JPH04124168A - Production of alpha-cyanoacrylate - Google Patents
Production of alpha-cyanoacrylateInfo
- Publication number
- JPH04124168A JPH04124168A JP24450790A JP24450790A JPH04124168A JP H04124168 A JPH04124168 A JP H04124168A JP 24450790 A JP24450790 A JP 24450790A JP 24450790 A JP24450790 A JP 24450790A JP H04124168 A JPH04124168 A JP H04124168A
- Authority
- JP
- Japan
- Prior art keywords
- cyanoacrylate
- parts
- distillation
- crude
- alpha
- 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.)
- Granted
Links
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 238000007670 refining Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- 229920001651 Cyanoacrylate Polymers 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- -1 cyanoacetic acid ester Chemical class 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 abstract description 3
- MLIREBYILWEBDM-UHFFFAOYSA-N anhydrous cyanoacetic acid Natural products OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 239000007789 gas Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- IQDPHMACOQAPBQ-UHFFFAOYSA-N 2-ethoxyethyl 2-cyanoprop-2-enoate Chemical compound CCOCCOC(=O)C(=C)C#N IQDPHMACOQAPBQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 3
- 229950010048 enbucrilate Drugs 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical class CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- IPDQIHIYQHAUCO-UHFFFAOYSA-N phenyl 2-cyanoprop-2-enoate Chemical compound N#CC(=C)C(=O)OC1=CC=CC=C1 IPDQIHIYQHAUCO-UHFFFAOYSA-N 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WNMUOLOGFSYABW-UHFFFAOYSA-N 2-butoxyethyl 2-cyanoprop-2-enoate Chemical compound CCCCOCCOC(=O)C(=C)C#N WNMUOLOGFSYABW-UHFFFAOYSA-N 0.000 description 1
- RANXVQXZDJJZOE-UHFFFAOYSA-N 2-chloroethyl 2-cyanoprop-2-enoate Chemical compound ClCCOC(=O)C(=C)C#N RANXVQXZDJJZOE-UHFFFAOYSA-N 0.000 description 1
- LEAXLYOYISOXNZ-UHFFFAOYSA-N 2-cyano-4,5,5-trifluoro-4-methylpent-2-enoic acid Chemical compound CC(C=C(C#N)C(=O)O)(C(F)F)F LEAXLYOYISOXNZ-UHFFFAOYSA-N 0.000 description 1
- JYTXVMYBYRTJTI-UHFFFAOYSA-N 2-methoxyethyl 2-cyanoprop-2-enoate Chemical compound COCCOC(=O)C(=C)C#N JYTXVMYBYRTJTI-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical class CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- DJACTCNGCHPGOI-UHFFFAOYSA-N butyl 2-cyanoacetate Chemical compound CCCCOC(=O)CC#N DJACTCNGCHPGOI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229930003836 cresol Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RPQUGMLCZLGZTG-UHFFFAOYSA-N octyl cyanoacrylate Chemical compound CCCCCCCCOC(=O)C(=C)C#N RPQUGMLCZLGZTG-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、接着剤として有用なα−シアノアクリレート
類の製造方法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an improvement in a method for producing α-cyanoacrylates useful as adhesives.
〈従来の技術〉
α−シアノアクリレート類は、−船釣にシアノ酢酸エス
テルとホルムアルデヒドを例えば有機溶媒中で縮合し、
得られた重合体を高温減圧下に解重合を行なって製造さ
れるが、この方法で得られる粗α−シアノアクリレート
類は、一般に純度も低く、接着性能、安定性等において
劣るため、該粗モノマーを蒸留精製し、高純度のα−シ
アノアクリレート類として得ている。<Prior art> α-cyanoacrylates are produced by condensing cyanoacetate and formaldehyde in an organic solvent, for example,
The resulting polymer is produced by depolymerizing it under high temperature and reduced pressure, but the crude α-cyanoacrylates obtained by this method generally have low purity and are inferior in adhesive performance, stability, etc. Monomers are distilled and purified to obtain highly pure α-cyanoacrylates.
ここで、蒸留精製する方法としては、五酸化リン、リン
酸、パラトルエンスルホン酸などの酸性物質及びハイド
ロキノン、ハイドロキノンモノメチルエーテル、カテコ
ール、ピロガロールなどの重合禁止剤を添加し、ＳＯｌ
等の酸性ガス気流下で減圧で加熱蒸留する方法が知られ
ている。Here, the distillation purification method involves adding acidic substances such as phosphorus pentoxide, phosphoric acid, and para-toluenesulfonic acid, and polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol.
A method is known in which distillation is carried out under reduced pressure under a stream of acidic gas.
〈発明が解決しようとする課題〉
しかしながら、これら従来の蒸留精製法では蒸留中のゲ
ル化を防ぐ目的で、特にＳＯ８等の酸性ガス気流下で蒸
留を行う必要があり、このため、得られたα−シアノア
クリレート類には、多量の酸性ガスが含まれ、それを更
に脱気等によって除去する必要があった。<Problem to be solved by the invention> However, in these conventional distillation purification methods, in order to prevent gelation during distillation, it is necessary to carry out distillation particularly under a stream of acidic gas such as SO8. α-Cyanoacrylates contain a large amount of acidic gas, which must be further removed by degassing or the like.
又、これらの酸性ガスはすべて廃ガスとして放出される
ため除害設備等の必要があり、工業的操作土及び環境面
においても問題かあった。In addition, since all of these acidic gases are released as waste gases, detoxification equipment and the like are required, which poses problems in terms of industrial operation soil and the environment.
従って、当業界ではかかる脱気工程等を必要とせず、か
つ有害な酸性ガスを用いない蒸留精製方法の出現か要望
されていた。Therefore, there has been a demand in the industry for a distillation purification method that does not require such a degassing step and does not use harmful acidic gases.
く課題を解決するための手段〉
本発明者らは、以上のような要請から、酸性ガスを用い
ない蒸留精製方法について鋭意研究、検討を行い、遂に
本発明の方法を見出した。Means for Solving the Problems In response to the above requirements, the present inventors conducted extensive research and examination on a distillation purification method that does not use acidic gas, and finally discovered the method of the present invention.
すなわち、本発明の方法は、α−シアノアクリレート類
を蒸留精製するに際し、ＢＦ、錯塩の存在下に蒸留精製
することを特徴とするα−シアノアクリレート類の製造
方法である。That is, the method of the present invention is a method for producing α-cyanoacrylates, which is characterized in that the α-cyanoacrylates are purified by distillation in the presence of BF and a complex salt.
本発明の特徴は、酸性ガスに替え、ＢＦ、錯塩を添加す
ることで安定した蒸留精製か行えることを見出した点に
ある。The feature of the present invention lies in the discovery that stable distillation purification can be performed by adding BF and complex salts instead of acidic gas.
本発明の方法に用いられるＢＦ、錯塩としては、具体的
にはＢＰ、とメチルエーテル、エチルエーテル、ｎ−プ
ロピルエーテル、イソプロピルエーテル、ｎ−ブチルエ
ーテル、テトラヒドロフラン等との錯塩であるＢＰ３エ
ーテル錯塩、ＢＦ３とギ酸、酢酸、プロピオン酸又は酪
酸との錯塩であるＢＦ＋カルボン酸錯塩、ＢＦ３とフェ
ノール、クレゾール、カテコール又はハイドロキノン等
の錯塩であるＢＰ、フェノール錯塩等を挙げることか出
来る。Examples of BF and complex salts used in the method of the present invention include BP3 ether complex salts, which are complex salts of BP and methyl ether, ethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, tetrahydrofuran, etc.; Examples include BF+carboxylic acid complexes, which are complex salts of BF3 and formic acid, acetic acid, propionic acid, or butyric acid; BP, phenol complex salts, which are complex salts of BF3 and phenol, cresol, catechol, or hydroquinone; and the like.
本発明にいうα−シアノアクリレ−１・類としては、具
体的にはメチル−α−シアノアクリレート、エチル−α
−シアノアクリレート、プロピルα−シアノアクリレー
ト、アリル−α−ノアノアクリレート、ブチル−α−シ
アノアクリレート、ヘプチル−α−シアノアクリレート
、ヘキシル−α−シアノアクリレ−１・、オクチル−α
−シアノアクリレート、デシル−α−ソアノアクリレー
トドデシルーα−シアノアクリレ−１・、（２−クロロ
エチル）−α−シアノアクリレート、（２−メトキシエ
チル）−α−シアノアクリレート、（２−エトキシエチ
ル）−α−シアノアクリレート、（２−ブトキシエチル
）−α−シアノアクリレート、ベンジル−α−シアノア
ク？ル−ト、フェニル−α−シアノアクリ１ノート、ト
リフルオロイソプロピル−α−シアノアクリレート等か
挙げられる。Specifically, the α-cyanoacrylates 1 and 2 mentioned in the present invention include methyl-α-cyanoacrylate, ethyl-α
-Cyanoacrylate, propyl α-cyanoacrylate, allyl α-cyanoacrylate, butyl α-cyanoacrylate, heptyl α-cyanoacrylate, hexyl α-cyanoacrylate-1, octyl-α
-Cyanoacrylate, decyl-α-soanoacrylate dodecyl-α-cyanoacrylate-1, (2-chloroethyl)-α-cyanoacrylate, (2-methoxyethyl)-α-cyanoacrylate, (2-ethoxyethyl)- α-cyanoacrylate, (2-butoxyethyl)-α-cyanoacrylate, benzyl-α-cyanoac? Examples include phenyl-alpha-cyanoacrylate, phenyl-α-cyanoacrylate, and trifluoroisopropyl-α-cyanoacrylate.
本発明の方法を実施するに当たっては、通常の方法で、
例えば、シアノ酢酸エステルとホルムアルデヒドを例え
ば育種溶媒中、触媒の存在下に縮合し、得られた重合体
を高温（約１５０°Ｃ以上）で減圧下に解重合を行なっ
て粗α−シアノアクリレート類を製造する。この粗α−
シアノアクリレート類に対して、本発明の蒸留精製方法
を適用するのが一般的である。In carrying out the method of the present invention, in the usual manner,
For example, cyanoacetate and formaldehyde are condensed in a breeding solvent in the presence of a catalyst, and the resulting polymer is depolymerized at high temperature (about 150°C or higher) under reduced pressure to produce crude α-cyanoacrylate. Manufacture. This rough α-
The distillation purification method of the present invention is generally applied to cyanoacrylates.
すなわち、上記の方法で製造された粗α−シアノアクリ
レート類に前記ＢＦ、錯塩を所定量添加した後、−船釣
に行われる方法、例えば１〜１０■Ｈｇの減圧下、温度
３０〜１３０℃、好ましくは３５〜１００℃で蒸溜する
ことによって行なわれる。That is, after adding a predetermined amount of the above-mentioned BF and complex salt to the crude α-cyanoacrylate produced by the above method, - the method used in boat fishing, for example, under a reduced pressure of 1 to 10 μHg, at a temperature of 30 to 130°C. , preferably by distillation at 35-100°C.
なお、更に着色の防止、セットタイムの向上等を目的と
して、蒸留等によって製造されたα−シアノアクリレー
トモノマーに対して、更に本発明の蒸留精製法を適用す
ることもでき、場合によっては更に好ましい結果を与え
る。Furthermore, for the purpose of preventing coloration, improving set time, etc., the distillation purification method of the present invention can be further applied to α-cyanoacrylate monomers produced by distillation, etc., and in some cases, it is more preferable. Give results.
本発明の蒸留精製法において、前記ＢＰ、錯塩の添加量
は、前記α−シアノアクリレ−１・類１００部に対して
通常０．０００１〜１重量部の範囲であり、好ましくは
０．０００５〜１重量部の範囲である。この範囲未満で
あると貯蔵安定性を低下させ、またこの範囲を越えると
硬化速度を過度に遅くさせる傾向を示すため、瞬間接着
剤としての機能を果たすことか出来なくなる。In the distillation purification method of the present invention, the amount of the BP and complex salt added is usually in the range of 0.0001 to 1 part by weight, preferably 0.0005 to 1 part by weight, based on 100 parts of the α-cyanoacrylate-1. Parts by weight range. If it is less than this range, the storage stability will be reduced, and if it exceeds this range, the curing rate will tend to be excessively slow, so that it will no longer be able to function as an instant adhesive.
本発明の蒸留精製方法において添加するＢＦＳ錯塩はそ
れ自身単独で目的とする効果を充分に発揮することが出
来るか、更に必要によっては、従来から知られている五
酸化リン、リン酸、パラトルエンスルホン酸等の酸性物
質及びハイドロキノン、ハイドロキノンモノメチルエー
テル、カテコール、ピロガロール等の重合禁止剤と併用
・添加することも可能であり、場合により、更に好まし
い結果を得ることができる。Is it possible for the BFS complex salt added in the distillation purification method of the present invention to sufficiently exhibit the desired effect by itself? It is also possible to use or add an acidic substance such as sulfonic acid and a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc., and more preferable results can be obtained depending on the case.
本発明の方法に実施するに際しては、窒素ガス、ヘリウ
ムガス等の不活性ガス気流下で蒸留を行なうことかより
好ましい。この場合は、従来行われている蒸留後の脱気
等、酸性ガス除去等の煩雑な操作を行う必要かないので
好都合である。When carrying out the method of the present invention, it is more preferable to carry out the distillation under a stream of an inert gas such as nitrogen gas or helium gas. In this case, it is convenient because there is no need to perform complicated operations such as deaeration after distillation and removal of acidic gases, which are conventionally performed.
通常は、以上の様にして得られた流出液に、更に安定剤
として、Ｓ０２、ＳＯ１、パラトルエンスルホン酸、プ
ロパンサルトン、メタンスルホン酸、ＢＰ、エーテル錯
塩、ＨＢＦ、等のアニオン重合禁止剤を任意の量を添加
することによって最終製品として仕上げることか出来る
。Usually, an anionic polymerization inhibitor such as S02, SO1, paratoluenesulfonic acid, propanesultone, methanesulfonic acid, BP, ether complex salt, HBF, etc. is added to the effluent obtained as described above as a stabilizer. The final product can be made by adding any amount of .
〈発明の効果〉
本発明の方法によれば、ＳＯｌ等の酸性ガスを用いずに
安定して蒸留精製を行なうことかでき、しかも酸性ガス
の除外設備の必要等か全く無く、更に蒸留後の酸性ガス
を除去する手間も省け、蒸留の後必要により適当な安定
剤を任意の量添加することによって最終製品とすること
が出来る等、実用的価値の高い方法である。更に得られ
たα−シソアノアクリレート類、従来必然的に含まれて
きた酸性ガスを全く含まないものとすることもでき、こ
のため、硬化速度が酸性ガスを用いた場合に比へ一般的
に短かく、かつ保存安定性に優れる等の作用効果を兼備
するものである。<Effects of the Invention> According to the method of the present invention, distillation purification can be carried out stably without using acidic gas such as SOl, and there is no need for acidic gas exclusion equipment. This method has high practical value, as it saves the effort of removing acidic gases, and allows the final product to be obtained by adding any amount of a suitable stabilizer after distillation. Furthermore, the obtained α-cysoanoacrylates can be completely free of acidic gas, which has conventionally been necessarily included, and therefore the curing speed is generally lower than that when acidic gas is used. It has the advantages of being short and having excellent storage stability.
〈実施例〉
以下、本発明の方法を実施例及び比較例によって更に詳
しく説明する。<Examples> Hereinafter, the method of the present invention will be explained in more detail with reference to Examples and Comparative Examples.
合成例１
粗エチルーα−シアノアクリレートの合成攪拌機、温度
計、水分離器、滴下ａ−トを備えた三ツロフラスコにバ
ラホルムアルデヒド６０部、トルエン２００部、ピペリ
ジン０．２部を仕込み、８０〜９０℃の温度に保ち、攪
拌しなからシアノ酢酸エチルエステル２２６部を６０分
かけて滴下した。滴下終了後生成水を共沸分離しなから
還流させ、理論量の水か留出するまで約６時間反応させ
、ポリマーのトルエン溶液を得た。この溶液を常圧脱溶
媒後、リン酸トリクレジル３０部、五酸化リン６部、ハ
イドロキノン３部を加えて、充分混合した。減圧脱溶媒
した後、続いて３ｍｍＨｇの減圧下て１７０〜２００°
Ｃに加熱して解重合を行い、エチル−α−シアノアクリ
レートの粗製品２１２部を得た。Synthesis Example 1 Synthesis of crude ethyl-α-cyanoacrylate 60 parts of rose formaldehyde, 200 parts of toluene, and 0.2 parts of piperidine were charged into a Mitsuro flask equipped with a stirrer, a thermometer, a water separator, and a dropping a-to. 226 parts of cyanoacetic acid ethyl ester was added dropwise to the mixture over 60 minutes while maintaining the temperature at .degree. C. and stirring. After the dropwise addition was completed, the produced water was separated azeotropically and then refluxed, and the reaction was allowed to proceed for about 6 hours until the theoretical amount of water was distilled off, to obtain a toluene solution of the polymer. After removing the solvent from this solution under normal pressure, 30 parts of tricresyl phosphate, 6 parts of phosphorus pentoxide, and 3 parts of hydroquinone were added and thoroughly mixed. After desolvation under reduced pressure, it was subsequently heated at 170 to 200° under a reduced pressure of 3 mmHg.
Depolymerization was carried out by heating at a temperature of 50° C. to obtain 212 parts of a crude product of ethyl-α-cyanoacrylate.
合成例２
合成例１において、シアノ酢酸エチルエステル２２６部
に代え、シアノ酢酸メチルエステル１９８部を用い、以
下同様にして粗メチルーα−シアノアクリレ−１−１８
７部を得た。Synthesis Example 2 In Synthesis Example 1, 198 parts of methyl cyanoacetate was used in place of 226 parts of ethyl cyanoacetate, and crude methyl-α-cyanoacrylate-1-18 was prepared in the same manner.
I got 7 copies.
合成例３
粗プロプルーα−シアノアクリレートの合成合成例１に
おいて、シアノ酢酸エチルエステル２２６部に代え、シ
アン酢酸プロプルエステル２５４部を用い、以下同様に
して粗プロブルーα−シアノアクリレート２３７部を得
た。Synthesis Example 3 Synthesis of Crude Problue α-Cyanoacrylate In Synthesis Example 1, 254 parts of cyanacetic acid propyl ester was used instead of 226 parts of ethyl cyanoacetate, and 237 parts of crude ProBlue α-cyanoacrylate was obtained in the same manner. Ta.
合成例４
粗ブチルーα−シアノアクリレートの合成合成例■にお
いて、シアノ酢酸エチルエステル２２６部に代え、シア
ノ酢酸ブチルエステル２８２部を用い、以下同様にして
粗ブチルーα−シアノアクリレート２６２部を得た。Synthesis Example 4 Synthesis of Crude Butyl-α-Cyanoacrylate In Synthesis Example 2, 282 parts of butyl cyanoacetate was used instead of 226 parts of ethyl cyanoacetate, and 262 parts of crude butyl-α-cyanoacrylate was obtained in the same manner.
合成例５
粗（２−エトキシエチル）−α−シアノアクリレートの
合成
合成例１において、シアノ酢酸エチルエステル２２６部
に代え、シアノ酢酸エトキシエチルエステル３１４部を
用い、以下同様にして粗（２−エトキシエチル）−α−
シアノアクリレート２９０部を得た。Synthesis Example 5 Synthesis of Crude (2-Ethoxyethyl)-α-Cyanoacrylate In Synthesis Example 1, 314 parts of cyanoacetate ethyl ester was used instead of 226 parts of cyanoacetate ethyl ester, and crude (2-ethoxyethyl)-α-cyanoacrylate was prepared in the same manner. ethyl) -α-
290 parts of cyanoacrylate were obtained.
実施例１〜１３
前記合成例１〜５に記載の方法によって得られた粗シア
ノアクリレート類（１００部）に対して、重合禁止剤と
してハイドロキノン（０，５部）及び五酸化リン（０，
１部）をそれぞれ添加し、本発明にいうＢＦ、錯塩とし
て表−１に示す各種ＢＰ、錯塩を夫々表−１に示す量を
添加し、１〜３ｍｍＨｇの減圧下、温度３５°Ｃ〜９０
℃で蒸留し、初留分の一部をカットした後、高純度の精
製モノマー（夫々９０部）を得た。この蒸留の状況を実
施例１〜１３として表−１に示した。Examples 1 to 13 Hydroquinone (0.5 parts) and phosphorus pentoxide (0.5 parts) as polymerization inhibitors were added to the crude cyanoacrylates (100 parts) obtained by the method described in Synthesis Examples 1 to 5 above.
1 part) were added, and various BPs and complex salts shown in Table 1 as BF and complex salts according to the present invention were added in the amounts shown in Table 1, respectively, and the temperature was 35°C to 90°C under reduced pressure of 1 to 3 mmHg.
After distillation at .degree. C. and cutting off a portion of the first distillate, highly purified purified monomers (90 parts each) were obtained. The situation of this distillation is shown in Table 1 as Examples 1 to 13.
比較例１〜３
比較のために、本発明ＢＰ、錯塩を用いずに従来の酸性
ガス（ＳＯ，ガス）気流下で前記同様減圧蒸留を行った
ものを比較例１及び２として、更に酸性ガスに替え窒素
ガス気流下で前記同様減圧蒸留を行ったものを比較例３
として、夫々表−１に示した。Comparative Examples 1 to 3 For comparison, as Comparative Examples 1 and 2, vacuum distillation was performed in the same manner as described above under a conventional acid gas (SO, gas) stream without using the BP of the present invention and a complex salt. Comparative Example 3 was obtained by performing vacuum distillation in the same manner as above under a nitrogen gas stream
are shown in Table 1.
以上の方法で得られた高純度α−シアノアクリレートを
用いて、鋼／鋼での硬化速度の測定及び７０°Ｃでの加
熱ゲル化日数による貯蔵安定性の試験を行った結果を表
−１に示した。Using the high-purity α-cyanoacrylate obtained by the above method, we conducted a measurement of the hardening rate on steel/steel and a storage stability test based on the number of days of heat gelation at 70°C.The results are shown in Table 1. It was shown to.
表−１における補足説明
（１）実施例３以外は全て窒素ガス気流下で蒸留を行な
った。Supplementary explanation for Table 1 (1) All cases except Example 3 were distilled under a nitrogen gas stream.
（２）安定剤については、実施例の全部及び比較例３で
は、蒸留によって得られた高純度のエチルシアノアクリ
レート １００部に対し、夫々表−１に示した安定剤を
夫々表−１に示す量を添加したものである。(2) Regarding stabilizers, in all Examples and Comparative Example 3, the stabilizers shown in Table 1 were added to 100 parts of high purity ethyl cyanoacrylate obtained by distillation. amount added.
比較例１では蒸留後Ｓｏ２ガスを多量に含んだままの状
態（脱気前のまま）を最終製品とし、また比較例２では
比較例１のエチルシアノアクリレートを脱気によってＳ
Ｏｔを０．００３部になるよう調整して製造したもの
である。In Comparative Example 1, the final product was a state that still contained a large amount of So2 gas after distillation (as before degassing), and in Comparative Example 2, the ethyl cyanoacrylate of Comparative Example 1 was degassed to produce S2 gas.
It was manufactured by adjusting Ot to 0.003 parts.
Claims (3)
、ＢＦ＿３錯塩の存在下に蒸留精製することを特徴とす
るα−シアノアクリレート類の製造方法。(1) A method for producing α-cyanoacrylates, which comprises distilling and refining α-cyanoacrylates in the presence of a BF_3 complex salt.
ト類１００部に対して０．０００１〜１重量部の範囲で
ある請求項（１）に記載の方法。(2) The method according to claim 1, wherein the amount of the BF_3 complex salt added is in the range of 0.0001 to 1 part by weight based on 100 parts of the α-cyanoacrylate.
）又は（２）のいずれかに記載の方法。(3) Claim (1) in which the distillation temperature is 30°C to 130°C.
) or (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24450790A JP2875867B2 (en) | 1990-09-13 | 1990-09-13 | Method for producing α-cyanoacrylates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24450790A JP2875867B2 (en) | 1990-09-13 | 1990-09-13 | Method for producing α-cyanoacrylates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04124168A true JPH04124168A (en) | 1992-04-24 |
| JP2875867B2 JP2875867B2 (en) | 1999-03-31 |
Family
ID=17119707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24450790A Expired - Fee Related JP2875867B2 (en) | 1990-09-13 | 1990-09-13 | Method for producing α-cyanoacrylates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2875867B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061337C (en) * | 1996-01-23 | 2001-01-31 | 住友化学工业株式会社 | Process for producing alpha-(tert-alkyl) cyanoacetic acid ester |
| WO2004106284A1 (en) | 2003-05-30 | 2004-12-09 | Toagosei Co., Ltd. | Method for producing purified 2-cyanoacrylate |
| JP2009256249A (en) * | 2008-04-17 | 2009-11-05 | Toagosei Co Ltd | Continuous production method of 2-cyanoacrylate |
| GB2443411B (en) * | 2006-11-02 | 2011-12-21 | Chemence Ltd | Process for producing a monomer |
| JP5000018B1 (en) * | 2011-03-03 | 2012-08-15 | 田岡化学工業株式会社 | Method for purifying 2-cyanoacrylate |
| CN109265368A (en) * | 2018-09-06 | 2019-01-25 | 营创三征(营口)精细化工有限公司 | Ethyl cyanoacetate synthesis technology |
-
1990
- 1990-09-13 JP JP24450790A patent/JP2875867B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061337C (en) * | 1996-01-23 | 2001-01-31 | 住友化学工业株式会社 | Process for producing alpha-(tert-alkyl) cyanoacetic acid ester |
| WO2004106284A1 (en) | 2003-05-30 | 2004-12-09 | Toagosei Co., Ltd. | Method for producing purified 2-cyanoacrylate |
| JPWO2004106284A1 (en) * | 2003-05-30 | 2006-07-20 | 東亞合成株式会社 | Method for producing purified 2-cyanoacrylate |
| US7709676B2 (en) | 2003-05-30 | 2010-05-04 | Toagosei Co., Ltd. | Method for producing purified 2-cyanoacrylate |
| JP4765624B2 (en) * | 2003-05-30 | 2011-09-07 | 東亞合成株式会社 | Method for producing purified 2-cyanoacrylate |
| GB2443411B (en) * | 2006-11-02 | 2011-12-21 | Chemence Ltd | Process for producing a monomer |
| JP2009256249A (en) * | 2008-04-17 | 2009-11-05 | Toagosei Co Ltd | Continuous production method of 2-cyanoacrylate |
| JP5000018B1 (en) * | 2011-03-03 | 2012-08-15 | 田岡化学工業株式会社 | Method for purifying 2-cyanoacrylate |
| WO2012117977A1 (en) * | 2011-03-03 | 2012-09-07 | 田岡化学工業株式会社 | 2-cyanoacrylate-purifying method |
| US8975433B2 (en) | 2011-03-03 | 2015-03-10 | Taoka Chemical Co., Ltd. | 2-cyanoacrylate-purifying method |
| TWI491585B (en) * | 2011-03-03 | 2015-07-11 | Taoka Chemical Co Ltd | Method for purifying 2-cyanoacrylate |
| CN109265368A (en) * | 2018-09-06 | 2019-01-25 | 营创三征(营口)精细化工有限公司 | Ethyl cyanoacetate synthesis technology |
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| Publication number | Publication date |
|---|---|
| JP2875867B2 (en) | 1999-03-31 |
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