JPH0770152A - Production of acyloxysilane - Google Patents
Production of acyloxysilaneInfo
- Publication number
- JPH0770152A JPH0770152A JP5219810A JP21981093A JPH0770152A JP H0770152 A JPH0770152 A JP H0770152A JP 5219810 A JP5219810 A JP 5219810A JP 21981093 A JP21981093 A JP 21981093A JP H0770152 A JPH0770152 A JP H0770152A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- acyloxysilane
- group
- fatty acid
- higher fatty
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 6
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 24
- 229930195729 fatty acid Natural products 0.000 abstract description 24
- 239000000194 fatty acid Substances 0.000 abstract description 24
- 150000004665 fatty acids Chemical class 0.000 abstract description 23
- -1 ethyl vinyl Chemical group 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 2
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- NLSDDIVVUMPRGE-UHFFFAOYSA-N dimethyl-di(tetradecoxy)silane Chemical compound CCCCCCCCCCCCCCO[Si](C)(C)OCCCCCCCCCCCCCC NLSDDIVVUMPRGE-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IFTYUSQBMVJBDK-UHFFFAOYSA-N 1-trimethylsilyloctadecan-1-one Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[Si](C)(C)C IFTYUSQBMVJBDK-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- KJDZDTDNIULJBE-QXMHVHEDSA-N cetoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCCCC(O)=O KJDZDTDNIULJBE-QXMHVHEDSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005472 straight-chain saturated fatty acid group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高級脂肪酸アシロキシ
シランの製造方法に関し、特に反応が簡便で高純度、高
収率で得られる製造方法に関する。高級脂肪酸アシロキ
シシランは、高級脂肪酸シリルエステルであり、樹脂組
成物の添加剤として各種組成物の特性の改善に用いられ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a higher fatty acid acyloxysilane, and more particularly to a method for producing a simple reaction with high purity and high yield. The higher fatty acid acyloxysilane is a higher fatty acid silyl ester, and is used as an additive for a resin composition to improve the properties of various compositions.
【０００２】[0002]
【従来の技術】従来、アシロキシシランの製造法として
は多くのものが知られている。その代表的な方法は、 １）ハロゲン化シラン化合物とカルボン酸とを反応させ
る方法（特開昭５４−１０３５００号公報に記載の方
法） Ｓｉ--Ｃｌ＋ＲＣＯＯＨ → ＳｉＯＣＯＲ＋ＨＣｌ ２）ハロゲン化シランとカルボン酸のアルカリ金属塩と
を反応させる方法 Ｓｉ--Ｃｌ＋ＲＣＯＯＭ → ＳｉＯＣＯＲ＋ＭＣｌ ３）アルコキシシラン化合物とカルボン酸を酸性又はア
ルカリ性の触媒の存在下で反応させる方法 ＳｉＯＲ＋ＲＣＯＯＨ → ＳｉＯＣＯＲ＋ＲＯＨ などを挙げることができる。2. Description of the Related Art Conventionally, many methods of producing acyloxysilane are known. Typical methods are: 1) Method of reacting halogenated silane compound with carboxylic acid (method described in JP-A-54-103500) Si--Cl + RCOOH → SiOCOR + HCl 2) Halogenated silane and carboxylic acid Method of reacting with alkali metal salt Si--Cl + RCOOM → SiOCOR + MCl 3) Method of reacting alkoxysilane compound and carboxylic acid in the presence of an acidic or alkaline catalyst SiOR + RCOOH → SiOCOR + ROH and the like can be mentioned.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
の従来法では、特に炭素数が６以上の高級脂肪酸アシロ
キシシランの製造においては多くの欠点を有する。１）
の方法では炭素数の少ないカルボン酸を使用する場合は
連続生産できるが、高級脂肪酸を使用する場合は反応に
多くの時間がかかる。また、ピリジン、トリエチルアミ
ンなどを脱塩化水素剤として使用すると、容易に反応は
進行するが、副生する塩酸塩を完全に取り除くのが困難
である。２）の方法では高級脂肪酸のアルカリ金属塩を
使用すると、生成する金属塩が微粒子状に分散している
ため取り除くのが非常に困難である。３）の方法では、
高級脂肪酸を使用すると、その反応性が低いため時間が
かかり、また触媒に使用した酸、アルカリを除くのが困
難である。以上の様に高級脂肪酸アシロキシシランの製
造においては、高級脂肪酸の反応性の低さ、あるいはア
シロキシシランが高沸点のため蒸留精製ができないこと
による不純物の混入などの問題がある。However, these conventional methods have many drawbacks, particularly in the production of higher fatty acid acyloxysilane having 6 or more carbon atoms. 1)
In the above method, continuous production can be performed when a carboxylic acid having a small number of carbon atoms is used, but when a higher fatty acid is used, the reaction takes a lot of time. When pyridine, triethylamine or the like is used as a dehydrochlorinating agent, the reaction proceeds easily, but it is difficult to completely remove the by-produced hydrochloride. In the method 2), when an alkali metal salt of higher fatty acid is used, it is very difficult to remove it because the metal salt produced is dispersed in fine particles. In the method of 3),
When a higher fatty acid is used, its reactivity is low and it takes time, and it is difficult to remove the acid and alkali used for the catalyst. As described above, in the production of higher fatty acid acyloxysilane, there is a problem that reactivity of higher fatty acid is low, or impurities cannot be mixed because the acyloxysilane cannot be purified by distillation because of high boiling point.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記従来技術
の問題点を解決するため低級脂肪酸アシロキシシランと
炭素数が６以上の高級脂肪酸とを反応させると、炭素数
が６以上の高級脂肪酸のアルキル基がアシロキシシラン
の低級アルキル基部分に置換され、短時間の反応により
高純度、高収率の高級脂肪酸アシロキシシランが得られ
ることを知見し、本発明に至ったものである。本発明の
目的は、簡便な製造法により短時間の反応で、高純度、
高収率で高級脂肪酸アシロキシシランを製造する方法を
提供することにある。すなわち本発明は、下記式（１）
で表される硅素化合物と、下記式（２）で表される炭素
数６以上のカルボン酸とを反応させ、下記式（３）で表
される高級脂肪酸アシロキシシランを製造する。 （Ｒ1 ＣＯＯ）n ＳｉＲ2 4-n ＋ ｎＲ3 ＣＯＯＨ 式（１） 式（２） → （Ｒ3 ＣＯＯ）n ＳｉＲ 2 4-n ＋ ｎＲ1 ＣＯＯＨ 式（３） 式中Ｒ1 は水素、メチル基またはエチル基を表し、Ｒ 2
はメチル基、エチル基、ビニル基、アリル基またはフェ
ニル基を表し、Ｒ3 はＣ6 〜Ｃ30の一価または二価の炭
化水素基を表し、ｎは１〜４の整数である。In order to solve the above-mentioned problems of the prior art, the present invention comprises reacting a lower fatty acid acyloxysilane with a higher fatty acid having 6 or more carbon atoms to obtain a higher fatty acid having 6 or more carbon atoms. The present inventors have found that the alkyl group of fatty acid is substituted with the lower alkyl group of acyloxysilane, and a high-purity, high-yield higher fatty acid acyloxysilane can be obtained by a reaction in a short time, which led to the present invention. . The object of the present invention is a simple production method, a short reaction time, high purity,
It is to provide a method for producing a higher fatty acid acyloxysilane in a high yield. That is, the present invention provides the following formula (1)
The higher fatty acid acyloxysilane represented by the following formula (3) is produced by reacting the silicon compound represented by the following with the carboxylic acid represented by the following formula (2) and having 6 or more carbon atoms. (R 1 COO) n SiR 2 4-n + nR 3 COOH Formula (1) Formula (2) → (R 3 COO) n SiR 2 4-n + nR 1 COOH Formula (3) In the formula, R 1 is hydrogen, Represents a methyl group or an ethyl group, R 2
Represents a methyl group, an ethyl group, a vinyl group, an allyl group or a phenyl group, R 3 represents a C 6 to C 30 monovalent or divalent hydrocarbon group, and n is an integer of 1 to 4.
【０００５】以下に、本発明を詳細に説明する。本発明
に用いる式（１）で表される硅素化合物は、低級アルキ
ル基をもつ脂肪酸アシロキシシランである。 （Ｒ1 ＣＯＯ）n ＳｉＲ2 4-n ・・・・ 式（１） Ｒ1 は水素、メチル基またはエチル基を表し、Ｒ2 はメ
チル基、エチル基、ビニル基、アリル基またはフェニル
基を表し、ｎは１〜４の整数である。具体的には、ジメ
チルジアセトキシシラン、メチルトリアセトキシシラ
ン、またはビニルトリアセトキシシラン化合物が例示さ
れる。The present invention will be described in detail below. The silicon compound represented by the formula (1) used in the present invention is a fatty acid acyloxysilane having a lower alkyl group. (R 1 COO) n SiR 2 4-n ... Formula (1) R 1 represents hydrogen, a methyl group or an ethyl group, and R 2 represents a methyl group, an ethyl group, a vinyl group, an allyl group or a phenyl group. Where n is an integer of 1 to 4. Specifically, a dimethyl diacetoxy silane, a methyl triacetoxy silane, or a vinyl triacetoxy silane compound is illustrated.
【０００６】本発明に用いる式（２）で表されるカルボ
ン酸Ｒ3 ＣＯＯＨは、炭素数６〜３０の高級カルボン酸
であり、カプリル酸、ペラルゴン酸、カプリン酸、ウン
デカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、
ステアリン酸、アラキン酸、ベヘン酸、リグノセリン
酸、セロチン酸、モンタン酸、メリシン酸などの直鎖飽
和脂肪酸；カプロレイン酸、オレイン酸、セトレイン
酸、ソルビン酸、リノール酸、リノレン酸などの不飽和
脂肪酸；安息香酸、フェニル酢酸などの芳香族カルボン
酸等のカルボン酸が例示される。The carboxylic acid R 3 COOH represented by the formula (2) used in the present invention is a higher carboxylic acid having 6 to 30 carbon atoms, and is caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristin. Acid, palmitic acid,
Straight-chain saturated fatty acids such as stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melissic acid; unsaturated fatty acids such as caproleic acid, oleic acid, cetoleic acid, sorbic acid, linoleic acid, linolenic acid; Examples thereof include carboxylic acids such as benzoic acid and aromatic carboxylic acids such as phenylacetic acid.
【０００７】反応は、発生する低級脂肪酸Ｒ1 ＣＯＯＨ
を反応系から除去することにより、式（３）で表される
高級脂肪酸アシロキシシランを得る。反応条件は特に限
定されないが、２００ｍｍＨｇ〜０．１ｍｍＨｇの減圧
下に式（１）と式（２）の化合物を室温〜１５０℃の温
度で加熱攪拌し、発生する低級脂肪酸を除去して行うの
がよい。溶媒は用いても用いなくてもよいが、用いる場
合は、反応に不活性な活性水素を持たない有機溶媒が好
ましく、ヘキサン、ヘプタン、ベンゼン、トルエン、キ
シレン、塩化メチレン、クロロホルムなどが挙げられ
る。特に、副生する低級カルボン酸と式（１）の硅素化
合物の沸点が近い場合は、有機溶媒で低級カルボン酸を
共沸させる方が望ましい。The reaction is a lower fatty acid R 1 COOH generated
Is removed from the reaction system to obtain a higher fatty acid acyloxysilane represented by the formula (3). The reaction conditions are not particularly limited, but the reaction is performed by heating and stirring the compounds of formulas (1) and (2) at room temperature to 150 ° C. under reduced pressure of 200 mmHg to 0.1 mmHg to remove the generated lower fatty acid. Is good. Although the solvent may or may not be used, when it is used, an organic solvent having no active hydrogen inert to the reaction is preferable, and examples thereof include hexane, heptane, benzene, toluene, xylene, methylene chloride, chloroform and the like. Particularly, when the boiling point of the by-produced lower carboxylic acid and the silicon compound of the formula (1) are close to each other, it is preferable to azeotropically distill the lower carboxylic acid with an organic solvent.
【０００８】以上の本発明の製造方法で得られる式
（３）の化合物は、（Ｒ3 ＣＯＯ）n ＳｉＲ 2 4-n で示
される高級脂肪酸アシロキシシランであり、具体的に
は、トリパルミトイルオキシビニルシラン、ジミリスチ
ルオキシジメチルシラン、ジステアロイルオキシジメチ
ルシラン、トリステアロイルオキシビニルシラン、ステ
アロイルトリメチルシランが例示される。これらの高級
脂肪酸アシロキシシランは、樹脂組成物の改質剤、チク
ソ性付与剤、貯蔵安定化剤に有用に用いられる。The compound of the formula (3) obtained by the above-mentioned production method of the present invention is a higher fatty acid acyloxysilane represented by (R 3 COO) n SiR 2 4-n , specifically, tripalmitoyl. Examples thereof include oxyvinylsilane, dimyristyloxydimethylsilane, distearoyloxydimethylsilane, tristearoyloxyvinylsilane and stearoyltrimethylsilane. These higher fatty acid acyloxysilanes are usefully used as modifiers of resin compositions, thixotropy imparting agents, and storage stabilizers.
【０００９】[0009]
【実施例】以下に、実施例により本発明を具体的に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。 （実施例１）パルミチン酸１００ｇ（０．３９０モル）
とトリアセトキシビニルシラン３０．２ｇ（０．１３モ
ル）の混合物を１１０℃、減圧下（４０ｍｍＨｇ）で加
熱攪拌したところ、酢酸の発生が見られた。１時間後に
減圧度を２ｍｍＨｇにし、酢酸を完全に除去した。理論
量の１０６．５ｇ（１００％）のトリパルミトイルオキ
シビニルシランが得られた。 1ＨＮＭＲにより求められ
た純度は９８％であった。 （実施例２）ミリスチン酸１００ｇ（０．４３８モ
ル）、ジアセトキシジメチルシラン３８．６ｇ（０．２
１９モル）、ｎ−ヘキサン５０ｍｌの混合物を９０℃で
生成する。酢酸をｎ−ヘキサンで共沸除去しながら加熱
攪拌した。１時間後、さらにｎ−ヘキサンを３０ｍｌ加
え、酢酸を共沸除去した。その後、減圧下（２ｍｍＨ
ｇ）で、残存するｎ−ヘキサン、酢酸を完全に除去し、
理論量１１２．０ｇ（１００％）のジミリスチルオキシ
ジメチルシランを得た。純度は９８％であった。 （実施例３）安息香酸１００ｇ（０．８１９モル）、ト
リアセチルメチルシラン６０．１ｇ（０．２７３モ
ル）、ｎ−ヘキサン５０ｍｌを用い、実施例２と同様に
トリベンゾイルオキシメチルシランを合成した。収率１
００％、純度９７％であった。実施例１〜３で得られた
化合物は下記構造式で示される。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. (Example 1) Palmitic acid 100 g (0.390 mol)
When a mixture of and 30.2 g (0.13 mol) of triacetoxyvinylsilane was heated and stirred at 110 ° C. under reduced pressure (40 mmHg), generation of acetic acid was observed. After 1 hour, the degree of vacuum was set to 2 mmHg to completely remove acetic acid. A theoretical amount of 106.5 g (100%) of tripalmitoyloxyvinylsilane was obtained. The purity determined by 1 HNMR was 98%. (Example 2) Myristic acid 100 g (0.438 mol) and diacetoxydimethylsilane 38.6 g (0.2
19 mol) and 50 ml of n-hexane at 90 ° C. The mixture was heated and stirred while azeotropically removing acetic acid with n-hexane. After 1 hour, 30 ml of n-hexane was further added to azeotropically remove acetic acid. Then, under reduced pressure (2 mmH
In g), the remaining n-hexane and acetic acid were completely removed,
A theoretical amount of 112.0 g (100%) of dimyristyloxydimethylsilane was obtained. The purity was 98%. (Example 3) Tribenzoyloxymethylsilane was synthesized in the same manner as in Example 2 using 100 g (0.819 mol) of benzoic acid, 60.1 g (0.273 mol) of triacetylmethylsilane and 50 ml of n-hexane. . Yield 1
The purity was 00% and the purity was 97%. The compounds obtained in Examples 1 to 3 are represented by the following structural formulas.
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】[0011]
【発明の効果】本発明の製造方法は、触媒等を用いない
ため従来法に比して特別な精製工程が不要で反応が簡便
であり反応時間が短い。また高級脂肪酸アシロキシシラ
ンが高純度、高収率で得られる。EFFECTS OF THE INVENTION Since the production method of the present invention does not use a catalyst or the like, the reaction is simple and the reaction time is short as compared with the conventional method because no special purification step is required. Further, the higher fatty acid acyloxysilane can be obtained with high purity and high yield.
Claims (1)
基、エチル基、ビニル基、アリル基、又はフェニル基で
ある。ｎは１〜４の整数である。）で表される硅素化合
物と 一般式 Ｒ3 ＣＯＯＨ （２） （Ｒ3 はＣ6 〜Ｃ30の一価又は二価の炭化水素基）で表
されるカルボン酸とを反応させることを特徴とするアシ
ロキシシランの製造方法。1. A compound represented by the general formula (R 1 COO) nSiR 2 4-n (1) (R 1 is a hydrogen group, a methyl group, an ethyl group, and R 2 is a methyl group, an ethyl group, a vinyl group, an allyl group, or phenyl. And a silicon compound represented by the general formula R 3 COOH (2) (R 3 is a C 6 to C 30 monovalent or divalent hydrocarbon group). A method for producing an acyloxysilane, which comprises reacting with a carboxylic acid represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5219810A JPH0770152A (en) | 1993-09-03 | 1993-09-03 | Production of acyloxysilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5219810A JPH0770152A (en) | 1993-09-03 | 1993-09-03 | Production of acyloxysilane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0770152A true JPH0770152A (en) | 1995-03-14 |
Family
ID=16741394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5219810A Withdrawn JPH0770152A (en) | 1993-09-03 | 1993-09-03 | Production of acyloxysilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0770152A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005503439A (en) * | 2001-09-21 | 2005-02-03 | シグマ・コーテイングス・ベー・ブイ | Preparation of organosilylated carboxylate monomers and their use in antifouling coatings |
| US7902313B2 (en) | 2003-03-26 | 2011-03-08 | Sigmakalon B.V. | Process for the preparation of poly(silyl ester)s, and their uses |
| US8153705B2 (en) | 2003-05-07 | 2012-04-10 | Sigmakalon B.V. | Silyl esters, their use in binder systems and paint compositions and a process for production thereof |
| 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 |
| US10316046B2 (en) | 2015-03-10 | 2019-06-11 | National Institute Of Advanced Industrial Science And Technology | Method for producing acyloxysilanes, acyloxysilanes obtained thereby, and use of same |
-
1993
- 1993-09-03 JP JP5219810A patent/JPH0770152A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005503439A (en) * | 2001-09-21 | 2005-02-03 | シグマ・コーテイングス・ベー・ブイ | Preparation of organosilylated carboxylate monomers and their use in antifouling coatings |
| US7902313B2 (en) | 2003-03-26 | 2011-03-08 | Sigmakalon B.V. | Process for the preparation of poly(silyl ester)s, and their uses |
| US8153705B2 (en) | 2003-05-07 | 2012-04-10 | Sigmakalon B.V. | Silyl esters, their use in binder systems and paint compositions and a process for production thereof |
| 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 |
| US10316046B2 (en) | 2015-03-10 | 2019-06-11 | National Institute Of Advanced Industrial Science And Technology | Method for producing acyloxysilanes, acyloxysilanes obtained thereby, and use of same |
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