boiling point is 90-90.
As a result, 57.8 g (yield based on ethyl acrylate of 58%) of 106 ° C./19 mmHg fraction was obtained.
【００２５】比較例３ 反応温度を２０〜３０℃に設定したことを除いて実施例
１と同様にして、合成液を調製した。アクリル酸エチル
を滴下して温度を２０〜３０℃に保ち、反応系を６時間
保持しても未反応のアクリル酸エチルが多量に残ってし
まった。合成液のガスクロマトグラフィー分析を行なう
と、実施例１の合成液のアクリル酸エチル含有量は２％
であるが、反応温度が２０〜３０℃で得られた合成液の
アクリル酸エチル含有量は１４％であった。２０〜３０
℃ではアクリル酸エチルとトリメトキシシランとの反応
速度がかなり遅くなっていることが確認された。Comparative Example 3 A synthetic solution was prepared in the same manner as in Example 1 except that the reaction temperature was set at 20 to 30 ° C. Even when ethyl acrylate was added dropwise to maintain the temperature at 20 to 30 ° C. and the reaction system was maintained for 6 hours, a large amount of unreacted ethyl acrylate remained. According to gas chromatography analysis of the synthesized solution, the content of ethyl acrylate in the synthesized solution of Example 1 was 2%.
However, the ethyl acrylate content of the synthesis solution obtained at a reaction temperature of 20 to 30 ° C. was 14%. 20-30
At ℃, it was confirmed that the reaction rate between ethyl acrylate and trimethoxysilane was considerably reduced.
【００２６】実施例２ 撹拌機、還流冷却管、温度計および２−エチルヘキシル
アクリレートフィード管を備えており、窒素ガスで置換
された５００リットルの反応容器に１３２ｋｇ（１０８
０ｍｏｌ）のトリメトキシシラン、２．８１ｋｇ（７２
ｍｍｏｌ）の白金−１，３−ジビニルテトラメチルジシ
ロキサン錯体のトルエン溶液、１．３３ｋｇ（１．７ｍ
ｏｌ）の１，３，５−トリメチル−２，４，６−トリス
（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベン
ジル）ベンゼン、１．３３ｋｇ（６．０ｍｏｌ）の２，
６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールを入
れ、窒素ガス存在下のまま撹拌加熱しながら室温で１７
０ｋｇ（９２４ｍｏｌ）のアクリル酸２−エチルヘキシ
ルを滴下した。その後、反応熱によって反応系を４０℃
〜５０℃に上昇させ、この温度範囲を保ちながらアクリ
ル酸２−エチルヘキシルを滴下した。滴下終了後、この
反応系を４０℃〜５０℃で３時間保持して反応を終了さ
せ合成液の減圧蒸留を行なうと、沸点１０７〜１１６℃
／２〜４ｍｍＨｇの留分２３１ｋｇ（アクリル酸２−エ
チルヘキシルに対して収率８２％）が得られた。ガスク
ロマトグラフィー分析によれば、この留分は主に下記式
(6)、(7)、(8) に示される構造を有する成分が含まれてい
た。Example 2 A 500-liter reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a 2-ethylhexyl acrylate feed tube was purged with 132 kg (108
0 mol) of trimethoxysilane, 2.81 kg (72
mmol) of a platinum-1,3-divinyltetramethyldisiloxane complex in 1.33 kg (1.7 m
ol) of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1.33 kg (6.0 mol) of 2,
6-Di-tert-butyl-4-methylphenol was added, and stirred at room temperature in the presence of nitrogen gas at room temperature for 17 hours.
0 kg (924 mol) of 2-ethylhexyl acrylate was added dropwise. Then, the reaction system is heated to 40 ° C. by the heat of the reaction.
５０50 ° C., and 2-ethylhexyl acrylate was added dropwise while maintaining this temperature range. After completion of the dropwise addition, the reaction system was maintained at 40 ° C. to 50 ° C. for 3 hours to terminate the reaction.
As a result, 231 kg of a fraction having a yield of 82% based on 2-ethylhexyl acrylate was obtained. According to gas chromatography analysis, this fraction is mainly
Components having the structures shown in (6), (7) and (8) were included.
【００２７】[0027]
【化６】 Embedded image
【００２８】[0028]
【化７】 Embedded image
【００２９】[0029]
【化８】 Embedded image
【００３０】クロマトグラムの面積比は（ (6)+(7)
） : (8) = 98 : 2 であった。The area ratio of the chromatogram is ((6) + (7)
): (8) = 98: 2.
【００３１】比較例４ 撹拌機、還流冷却管、温度計およびトリメトキシシラン
フィード管を備えており、窒素ガスで置換された５００
リットルの反応容器に１０５ｋｇ（５７１ｍｏｌ）のア
クリル酸２エチルヘキシル、１．１０ｋｇ（２８ｍｍｏ
ｌ）の白金−１，３−ジビニルテトラメチルジシロキサ
ン錯体のトルエン溶液、０．７８ｋｇ（１．０ｍｍｏ
ｌ）の１，３，５−トリメチル−２，４，６−トリス
（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベン
ジル）ベンゼン、０．７８ｋｇ（３．５ｍｏｌ）の２，
６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールを入
れ、窒素ガス存在下、撹拌加熱しながら温度を６０℃に
上昇させた。次いで、窒素ガス存在下のまま温度を６０
℃〜７０℃に保ち７８ｋｇ（６３８ｍｏｌ）のトリメト
キシシランをアクリル酸２エチルヘキシルに滴下した。
滴下終了後、７０℃〜８５℃でこの反応系を４時間保持
し反応を終了させ合成液の減圧蒸留を行なうと、沸点１
０９〜１１６℃／２〜３ｍｍＨｇの留分が１０６ｋｇ
（アクリル酸２−エチルヘキシルに対して収率６１％）
得られた。Comparative Example 4 A stirrer, a reflux condenser, a thermometer and a trimethoxysilane feed tube were provided.
In a liter reaction vessel, 105 kg (571 mol) of 2-ethylhexyl acrylate, 1.10 kg (28 mmol)
l) of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex of 0.78 kg (1.0 mmol)
l) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 0.78 kg (3.5 mol) of 2,
6-Di-tert-butyl-4-methylphenol was added, and the temperature was increased to 60 ° C. while stirring and heating in the presence of nitrogen gas. Next, the temperature was increased to 60 in the presence of nitrogen gas.
While maintaining the temperature at 70 ° C to 70 ° C, 78 kg (638 mol) of trimethoxysilane was added dropwise to 2-ethylhexyl acrylate.
After completion of the dropwise addition, the reaction system was maintained at 70 ° C. to 85 ° C. for 4 hours to terminate the reaction, and the synthesis solution was subjected to reduced pressure distillation.
106 kg of the fraction of 09-116 ° C / 2-3 mmHg
(61% yield based on 2-ethylhexyl acrylate)
Obtained.
【００３２】実施例３ 撹拌機、還流冷却管、温度計および２−エチルヘキシル
アクリレートフィード管を備えており、窒素ガスで置換
された２００ｍｌの四口フラスコに５８．４ｇ（０．５
５ｍｏｌ）のジメトキシメチルシラン、１．０１ｇ（２
６μｍｏｌ）の白金−１，３−ジビニルテトラメチルジ
シロキサン錯体のトルエン溶液、０．６５ｇの１，３，
５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ
ｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、
０．６５ｇの２，６−ジ−ｔｅｒｔ−ブチル−４−メチ
ルフェノールを入れ、窒素ガス存在下、撹拌加熱しなが
ら温度４３℃に上昇させた。次いで、窒素ガス存在下の
まま温度を４０〜５０℃に保ちながら９２．１ｇ（０．
５０ｍｏｌ）のアクリル酸２−エチルヘキシルをジメト
キシメチルシランに滴下した。滴下終了後、この反応系
を４０〜５０℃で２時間保持して反応を終了させ合成液
の減圧蒸留を行なうと、沸点９３〜１０２℃／２ｍｍＨ
ｇの留分が８４．４ｇ（アクリル酸２−エチルヘキシル
に対して収率７０％）得られた。ガスクロマトグラフィ
ー分析によれば、この留分は主に下記式(9)、(10)に示さ
れる構造を有する成分が含まれていた。Example 3 58.4 g (0.5 g) of a 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a 2-ethylhexyl acrylate feed tube, and purged with nitrogen gas.
5 mol) of dimethoxymethylsilane, 1.01 g (2
6 μmol) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex, 0.65 g of 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
tert-butyl-4-hydroxybenzyl) benzene,
0.65 g of 2,6-di-tert-butyl-4-methylphenol was added, and the temperature was raised to 43 ° C. while stirring and heating in the presence of nitrogen gas. Next, 92.1 g (0. 1 g) was maintained in the presence of nitrogen gas while maintaining the temperature at 40 to 50 ° C.
50 mol) of 2-ethylhexyl acrylate was added dropwise to dimethoxymethylsilane. After completion of the dropping, the reaction system was maintained at 40 to 50 ° C. for 2 hours to terminate the reaction, and the synthesis solution was subjected to distillation under reduced pressure.
84.4 g (yield 70% based on 2-ethylhexyl acrylate) was obtained. According to gas chromatography analysis, this fraction mainly contained a component having a structure represented by the following formulas (9) and (10).
【００３３】[0033]
【化９】 Embedded image
【００３４】[0034]
【化１０】 Embedded image
【００３５】クロマトグラムの面積比は(9) : (10) = 9
6 : 4 であった。The area ratio of the chromatogram is (9) :( 10) = 9
6: 4.
【００３６】比較例５ 撹拌機、還流冷却管、温度計および滴下ロートを備えて
おり、窒素ガスで置換された３リットルの四口フラスコ
に１４７４．２ｇ（８．０ｍｏｌ）のアクリル酸エチ
ル、１．２０ｇ（３１μｍｏｌ）の白金−１，３−ジビ
ニルテトラメチルジシロキサン錯体のトルエン溶液、
１．２ｇの１，３，５−トリメチル−２，４，６−トリ
ス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベ
ンジル）ベンゼン、１．２ｇの２，６−ジ−ｔｅｒｔ−
ブチル−４−メチルフェノールを入れ、窒素ガス存在
下、撹拌加熱しながら温度を８０℃に上昇させた。次い
で、窒素ガス存在下のまま温度を８０℃〜１００℃に保
ちながら９３４．６ｇ（８．８０ｍｏｌ）のジメトキシ
メチルシランをアクリル酸エチルに滴下した。滴下終了
後、８０℃〜９０℃で反応系を保持して反応を終了させ
合成液の減圧蒸留を行なうと、沸点１３８〜１４２℃／
６ｍｍＨｇの留分が１０８０．０ｇ（アクリル酸２−エ
チルヘキシルに対して収率４７％）得られた。ガスクロ
マトグラフィー分析によれば、この留分中に式(9) で示
される化合物は８９％であった。Comparative Example 5 1474.2 g (8.0 mol) of ethyl acrylate was placed in a 3 liter four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. .20 g (31 μmol) of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex,
1.2 g of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1.2 g of 2,6-di-tert-
Butyl-4-methylphenol was added, and the temperature was increased to 80 ° C. while stirring and heating in the presence of nitrogen gas. Next, 934.6 g (8.80 mol) of dimethoxymethylsilane was added dropwise to ethyl acrylate while maintaining the temperature at 80 ° C. to 100 ° C. in the presence of nitrogen gas. After completion of the dropwise addition, the reaction system is maintained at 80 ° C. to 90 ° C. to terminate the reaction, and the resultant solution is subjected to distillation under reduced pressure.
1080.0 g (yield: 47% based on 2-ethylhexyl acrylate) of 6 mmHg fraction was obtained. According to gas chromatography analysis, the content of the compound represented by the formula (9) was 89% in this fraction.
───────────────────────────────────────────────────── 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 の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 の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５−155891（ＪＰ，Ａ) 特開 平７−258274（ＪＰ，Ａ) 特開 昭61−158988（ＪＰ，Ａ) 特開 昭62−283983（ＪＰ，Ａ) 「化学実験法」（1970−７−10）東京 化学同人，第209−212頁. (58)調査した分野(Int.Cl.7，ＤＢ名) C07F 7/18 ＣＡＰＬＵＳ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩＤＳ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Yamamoto 1 at 28 Nishifukushima, Nishifukushima, Nakakushijo-gun, Niigata Pref. Shinetsu Chemical Industry Co., Ltd. Synthetic Technology Research Center (72) Inventor Mikio Endo No. 28, Nishifukushima, Kushiro-mura, Japan Shin-Etsu Chemical Co., Ltd., Synthetic Technology Laboratory (56) Reference 158988 (JP, A) JP-A-62-283983 (JP, A) "Chemical Experimental Methods" (1970-7-10) Tokyo Chemical Dojin, pp. 209-212. (58) Fields investigated (Int. . 7, DB name) C07F 7/18 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)
Claims (4)
で、ＨＳｉＲ1 n（ＯＲ2 )3-n（式中のＲ1 およびＲ2 は
炭素数１〜４の一価炭化水素基、ｎは０〜２の整数）で
示されるアルコキシシランに、ＣＨ2 ＣＨＣＯＯＲ3
（式中のＲ3 は炭素数１〜１２の一価炭化水素基）で示
されるアクリル酸エステルを滴下して反応させ、反応温
度を４０〜５０℃に制御することを特徴とする２−アル
コキシシリルプロピオン酸エステルの製造方法。1. In the presence of a platinum-based catalyst and a polymerization inhibitor, HSiR 1 n (OR 2 ) 3-n (wherein R 1 and R 2 are monovalent hydrocarbon groups having 1 to 4 carbon atoms, n Is an integer of 0 to 2), and CH 2 CHCOOR 3
(R 3 in the formula is a monovalent hydrocarbon group having 1 to 12 carbon atoms) An acrylic acid ester represented by the formula (1) is dropped and reacted, and the reaction temperature is controlled at 40 to 50 ° C. A method for producing a silyl propionate.
酸アルカリ、ビス（エチレン白金）クロライド、白金
（Ｉ）アセチルアセトネート、白金−ビニルシロキサン
錯体から選ばれる少なくとも１種類の触媒であり、その
触媒の量がアクリル酸エステル１ｍｏｌに対して白金金
属換算で１μｍｏｌ〜１０００μｍｏｌであることを特
徴とする請求項１に記載の２−アルコキシシリルプロピ
オン酸エステルの製造方法。2. The platinum-based catalyst is at least one catalyst selected from chloroplatinic acid, alkali chloroplatinate, bis (ethylene platinum) chloride, platinum (I) acetylacetonate, and platinum-vinylsiloxane complex, The method for producing 2-alkoxysilylpropionate according to claim 1, wherein the amount of the catalyst is 1 μmol to 1000 μmol in terms of platinum metal per 1 mol of the acrylate.
−ブチル−４−メチルフェノ−ル、２，６−ジ−ｔｅｒ
ｔ−ブチル−４−エチルフェノ−ル、２，６−ジ−ｔｅ
ｒｔ−ブチルフェノ−ル、２，２´−メチレン−ビス
（６−ｔｅｒｔ−ブチル−４−メチルフェノ−ル）、
１，３，５−トリメチル−２，４，６−トリス（３，５
−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベ
ンゼン、モノメトキシハイドロキノンから選ばれる少な
くとも１種類のフェノール類であり、その重合禁止剤の
量がアクリル酸エステル１ｍｏｌに対して０．０００１
〜０．０１ｍｏｌであることを特徴とする請求項１また
は２に記載の２−アルコキシシリルプロピオン酸エステ
ルの製造方法。3. The method according to claim 2, wherein the polymerization inhibitor is 2,6-di-tert.
-Butyl-4-methylphenol, 2,6-di-ter
t-butyl-4-ethylphenol, 2,6-di-te
rt-butylphenol, 2,2'-methylene-bis (6-tert-butyl-4-methylphenol),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene and at least one phenol selected from monomethoxyhydroquinone, and the amount of the polymerization inhibitor is 0.0001 to 1 mol of the acrylate ester.
The method for producing a 2-alkoxysilylpropionate according to claim 1 or 2, wherein the amount is from 0.01 to 0.01 mol.
内で行うことを特徴とする請求項１〜３のいずれかに記
載の２−アルコキシシリルプロピオン酸エステルの製造
方法。4. The method for producing a 2-alkoxysilylpropionate according to claim 1, wherein the reaction is carried out in a vessel filled with an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6088420A JP3009327B2 (en) | 1994-04-26 | 1994-04-26 | Method for producing 2-alkoxysilylpropionate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6088420A JP3009327B2 (en) | 1994-04-26 | 1994-04-26 | Method for producing 2-alkoxysilylpropionate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07291980A JPH07291980A (en) | 1995-11-07 |
| JP3009327B2 true JP3009327B2 (en) | 2000-02-14 |
Family
ID=13942298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6088420A Expired - Fee Related JP3009327B2 (en) | 1994-04-26 | 1994-04-26 | Method for producing 2-alkoxysilylpropionate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3009327B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5051392B2 (en) * | 2008-10-02 | 2012-10-17 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition and automotive control device sealed with the composition |
| JP5046404B2 (en) * | 2009-09-25 | 2012-10-10 | 信越化学工業株式会社 | One-end reactive organopolysiloxane having a polyalkylene oxide group at the ω end and a method for producing the same. |
| US11884820B2 (en) * | 2018-08-03 | 2024-01-30 | Shin-Etsu Chemical Co., Ltd. | Silicone gel composition and cured product thereof, and power module |
-
1994
- 1994-04-26 JP JP6088420A patent/JP3009327B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 「化学実験法」（１９７０−７−１０）東京化学同人，第２０９−２１２頁． |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07291980A (en) | 1995-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0312075B2 (en) | ||
| FR2551066A1 (en) | HYDROSILYLATION CATALYST AND HYDROSILYLATION METHOD | |
| US6815554B2 (en) | Process for preparing unsaturated organosilicon compounds | |
| EP1237894B1 (en) | Process for producing epoxyorganosilicon compounds | |
| JP3651572B2 (en) | Process for producing partially added cyclic organohydrogensiloxane | |
| EP3195932A1 (en) | Hydrosilylation reaction catalyst | |
| JP2837190B2 (en) | Stabilization method of organosilane having methacryloxy group or acryloxy group | |
| JPH089005B2 (en) | Method for producing hydrosilylation catalyst | |
| JP2002501925A (en) | New amino organofunctional siloxanes | |
| CN101039949B (en) | Method of producing silylalkoxymethyl halide | |
| JPH07145177A (en) | Synthesizing method for beta-cyanoalkylsilane | |
| JP3009327B2 (en) | Method for producing 2-alkoxysilylpropionate | |
| JP3555646B2 (en) | Method for producing chlorosilane containing acryloxy group or methacryloxy group | |
| JP5333971B2 (en) | Process for producing organosilicon compound containing β-cyanoester group | |
| JP6908453B2 (en) | Organoxysiloxane production method and boron compounds | |
| JP4009335B2 (en) | Method for producing organosilicon compound containing acryloxy group or methacryloxy group | |
| EP0656363A1 (en) | Process for preparing a silane having a tertiary hydrocarbon group at the alpha position thereof | |
| JP3122358B2 (en) | Method for producing 3-chloropropylsilanes | |
| JP2775239B2 (en) | Catalytic alkylation method | |
| JP2507251B2 (en) | 2-trimethoxysilylpropionate | |
| JP2864866B2 (en) | Method for producing organosilicon compound | |
| JP3856087B2 (en) | Method for producing 3-aminopropyl monoorganodiorganooxysilane | |
| JPH0631272B2 (en) | Manufacturing method of silyl ketene acetal | |
| JP3823337B2 (en) | Method for producing γ- (meth) acryloxypropylsilane compound | |
| JP5102950B2 (en) | Method for producing amine compound by reduction of amide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081203 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091203 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101203 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101203 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111203 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111203 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121203 Year of fee payment: 13 |
|
| LAPS | Cancellation because of no payment of annual fees |