JPH058714B2 - - Google Patents
Info
- Publication number
- JPH058714B2 JPH058714B2 JP60129786A JP12978685A JPH058714B2 JP H058714 B2 JPH058714 B2 JP H058714B2 JP 60129786 A JP60129786 A JP 60129786A JP 12978685 A JP12978685 A JP 12978685A JP H058714 B2 JPH058714 B2 JP H058714B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- silicon
- toluene
- fraction
- group
- 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 - Lifetime
Links
- 239000007788 liquid Substances 0.000 claims description 27
- -1 isocyanate compound Chemical class 0.000 claims description 26
- 239000012948 isocyanate Substances 0.000 claims description 15
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- 238000009835 boiling Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 229960005480 sodium caprylate Drugs 0.000 description 2
- 229940045845 sodium myristate Drugs 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 2
- FIWQZURFGYXCEO-UHFFFAOYSA-M sodium;decanoate Chemical compound [Na+].CCCCCCCCCC([O-])=O FIWQZURFGYXCEO-UHFFFAOYSA-M 0.000 description 2
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- MCFVRESNTICQSJ-RJNTXXOISA-L calcium sorbate Chemical compound [Ca+2].C\C=C\C=C\C([O-])=O.C\C=C\C=C\C([O-])=O MCFVRESNTICQSJ-RJNTXXOISA-L 0.000 description 1
- 235000010244 calcium sorbate Nutrition 0.000 description 1
- 239000004303 calcium sorbate Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 229920006267 polyester film Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 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
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、含ケイ素イソシアネート化合物の精
製方法、特に各種シリル基含有化合物の製造原料
として有用な、アルコキシ−ケイ素結合を包含す
るシリルアルキルイソシアネート化合物の製造方
法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for purifying silicon-containing isocyanate compounds, and in particular to a silylalkyl isocyanate compound containing an alkoxy-silicon bond, which is useful as a raw material for producing various silyl group-containing compounds. Relating to a manufacturing method.
従来、先に本発明者らが見出したアルコキシ−
ケイ素結合を包含するシリルアルキルアミンと塩
化カルボニルとを、不活性溶剤中第三級アミンの
存在下で反応させて得られる含ケイ素イイシアネ
ート化合物（特願昭59−265468号）では、反応終
了後第三級アミンの塩酸塩の結晶を反応液より
別し、液を蒸留することにより単離を行つてき
た。しかしながら、単に蒸留するだけでは液中
に溶解している微量の第三級アミン塩酸塩及び／
又は解離等により発生した塩化水素が目的物中に
含まれている。
Conventionally, the alkoxy-
In the silicon-containing isocyanate compound obtained by reacting a silylalkylamine containing a silicon bond with carbonyl chloride in the presence of a tertiary amine in an inert solvent (Japanese Patent Application No. 59-265468), after the reaction is completed, Crystals of tertiary amine hydrochloride salts have been separated from the reaction solution and isolated by distilling the solution. However, if only distillation is performed, trace amounts of tertiary amine hydrochloride and/or
Or hydrogen chloride generated due to dissociation, etc. is contained in the target product.
このために１週間以上の長期間保存の場合、経
時変化を起しやすく、濁りを発生する等の問題が
あつた。 For this reason, when stored for a long period of one week or more, there were problems such as easy change over time and generation of turbidity.
しかして、一般に微量の第三級アミンの塩酸塩
及び／又は塩化水素を中和処理し、得られる含ケ
イ素イソシアネート化合物を安定化することが考
えられる。
Therefore, it is generally considered to neutralize trace amounts of tertiary amine hydrochloride and/or hydrogen chloride to stabilize the resulting silicon-containing isocyanate compound.
しかしながら、アルカリ金属あるいはアルカリ
土類金属の水酸化物又は炭酸塩、例えば水酸化ナ
トリウム、水酸化カルシウム、水酸化マグネシウ
ム、炭酸カルシウムなどを中和剤として用いた場
合、生成した水が製品と反応したり、使用した塩
が水に溶解して強アルカリ性となり目的物に悪影
響を及ぼすことがわかつた。 However, when alkali metal or alkaline earth metal hydroxides or carbonates, such as sodium hydroxide, calcium hydroxide, magnesium hydroxide, and calcium carbonate, are used as neutralizing agents, the water produced may react with the product. It was also found that the salt used dissolves in water and becomes strongly alkaline, which has an adverse effect on the target product.
したがつて、目的物の品質を安定化するのに最
適の中和剤を探す必要がある。 Therefore, it is necessary to search for the best neutralizing agent to stabilize the quality of the target product.
本発明の特徴は、目的とする高純度で安定なイ
ソシアネート化合物を、特定の中和剤を加えて精
製することにより得る方法を提供することにあ
る。 A feature of the present invention is to provide a method for obtaining a target highly pure and stable isocyanate compound by purifying it by adding a specific neutralizing agent.
本発明を概説すれば、本発明は、含ケイ素イソ
シアネート化合物の精製方法に関する発明であつ
て、塩化カルボニルと下記一般式：
（式中R1，R2及びR3は、同一又は異なり、炭
化水素基、アルコキシ基又はシロキシ基を示す
が、その少なくとも１つはアルコキシ基であり、
ｎは１〜４の数を示す）で表される含ケイ素アル
キルアミンとを、不活性有機溶媒中、第三級アミ
ンの存在下で反応させることにより得られる下記
一般式：
（式中R1，R2，R3及びｎは前記式と同義で
ある）で表される含ケイ素イソシアネート化合物
含有液を精製する方法において、不飽和脂肪酸、
高級飽和脂肪酸及び芳香族カルボン酸よりなる群
から選択した１種のカルボン酸のアルカリ金属塩
又はアルカリ土類金属塩で処理する工程を包含す
ることを特徴とする。
To summarize the present invention, the present invention relates to a method for purifying a silicon-containing isocyanate compound, which includes carbonyl chloride and the following general formula: (In the formula, R 1 , R 2 and R 3 are the same or different and represent a hydrocarbon group, an alkoxy group or a siloxy group, at least one of which is an alkoxy group,
The following general formula obtained by reacting a silicon-containing alkylamine represented by (n represents a number of 1 to 4) in an inert organic solvent in the presence of a tertiary amine: In a method for purifying a liquid containing a silicon-containing isocyanate compound represented by the formula (wherein R 1 , R 2 , R 3 and n have the same meanings as the above formula), an unsaturated fatty acid,
It is characterized by including a step of treatment with an alkali metal salt or alkaline earth metal salt of one type of carboxylic acid selected from the group consisting of higher saturated fatty acids and aromatic carboxylic acids.
本発明者らは前記反応により得られた反応液よ
り第三級アミン塩酸塩を別した別より溶剤を
留去した残留液又はこれを蒸留した留出液を前記
したカルボン酸のアルカリ又はアルカリ土類金属
塩類で処理する工程を設けることにより、高純度
で安定な目的とするイソシアネート化合物が得ら
れることを見出した。なお、該処理後、PH６〜７
に調整した後、蒸留精製すれば、更に純度、安定
性を上げることができることも判明した。 The present inventors have obtained the above-mentioned carboxylic acid alkali or alkaline solution by distilling off the solvent from the reaction solution obtained by the above-mentioned reaction and distilling off the solvent. It has been found that by providing a step of treatment with similar metal salts, a highly pure and stable target isocyanate compound can be obtained. In addition, after this treatment, the pH is 6 to 7.
It has also been found that purification and stability can be further improved by distillation purification after adjustment.
本発明方法に使用されるカルボン酸のアルカリ
又はアルカリ土類金属塩のうち、高級飽和脂肪酸
の例としては、カプリル酸、ラウリン酸、ミリス
チン酸、ステアリン難等を、また不飽和脂肪酸の
例としては、オレイン酸、ソルビン酸等を、更に
芳香族カルボン酸の例としては、安息香酸、フタ
ル酸等を挙げることができる。 Among the alkali or alkaline earth metal salts of carboxylic acids used in the method of the present invention, examples of higher saturated fatty acids include caprylic acid, lauric acid, myristic acid, and stearic acid, and examples of unsaturated fatty acids include Examples of aromatic carboxylic acids include benzoic acid and phthalic acid.
また、アルカリ又はアルカリ土類金属として
は、Na，Ｋ，Mg，Ca，Ba等を挙げることがで
きる。 Furthermore, examples of the alkali or alkaline earth metals include Na, K, Mg, Ca, Ba, and the like.
これらカルボン酸のアルカリ、又はアルカリ土
類金属塩の使用量は、目的物中に存在する塩化水
素と当量以上が好ましい。 The amount of the alkali or alkaline earth metal salt of these carboxylic acids to be used is preferably equal to or more than the amount of hydrogen chloride present in the target product.
処理方法としては、反応液から第三級アミン塩
酸塩を過した液、液より溶剤を留去した残
留液、又はこれを蒸留した留出液のいずれの段階
でもよいが、カルボン酸のアルカリ又はアルカリ
土類金属塩を加え、充分にかくはんし、PHが６〜
７になつた後析出したカルボン酸、アルカリ又は
アルカリ土類金属塩化物及び／又は過剰のカルボ
ン酸のアルカリ又はアルカリ土類金属塩を過
し、液を望ましくは蒸留することにより高純度
で安定な目的物を単離することができる。 The treatment may be carried out at any stage, such as by removing the tertiary amine hydrochloride from the reaction solution, by distilling the solvent off from the solution, or by distilling this into a distillate. Add alkaline earth metal salt and stir thoroughly until pH is 6~
7, the precipitated carboxylic acid, alkali or alkaline earth metal chloride and/or excess alkali or alkaline earth metal salt of the carboxylic acid are filtered, and the liquid is preferably distilled to obtain a highly pure and stable product. The target product can be isolated.
次に実施例により本発明を更に詳細に説明する
が、本発明はこれら実施例に限定されるものでは
ない。
Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにτ−トリエトキシシリルプロピルアミ
ン22.1ｇ、Ｎ，Ｎ−ジメチルアニリン27.9ｇをト
ルエン50mlに溶解した溶液を−５〜−10℃、３時
間で滴下し、反応させた。反応後、Ｎ，Ｎ−ジメ
チルアニリン塩酸塩の結晶を別し、液を蒸留
したところ、トルエン回収ののち、沸点88〜91
℃／4.5mmHgの留分として、τ−トリエトキシシ
リルプロピルイソシアネート19.8ｇを得た。Example 1 9.9 g of carbonyl chloride was dissolved in 150 ml of toluene, and a solution of 22.1 g of τ-triethoxysilylpropylamine and 27.9 g of N,N-dimethylaniline dissolved in 50 ml of toluene was heated at -5 to -10°C for 30 minutes. It was added dropwise over a period of time to react. After the reaction, the crystals of N,N-dimethylaniline hydrochloride were separated and the liquid was distilled, and after recovering toluene, the boiling point was 88-91.
19.8 g of τ-triethoxysilylpropyl isocyanate was obtained as a fraction of °C/4.5 mmHg.
これにステアリン酸カルシウム２ｇを加え４時
間かくはんすると、PH７となる。過剰のステアリ
ン酸カルシウム及び析出物を別し、液を蒸留
したところ、沸点87〜89℃／４mmHgの留分とし
てτ−トリエトキシシリルプロピルイソシアネー
ト17.8ｇを得た。 When 2g of calcium stearate is added to this and stirred for 4 hours, the pH becomes 7. Excess calcium stearate and precipitates were separated and the liquid was distilled to obtain 17.8 g of τ-triethoxysilylpropylisocyanate as a fraction with a boiling point of 87-89°C/4 mmHg.
ステアリン酸カルシウム未添加の場合は、１週
間保存で濁りを生じたが、本品は６か月間の長期
間保存でも安定であつた。 When calcium stearate was not added, turbidity occurred after one week of storage, but this product remained stable even after six months of long-term storage.
実施例 ２
実施例１でトルエンを回収した液にミリスチン
酸ナトリウム4.0ｇを加え、PH７となるまでかく
はんする。過剰のミリスチン酸ナトリウム及び析
出物を別し、液を蒸留したところ、沸点93〜
95℃／６mmHgの留分としてτ−トリエトキシシ
リルプロピルイソシアネート18.8ｇを得た。本品
は６か月間以上保存しても経時変化がなく安定で
あつた。Example 2 Add 4.0 g of sodium myristate to the liquid from which toluene was recovered in Example 1, and stir until the pH reaches 7. Excess sodium myristate and precipitates were separated and the liquid was distilled, and the boiling point was 93~
18.8 g of τ-triethoxysilylpropyl isocyanate was obtained as a 95°C/6 mmHg fraction. This product remained stable with no change over time even when stored for more than 6 months.
実施例 ３
実施例１でＮ，Ｎ−ジメチルアニリン塩酸塩の
結晶を別した液にステアリン酸ナトリウム
18.0ｇを加え、PH７となるまでかくはんする。過
剰のステアリン酸ナトリウム及び析出物を別
し、液を蒸留したところ、沸点81〜83℃／３mm
Hgの留分としてτ−トリエトキシシリルプロピ
ルイソシアネート18.9ｇを得た。本品は６か月間
以上保存しても安定で濁りを生じなかつた。Example 3 Sodium stearate was added to the liquid from which the crystals of N,N-dimethylaniline hydrochloride were separated in Example 1.
Add 18.0g and stir until the pH reaches 7. Excess sodium stearate and precipitates were separated and the liquid was distilled, and the boiling point was 81-83℃/3mm.
18.9 g of τ-triethoxysilylpropyl isocyanate was obtained as a Hg fraction. This product remained stable and did not become cloudy even when stored for more than 6 months.
実施例 ４
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにτ−ジエトキシメチルシリルプロピル
アミン19.1ｇ、Ｎ，Ｎ−ジメチルアニリン24.2ｇ
をトルエン50mlに溶解した溶液を−５〜−10℃、
３時間で滴下し、反応させた。反応後ジメチルア
ニリン塩酸塩の結晶を別し、液よりトルエン
を回収したのち、沸点80〜85℃／６mmHgの留分
をとり、ソルビン酸カルシウム6.3ｇを加え３時
間かくはんし、この液を蒸留すると沸点82〜85
℃／６mmHgの留分としてτ−ジエトキシメチル
シリルプロピルイソシアネート17.6ｇを得た。本
品は６か月以上保存しても安定であつた。Example 4 Dissolve 9.9 g of carbonyl chloride in 150 ml of toluene, and add 19.1 g of τ-diethoxymethylsilylpropylamine and 24.2 g of N,N-dimethylaniline.
A solution of dissolved in 50 ml of toluene was heated at -5 to -10℃.
It was added dropwise over 3 hours to react. After the reaction, the crystals of dimethylaniline hydrochloride were separated, toluene was recovered from the liquid, a fraction with a boiling point of 80-85℃/6mmHg was taken, 6.3g of calcium sorbate was added, stirred for 3 hours, and this liquid was distilled. boiling point 82~85
17.6 g of τ-diethoxymethylsilylpropyl isocyanate was obtained as a fraction at °C/6 mmHg. This product remained stable even when stored for more than 6 months.
実施例 ５
塩化メチレン150mlに塩化カルボニル9.9ｇを溶
解させ、これにτ−ジエトキシメチルシリルプロ
ピルアミン19.1ｇ、トリエチルアミン23.3ｇを塩
化メチレン50mlに溶解した溶液を−５〜−10℃、
３時間で滴下し、反応させた。反応後トリエチル
アミン塩酸塩の結晶を別し、液より塩化メチ
レンを回収したのち、沸点91〜93℃／９mmHgの
留分をとり、オレイン酸ナトリウム９ｇを加え、
20分間かくはんすると、PH７となる。過剰のオレ
イン酸ナトリウム及び析出物を別し、液を蒸
留したところ、沸点80〜82℃／５mmHgの留分と
してτ−ジエトキシメチルシリルプロピルイソシ
アネート15.7ｇを得た。本品は６か月間以上保存
しても安定であつた。Example 5 9.9 g of carbonyl chloride was dissolved in 150 ml of methylene chloride, and a solution of 19.1 g of τ-diethoxymethylsilylpropylamine and 23.3 g of triethylamine dissolved in 50 ml of methylene chloride was heated at -5 to -10°C.
It was added dropwise over 3 hours to react. After the reaction, the crystals of triethylamine hydrochloride were separated, methylene chloride was recovered from the liquid, a fraction with a boiling point of 91 to 93°C/9 mmHg was taken, and 9 g of sodium oleate was added.
Stir for 20 minutes and the pH will be 7. Excess sodium oleate and precipitate were separated and the liquid was distilled to obtain 15.7 g of τ-diethoxymethylsilylpropylisocyanate as a fraction with a boiling point of 80-82°C/5 mmHg. This product remained stable even when stored for more than 6 months.
実施例 ６
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにτ−ジエトキシ（トリメチルシロキ
シ）シリルプロピルアミン29.5ｇ、トリエチルア
ミン23.3ｇをトルエン50mlに溶解した溶液を−５
〜−10℃、３時間で滴下し、反応させた。反応後
トリエチルアミン塩酸塩の結晶を別し、液よ
りトルエンを回収した残留液にカプリル酸ナトリ
ウム4.5ｇを加え、20分かくはんするとPH７とな
る。過剰のカプリル酸ナトリウム及び析出物を
別し、液を蒸留したところ、沸点84〜86℃／８
mmHgの留分として、τ−ジエトキシ（トリメチ
ルシロキシ）シリルプロピルイソシアネート21.5
ｇを得た。本品は６か月間以上保存しても安定で
あつた。Example 6 9.9 g of carbonyl chloride was dissolved in 150 ml of toluene, and a solution of 29.5 g of τ-diethoxy(trimethylsiloxy)silylpropylamine and 23.3 g of triethylamine dissolved in 50 ml of toluene was added to -5.
It was added dropwise at ~-10°C for 3 hours to react. After the reaction, the crystals of triethylamine hydrochloride are separated, and toluene is recovered from the liquid. 4.5 g of sodium caprylate is added to the residual liquid and stirred for 20 minutes, resulting in a pH of 7. Excess sodium caprylate and precipitate were separated and the liquid was distilled, and the boiling point was 84-86℃/8
τ-diethoxy(trimethylsiloxy)silylpropylisocyanate 21.5 as a fraction of mmHg
I got g. This product remained stable even when stored for more than 6 months.
実施例 ７
エチルエーテル150mlに塩化カルボニル9.9ｇを
溶解させ、これにτ−トリエトキシシリルプロピ
ルアミン22.1ｇ、ピリジン18.2ｇをエチルエーテ
ル50mlに溶解した溶液を−５〜−10℃、３時間で
滴下し、反応させた。反応後ピリジン塩酸塩の結
晶を別し、液を蒸留した。エチルエーテルを
回収したのち、沸点95〜100℃／８mmHgの留分と
して、τ−トリエトキシシリルプロピルイソシア
ネート17.3ｇを得た。Example 7 9.9 g of carbonyl chloride was dissolved in 150 ml of ethyl ether, and a solution of 22.1 g of τ-triethoxysilylpropylamine and 18.2 g of pyridine dissolved in 50 ml of ethyl ether was added dropwise at -5 to -10°C for 3 hours. and reacted. After the reaction, the crystals of pyridine hydrochloride were separated and the liquid was distilled. After collecting ethyl ether, 17.3 g of τ-triethoxysilylpropyl isocyanate was obtained as a fraction with a boiling point of 95-100°C/8 mmHg.
これにステアリン酸バリウム1.2ｇを加え、３
時間かくはんするとPH７となる。過剰のステアリ
ン酸バリウム及び析出物を別し、液を蒸留し
たところ沸点90〜93℃／５mmHgの留分としてτ
−トリエトキシシリルプロピルイソシアネート
15.9ｇを得た。本品は純度99％で長期間安定であ
る。 Add 1.2g of barium stearate to this and
After stirring for a while, the pH becomes 7. Excess barium stearate and precipitates were separated and the liquid was distilled, resulting in τ as a fraction with a boiling point of 90-93℃/5mmHg.
-triethoxysilylpropyl isocyanate
15.9g was obtained. This product has a purity of 99% and is stable for a long time.
実施例 ８
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにα−ジエトキシメチルシリルメチルア
ミン16.3ｇ、Ｎ，Ｎ−ジメチルアニリン24.2ｇを
トルエン50mlに溶解した溶液を−５〜−10℃、３
時間で滴下し、反応させた。反応後、N.N−ジ
メチルアニリン塩酸塩の結晶を別し、液を蒸
留した。トルエンを回収した残留液にカプリン酸
ナトリウム3.9ｇを加え20分間かくはんするとPH
７となる。過剰のカプリン酸ナトリウム及び析出
物を別し液を蒸留したところ、沸点86〜88
℃／20mmHgの留分として、αジエトキシメチル
シリルメチルイソシアネート11.0ｇを得た。本品
は６か月間以上保存しても安定であつた。Example 8 9.9 g of carbonyl chloride was dissolved in 150 ml of toluene, and a solution of 16.3 g of α-diethoxymethylsilylmethylamine and 24.2 g of N,N-dimethylaniline dissolved in 50 ml of toluene was heated at -5 to -10°C. 3
It was added dropwise over a period of time to react. After the reaction, the crystals of NN-dimethylaniline hydrochloride were separated and the liquid was distilled. Add 3.9g of sodium caprate to the residual liquid from which toluene has been recovered and stir for 20 minutes to determine the pH.
It becomes 7. When excess sodium caprate and precipitates were removed and the liquid was distilled, the boiling point was 86-88.
11.0 g of α-diethoxymethylsilylmethyl isocyanate was obtained as a fraction at °C/20 mmHg. This product remained stable even when stored for more than 6 months.
実施例 ９
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにδ−ジメチルメトキシシリルブチルア
ミン14.5ｇ、Ｎ，Ｎ−ジメチルアニリン27.9ｇを
トルエン50mlに溶解した溶液を−５〜−10℃、３
時間で滴下し、反応させた。反応後、Ｎ，Ｎ−ジ
メチルアニリン塩酸塩の結晶を別し、液を蒸
留した。トルエンを回収ののち、沸点95〜100
℃／12mmHgの留分として、δ−ジメチルメトキ
シシリルブチルイソシアネート12.8ｇを得た。Example 9 9.9 g of carbonyl chloride was dissolved in 150 ml of toluene, and a solution of 14.5 g of δ-dimethylmethoxysilylbutylamine and 27.9 g of N,N-dimethylaniline dissolved in 50 ml of toluene was heated at -5 to -10°C for 30 minutes.
It was added dropwise over a period of time to react. After the reaction, the crystals of N,N-dimethylaniline hydrochloride were separated and the liquid was distilled. After recovering toluene, the boiling point is 95-100.
12.8 g of δ-dimethylmethoxysilylbutyl isocyanate was obtained as a fraction at °C/12 mmHg.
これにステアリン酸マグネシウム１ｇを加えか
くはんするとPH７となる。過剰のステアリン酸マ
グネシウム及び析出物を別し、液を蒸留する
と沸点98〜100℃／12mmHgの留分としてδ−ジメ
チルメトキシシリルブチルイソシアネート11.5ｇ
を得た。本品は６か月間以上保存しても安定であ
つた。 When 1 g of magnesium stearate is added to this and stirred, the pH becomes 7. Excess magnesium stearate and precipitates were separated, and the liquid was distilled to yield 11.5 g of δ-dimethylmethoxysilylbutyl isocyanate as a fraction with a boiling point of 98-100°C/12 mmHg.
I got it. This product remained stable even when stored for more than 6 months.
実施例 10
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにτ−ジエトキシメチルシリルプロピル
アミン19.1ｇ、Ｎ，Ｎ−ジメチルアニリン24.2ｇ
をトルエン50mlに溶解させ、−５〜−10℃、３時
間でその溶液を滴下し、反応させた。反応後、
Ｎ，Ｎ−ジメチルアニリン塩酸塩を別し、液
よりトルエンを回収したのち、沸点91〜93℃／９
mmHgの留分をとり、安息香酸ナトリウム１ｇを
加え、３時間かくはんするPH７となる。過剰の安
息香酸ナトリウム及び析出物を別し、液を蒸
留したところ沸点80〜82℃／５mmHgの留分とし
てτ−ジエトキシメチルシリルプロピルイソシア
ネート15.6ｇを得た。本品は６か月以上保存して
も安定であつた。Example 10 Dissolve 9.9 g of carbonyl chloride in 150 ml of toluene, and add 19.1 g of τ-diethoxymethylsilylpropylamine and 24.2 g of N,N-dimethylaniline.
was dissolved in 50 ml of toluene, and the solution was added dropwise to react at -5 to -10°C for 3 hours. After the reaction,
After separating N,N-dimethylaniline hydrochloride and recovering toluene from the liquid, boiling point 91-93℃/9
Take the mmHg fraction, add 1 g of sodium benzoate, and stir for 3 hours to obtain a pH of 7. Excess sodium benzoate and precipitate were separated, and the liquid was distilled to obtain 15.6 g of τ-diethoxymethylsilylpropylisocyanate as a fraction with a boiling point of 80-82°C/5 mmHg. This product remained stable even when stored for more than 6 months.
実施例 11
トルエン150mlに塩化カルボニル9.9ｇを溶解さ
せ、これにτ−ジエトキシメチルシリルプロピル
アミン19.1ｇ、Ｎ，Ｎ−ジメチルアニリン24.2ｇ
をトルエン50mlに溶解させ−５〜−10℃、３時間
でその溶液を滴下し、反応させた。反応後、Ｎ，
Ｎ−ジメチルアニリン塩酸塩を別し、液より
トルエンを回収したのち、沸点91〜93℃／９mm
Hgの留分をとりフタル酸二カリウム0.8ｇを加
え、３時間かくはんするPH７となる。過剰のフタ
ル酸二カリウム及び析出物を別し、液を蒸留
したところ、沸点80〜82℃／５mmHgの留分とし
て、τ−ジエトキシメチルシリルプロピルイソシ
アネート15.6ｇを得た。本品は６か月以上保存し
ても安定であつた。Example 11 Dissolve 9.9 g of carbonyl chloride in 150 ml of toluene, and add 19.1 g of τ-diethoxymethylsilylpropylamine and 24.2 g of N,N-dimethylaniline.
was dissolved in 50 ml of toluene, and the solution was added dropwise at -5 to -10°C for 3 hours to react. After reaction, N,
After separating N-dimethylaniline hydrochloride and recovering toluene from the liquid, the boiling point was 91-93℃/9mm.
Take the Hg fraction, add 0.8 g of dipotassium phthalate, and stir for 3 hours to reach a pH of 7. Excess dipotassium phthalate and precipitate were separated and the liquid was distilled to obtain 15.6 g of τ-diethoxymethylsilylpropylisocyanate as a fraction with a boiling point of 80-82°C/5 mmHg. This product remained stable even when stored for more than 6 months.
以上詳細に説明したように、本発明方法によれ
ば、高純度且つ安定な目的とする含ケイ素イソシ
アネート化合物を得ることができる。
As explained in detail above, according to the method of the present invention, a highly pure and stable silicon-containing isocyanate compound can be obtained.
本発明方法の目的化合物は、イソシアネート基
とアルコキシ基とを持つため、種々の用途に有用
であり、例えばガラス繊維、ポリエステルフイル
ムなどのカツプリング剤、樹脂のコーテイング剤
などに用いられる。 Since the target compound of the method of the present invention has an isocyanate group and an alkoxy group, it is useful for various purposes, and is used, for example, as a coupling agent for glass fibers, polyester films, etc., and as a coating agent for resins.
Claims (1)
化水素基、アルコキシ基又はシロキシ基を示す
が、その少なくとも１つはアルコキシ基であり、
ｎは１〜４の数を示す）で表される含ケイ素アル
キルアミンとを、不活性有機溶媒中、第三級アミ
ンの存在下で反応させることにより得られる下記
一般式： （式中R1，R2，R3及びｎは前記式と同義で
ある）で表される含ケイ素イソシアネート化合物
含有液を精製する方法において、不飽和脂肪酸、
高級飽和脂肪酸及び芳香族カルボン酸よりなる群
から選択した１種のカルボン酸のアルカリ金属塩
又はアルカリ土類金属塩で処理する工程を包含す
ることを特徴とする含ケイ素イソシアネート化合
物の精製方法。[Claims] 1 Carbonyl chloride and the following general formula; (In the formula, R 1 , R 2 and R 3 are the same or different and represent a hydrocarbon group, an alkoxy group or a siloxy group, at least one of which is an alkoxy group,
The following general formula obtained by reacting a silicon-containing alkylamine represented by (n represents a number of 1 to 4) in an inert organic solvent in the presence of a tertiary amine: In a method for purifying a liquid containing a silicon-containing isocyanate compound represented by the formula (wherein R 1 , R 2 , R 3 and n have the same meanings as the above formula), an unsaturated fatty acid,
1. A method for purifying a silicon-containing isocyanate compound, comprising the step of treating with an alkali metal salt or alkaline earth metal salt of one type of carboxylic acid selected from the group consisting of higher saturated fatty acids and aromatic carboxylic acids.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60129786A JPS61289094A (en) | 1985-06-17 | 1985-06-17 | Purification of silicon-containing isocyanate compound |
| FR858518711A FR2574796B1 (en) | 1984-12-18 | 1985-12-17 | PROCESS FOR THE PREPARATION OF SILICON-CONTAINING ISOCYANATE COMPOUNDS |
| US06/810,314 US4654428A (en) | 1984-12-18 | 1985-12-17 | Process for preparation of silicon-containing isocyanate compounds |
| DE19853544601 DE3544601A1 (en) | 1984-12-18 | 1985-12-17 | METHOD FOR PRODUCING SILICON-CONTAINING ISOCYANATE COMPOUNDS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60129786A JPS61289094A (en) | 1985-06-17 | 1985-06-17 | Purification of silicon-containing isocyanate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61289094A JPS61289094A (en) | 1986-12-19 |
| JPH058714B2 true JPH058714B2 (en) | 1993-02-02 |
Family
ID=15018191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60129786A Granted JPS61289094A (en) | 1984-12-18 | 1985-06-17 | Purification of silicon-containing isocyanate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61289094A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10323049B2 (en) | 2014-12-24 | 2019-06-18 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound containing isocyanate group, process for producing same, adhesive, pressure-sensitive adhesive, and coating material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06228161A (en) * | 1993-01-29 | 1994-08-16 | Shin Etsu Chem Co Ltd | Method for producing isocyanate group-containing organopolysiloxane |
| US5393910A (en) * | 1993-10-20 | 1995-02-28 | Osi Specialties, Inc. | Process for making isocyanatoorganosilanes |
| DE10237270A1 (en) | 2002-08-14 | 2004-03-04 | Consortium für elektrochemische Industrie GmbH | Silane crosslinkable coating formulations |
| DE102007006147A1 (en) * | 2007-02-07 | 2008-08-14 | Wacker Chemie Ag | Process for the preparation of isocyanatoorganosilanes |
| CA2873674A1 (en) * | 2012-05-29 | 2013-12-05 | Momentive Performance Materials Gmbh | Preparation of isocyanato silanes |
-
1985
- 1985-06-17 JP JP60129786A patent/JPS61289094A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10323049B2 (en) | 2014-12-24 | 2019-06-18 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound containing isocyanate group, process for producing same, adhesive, pressure-sensitive adhesive, and coating material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61289094A (en) | 1986-12-19 |
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