CN104402763A - Preparation method of environment-friendly type alpha-cyanoacrylate - Google Patents
Preparation method of environment-friendly type alpha-cyanoacrylate Download PDFInfo
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- CN104402763A CN104402763A CN201410608429.9A CN201410608429A CN104402763A CN 104402763 A CN104402763 A CN 104402763A CN 201410608429 A CN201410608429 A CN 201410608429A CN 104402763 A CN104402763 A CN 104402763A
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Abstract
The invention discloses a preparation method of environment-friendly type alpha-cyanoacrylate, which takes cyanoacetates and formaldehyde or paraformaldehyde as raw materials, under existence of a basic catalyst, an organic solvent which enables azeotropy with water can be taken as a dehydrant, then a condensation reaction is carried out, after completely dehydrating, an environment-friendly type plasticizer, an anionic polymerization inhibitor and an environment-friendly type free radical polymerization inhibitor are added for cracking, and then are rectified to obtain the alpha-cyanoacrylate monomer. The preparation method of the present invention selects the organic solvent for azeotropy and dehydration, the environmental protection plasticizer and the polymerization inhibitor are employed during the cracking process, then the environment-friendly type alpha-cyanoacrylate can be obtained with high yield, and the preparation method is suitable for field with high requirement on environmental protection.
Description
Technical field
The present invention relates to sizing agent field, more precisely, relate to a kind of preparation method of α-cyanoacrylate.
Background technology
α-cyanoacrylate compounds, due to the characteristic of its high anionoid polymerization, meets water and polymerizing curable, thus produces certain bonding force on adhesives surface, can be used for iron and steel, non-ferrous metal, rubber, leather, plastics, pottery, glass, timber etc.
At present, the main preparation technology of α-cyanoacrylate is: in organic solvent, by cyan-acetic ester and formaldehyde or paraformaldehyde, condensation polymerization reaction is carried out under the existence of basic catalyst, by dewatering agent, water is removed afterwards, then add a certain amount of softening agent and stopper, pass through Pintsch process, obtain the crude monomer of α-cyanoacrylate, obtain corresponding monomer finally by rectified purified.
According to above-mentioned technique, organic solvent mostly is benzene, the contour malicious organic solvent of ethylene dichloride, can add softening agent (as dioctyl phthalate (DOP), dibutyl phthalate etc.) and hydroquinones radical polymerization inhibitor in cracking process.The shortcoming of this preparation technology, on the one hand, this type of organic solvent and additive easily produce environment and pollute, and on the other hand, also have certain infringement to the health of producers.According to the product of above-mentioned explained hereafter, while discontented toe ring guaranteed request, the demand in some client and market can not be met, as nail lacquer etc.
Summary of the invention
The present invention, in order to solve problems of the prior art, provides a kind of preparation method of environment-friendly type α-cyanoacrylate.
Technical scheme of the present invention is: a kind of environment-friendly type α-cyanoacrylate preparation method, and the method comprises the following steps:
With cyanoacetate and formaldehyde or paraformaldehyde for raw material, under the existence of basic catalyst, with can with the organic solvent of water azeotropic for dewatering agent, carry out condensation reaction, after dehydration completely, add environment-friendlyplasticizer plasticizer, negatively charged ion stopper, environment-friendly type radical polymerization inhibitor carry out cracking, and carry out rectifying to it, obtain α-cyanoacrylatemonomer;
Wherein, described organic solvent is selected from one or more combinations in normal heptane, normal hexane, hexanaphthene, toluene, dimethylbenzene, methylene dichloride, propylene dichloride, ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, methylcarbonate, diethyl carbonate, methyl alcohol, ethanol, propyl carbinol;
Described environment-friendlyplasticizer plasticizer is selected from one or more the combination in synthesis vegetable esters, citric acid ester plasticizer, epoxy plasticiser;
Described environment-friendly type radical polymerization inhibitor is selected from MEHQ, 2-Tert. Butyl Hydroquinone, 2, one or more combination in 6-di-tert-butyl hydroquinone, 2,5 di tert butyl hydroquinone, butylated hydroxy anisole, methyl gallate, Tenox PG.
Preferably, described citric acid ester plasticizer is triethyl citrate, tributyl citrate, tributyl acetylcitrate, ATOC.
Preferably, described epoxy plasticiser is epoxy soybean oil, epoxy acetyl linolenic acid methyl esters, epoxyfuoic-oleic, epoxy silkworm chrysalis oil acid butyl ester, ethyl hexyl ester of epoxidized soybean oil, 9,10-octyl epoxy stearates.
Preferably, wherein, the molar ratio of cyanoacetate and formaldehyde or paraformaldehyde is 1.00-1.05:1.00, the input amount of dehydrated organic solvent is 100-200ml/mol formaldehyde/paraformaldehyde, the input amount of basic catalyst is 0.2-0.6ml/mol formaldehyde/paraformaldehyde, environment-friendlyplasticizer plasticizer input amount is 5-20g/mol formaldehyde/paraformaldehyde, negatively charged ion stopper input amount is 2-5g/mol formaldehyde/paraformaldehyde, and environment-friendly type radical polymerization inhibitor input amount is 1-3g/mol formaldehyde/paraformaldehyde.
Preferably, described cyanoacetate is selected from one or more in ethyl cyanacetate, methyl-cyanacetate, the positive butyl ester of cyanoacetic acid, t-butylcyanoacetate, cyanoacetic acid n-octyl, cyanoacetic acid ethoxy ethyl ester, cyanoacetic acid methoxy acrylate.
Preferably, described basic catalyst is selected from one or more the combination in strongly alkaline compound, pyridines catalyzer, amines catalyst etc.
Preferably, described strongly alkaline compound is sodium hydroxide, potassium hydroxide or hydrated barta.
Preferably, described pyridines catalyzer is hexahydropyridine.
Preferably, described amines catalyst is methyldiethanolamine, dimethylethanolamine or triethylamine.
Preferably, described negatively charged ion stopper is selected from one or more combinations in metaphosphoric acid, toxilic acid, maleic anhydride, alkylsulphonic acid, Vanadium Pentoxide in FLAKES, alkyl sulfite esters, sultone, sulfurous gas and sulphur trioxide.
Preparation method of the present invention, select nontoxic organic solvent azeotropic dehydration in the condensation process, in cracking process, adopt the softening agent, stopper etc. of environment-friendly type simultaneously, the environment-friendly type α-cyanoacrylate of environment-protecting asepsis can be obtained, yield is high simultaneously, is applicable to the field higher to environmental requirement.
Embodiment
Below by embodiment, the present invention will be further described, but these embodiments do not limit the scope of the invention.
The cyanoacrylate mentioned in the present invention can be understood as compound corresponding to formula below:
Wherein R is alkyl, thiazolinyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or haloalkyl, special has methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl, allyl group, methacrylic, butenyl, propargyl, cyclohexyl, benzyl, phenyl, 2-chloroethyl, 3-chloropropyl, 2-chlorobutyl, trifluoroethyl, 2-methoxy ethyl, 3-methoxybutyl, 2-ethoxyethyl group.
Above-mentioned cyanoacrylate adhesive is that everybody is known, and preferred monomer is allyl group, methoxy ethyl, ethoxyethyl group, methyl, ethyl, propyl group, sec.-propyl or butyl ester.
Cyanoacetate described herein, including, but not limited to ethyl cyanacetate, methyl-cyanacetate, the positive butyl ester of cyanoacetic acid, t-butylcyanoacetate, cyanoacetic acid n-octyl, cyanoacetic acid ethoxy ethyl ester, cyanoacetic acid methoxy acrylate etc.
The product of described formaldehyde is selected from formaldehyde and paraformaldehyde.
Described basic catalyst be selected from strongly alkaline compound (as, sodium hydroxide, potassium hydroxide, hydrated barta etc.), pyridines catalyzer (as, hexahydropyridine), one or more combination in amines catalyst (e.g., methyldiethanolamine, dimethylethanolamine, triethylamine etc.) etc.
Non-toxic type organic solvent described herein, including, but not limited to normal heptane, normal hexane, hexanaphthene, toluene, dimethylbenzene, methylene dichloride, propylene dichloride, ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, methylcarbonate, diethyl carbonate, methyl alcohol, ethanol, propyl carbinol etc.Above-mentioned non-toxic type organic solvent can be selected from wherein one or more combinations.
Environment-friendlyplasticizer plasticizer described be herein selected from synthesis vegetable esters, citric acid ester plasticizer (as, triethyl citrate, tributyl citrate, tributyl acetylcitrate, ATOC etc.), epoxy plasticiser (as, epoxy soybean oil, epoxy acetyl linolenic acid methyl esters, epoxyfuoic-oleic, epoxy silkworm chrysalis oil acid butyl ester, ethyl hexyl ester of epoxidized soybean oil, 9,10-octyl epoxy stearates etc.) etc. in one or more combination.
Negatively charged ion stopper described is herein selected from one or more combinations in metaphosphoric acid, toxilic acid, maleic anhydride, alkylsulphonic acid, Vanadium Pentoxide in FLAKES, alkyl sulfite esters, sultone, sulfurous gas and sulphur trioxide etc.
Environment-friendly type radical polymerization inhibitor described is herein selected from MEHQ, 2-Tert. Butyl Hydroquinone, 2,6-di-tert-butyl hydroquinones, 2,5 di tert butyl hydroquinone, butylated hydroxy anisole, methyl gallate, Tenox PG etc.
Embodiment 1
Be applied to the preparation of ethyl α-cyanoacrylate
Ethyl cyanacetate and toluene are joined in 1000ml there-necked flask, when temperature rises to 60 DEG C, add the mixed solution of hexahydropyridine and formalin, after dropwising, heating and thermal insulation, backflow 1h is kept in 60 DEG C, carry out azeotropic dehydration 2h afterwards, add tributyl citrate afterwards, Vanadium Pentoxide in FLAKES, MEHQ etc., cracking is carried out at 170 DEG C of temperature and 1mmHg vacuum, obtain the crude monomer of ethyl α-cyanoacrylate, through rectifying, can obtain purity be 99.9% ethyl α-cyanoacrylate refine monomer, yield is calculated as 80%.
Wherein, the molar ratio of ethyl cyanacetate and formalin is 1.00:1, toluene input amount is 100ml/mol formaldehyde, hexahydropyridine input amount is 0.2ml/mol formaldehyde, tributyl citrate input amount is 5g/mol formaldehyde, Vanadium Pentoxide in FLAKES input amount is 2g/mol formaldehyde, and MEHQ input amount is 1g/mol formaldehyde.
Wherein: to be the implication of 100-200ml/mol formaldehyde/paraformaldehyde be toluene input amount: based on the formaldehyde of every mole or paraformaldehyde, the formaldehyde of every mole or paraformaldehyde add 100-200ml/mol toluene, lower with.
Embodiment 2
Be applied to the preparation of alpha-cyanoacrylate methoxy acrylate
Paraformaldehyde and propylene dichloride are joined in 1000ml there-necked flask, when temperature rises to 60 DEG C, add the mixed solution of sodium hydroxide and cyanoacetic acid methoxy acrylate, after dropwising, heating and thermal insulation, backflow 1.5h is kept in 60-90 DEG C, carry out azeotropic dehydration 3h, add synthesis vegetable esters afterwards, Vanadium Pentoxide in FLAKES, 2, 5-di-tert-butyl hydroquinone etc., cracking is carried out at 200 DEG C of temperature and 10mmHg vacuum, obtain the crude monomer of alpha-cyanoacrylate methoxy acrylate, through rectifying, can obtain purity be 99.9% ethyl α-cyanoacrylate refine monomer, calculated yield is 75%.
Wherein, the molar ratio of cyanoacetic acid methoxy acrylate and paraformaldehyde is 1.04:1, propylene dichloride input amount is 200ml/mol paraformaldehyde, sodium hydroxide input amount is 0.6ml/mol paraformaldehyde, synthesis vegetable esters input amount is 20g/mol paraformaldehyde, Vanadium Pentoxide in FLAKES input amount is 5g/mol paraformaldehyde, and 2,5-Tert. Butyl Hydroquinone input amount is 3g/mol paraformaldehyde.
Embodiment 3
Be applied to the preparation of α-cyanoacrylaten-butyl
Formalin and methylcarbonate are joined in 1000ml there-necked flask, when temperature rises to 65 DEG C, add the mixed solution of potassium hydroxide and the positive butyl ester of cyanoacetic acid, after dropwising, heating and thermal insulation, backflow 3h is kept in 80 DEG C, carry out azeotropic dehydration 3.5h, add epoxy soybean oil afterwards, Vanadium Pentoxide in FLAKES, butylated hydroxy anisole etc., cracking is carried out at 190 DEG C of temperature and 5mmHg vacuum, obtain the crude monomer of α-cyanoacrylaten-butyl, through rectifying, can obtain purity be 99.9% α-cyanoacrylaten-butyl refine monomer, yield is 70%.
Wherein, the molar ratio of the positive butyl ester of cyanoacetic acid and formalin is 1.02:1, methylcarbonate input amount is 100ml/mol formaldehyde, potassium hydroxide input amount is 0.4ml/mol formaldehyde, epoxy soybean oil input amount is 15g/mol formaldehyde, Vanadium Pentoxide in FLAKES input amount is 3g/mol formaldehyde, and butylated hydroxy anisole input amount is 2g/mol formaldehyde.
Preparation method of the present invention, select nontoxic organic solvent azeotropic dehydration in the condensation process, in cracking process, adopt the softening agent, stopper etc. of environment-friendly type simultaneously, can obtain the environment-friendly type α-cyanoacrylate of environment-protecting asepsis, yield is high simultaneously.
Above-described embodiment is only example character.For those skilled in the art, be appreciated that and can carry out multiple change, amendment, replacement and sex change to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is claims and equivalents thereof again.
Claims (10)
1. an environment-friendly type α-cyanoacrylate preparation method, is characterized in that, the method comprises the following steps:
With cyanoacetate and formaldehyde or paraformaldehyde for raw material, under the existence of basic catalyst, with can with the organic solvent of water azeotropic for dewatering agent, carry out condensation reaction, after dehydration completely, add environment-friendlyplasticizer plasticizer, negatively charged ion stopper, environment-friendly type radical polymerization inhibitor carry out cracking, and carry out rectifying to it, obtain α-cyanoacrylatemonomer;
Wherein, described organic solvent is selected from one or more combinations in normal heptane, normal hexane, hexanaphthene, toluene, dimethylbenzene, methylene dichloride, propylene dichloride, ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, methylcarbonate, diethyl carbonate, methyl alcohol, ethanol, propyl carbinol;
Described environment-friendlyplasticizer plasticizer is selected from one or more the combination in synthesis vegetable esters, citric acid ester plasticizer, epoxy plasticiser;
Described environment-friendly type radical polymerization inhibitor is selected from MEHQ, 2-Tert. Butyl Hydroquinone, 2, one or more combination in 6-di-tert-butyl hydroquinone, 2,5 di tert butyl hydroquinone, butylated hydroxy anisole, methyl gallate, Tenox PG.
2. preparation method according to claim 1, is characterized in that: described citric acid ester plasticizer is triethyl citrate, tributyl citrate, tributyl acetylcitrate, ATOC.
3. preparation method according to claim 1, it is characterized in that: described epoxy plasticiser is epoxy soybean oil, epoxy acetyl linolenic acid methyl esters, epoxyfuoic-oleic, epoxy silkworm chrysalis oil acid butyl ester, ethyl hexyl ester of epoxidized soybean oil, 9,10-octyl epoxy stearates.
4. preparation method according to claim 1, it is characterized in that: wherein, the molar ratio of cyanoacetate and formaldehyde or paraformaldehyde is 1.00-1.05:1.00, the input amount of dehydrated organic solvent is 100-200ml/mol formaldehyde/paraformaldehyde, the input amount of basic catalyst is 0.2-0.6ml/mol formaldehyde/paraformaldehyde, environment-friendlyplasticizer plasticizer input amount is 5-20g/mol formaldehyde/paraformaldehyde, negatively charged ion stopper input amount is 2-5g/mol formaldehyde/paraformaldehyde, and environment-friendly type radical polymerization inhibitor input amount is 1-3g/mol formaldehyde/paraformaldehyde.
5., according to the method described in claim 1, it is characterized in that: described cyanoacetate be selected from ethyl cyanacetate, methyl-cyanacetate, the positive butyl ester of cyanoacetic acid, t-butylcyanoacetate, cyanoacetic acid n-octyl, cyanoacetic acid ethoxy ethyl ester, cyanoacetic acid methoxy acrylate one or more.
6. according to the method described in claim 1, it is characterized in that: described basic catalyst is selected from one or more the combination in strongly alkaline compound, pyridines catalyzer, amines catalyst etc.
7. according to the method described in claim 6, it is characterized in that: described strongly alkaline compound is sodium hydroxide, potassium hydroxide or hydrated barta.
8. according to the method described in claim 6, it is characterized in that: described pyridines catalyzer is hexahydropyridine.
9. according to the method described in claim 6, it is characterized in that: described amines catalyst is methyldiethanolamine, dimethylethanolamine or triethylamine.
10. according to the method described in claim 1, it is characterized in that: described negatively charged ion stopper is selected from one or more combinations in metaphosphoric acid, toxilic acid, maleic anhydride, alkylsulphonic acid, Vanadium Pentoxide in FLAKES, alkyl sulfite esters, sultone, sulfurous gas and sulphur trioxide.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106349984A (en) * | 2016-08-24 | 2017-01-25 | 湖南浩森胶业有限公司 | Glue production process |
| CN109678758A (en) * | 2019-01-31 | 2019-04-26 | 河北诚信集团有限公司 | A kind of synthetic method of a-cyanoacrylate |
| CN110172303A (en) * | 2019-05-24 | 2019-08-27 | 浙江久而久化学有限公司 | A kind of stone adhesive and preparation method thereof |
| CN112266337A (en) * | 2020-09-30 | 2021-01-26 | 诺一迈尔(山东)医学科技有限公司 | Preparation method of low-aldehyde alpha-cyanoacrylate medical adhesive |
| CN112457784A (en) * | 2020-11-30 | 2021-03-09 | 山东禹王和天下新材料有限公司 | Quick-drying stone repairing adhesive and preparation method thereof |
| CN113648451A (en) * | 2021-08-19 | 2021-11-16 | 青岛大学 | Novel alpha-cyanoacrylate medical adhesive and preparation method thereof |
| CN114561154A (en) * | 2022-02-28 | 2022-05-31 | 浙江久而久化学有限公司 | UV (ultraviolet) and moisture dual-solid instant adhesive and preparation method thereof |
| CN115321959A (en) * | 2022-08-22 | 2022-11-11 | 广东环波新材料有限责任公司 | Environment-friendly LTCC ceramic slurry and substrate preparation method |
| CN116217433A (en) * | 2023-05-10 | 2023-06-06 | 潍坊德高新材料有限公司 | Preparation method of cyanoacrylate monomer |
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| CN110172303A (en) * | 2019-05-24 | 2019-08-27 | 浙江久而久化学有限公司 | A kind of stone adhesive and preparation method thereof |
| CN112266337A (en) * | 2020-09-30 | 2021-01-26 | 诺一迈尔(山东)医学科技有限公司 | Preparation method of low-aldehyde alpha-cyanoacrylate medical adhesive |
| CN112266337B (en) * | 2020-09-30 | 2022-10-25 | 诺一迈尔(山东)医学科技有限公司 | Preparation method of low-aldehyde alpha-cyanoacrylate medical adhesive |
| CN112457784A (en) * | 2020-11-30 | 2021-03-09 | 山东禹王和天下新材料有限公司 | Quick-drying stone repairing adhesive and preparation method thereof |
| CN113648451A (en) * | 2021-08-19 | 2021-11-16 | 青岛大学 | Novel alpha-cyanoacrylate medical adhesive and preparation method thereof |
| CN114561154A (en) * | 2022-02-28 | 2022-05-31 | 浙江久而久化学有限公司 | UV (ultraviolet) and moisture dual-solid instant adhesive and preparation method thereof |
| CN114561154B (en) * | 2022-02-28 | 2022-10-28 | 浙江久而久化学有限公司 | UV (ultraviolet) and moisture dual-solid instant adhesive and preparation method thereof |
| CN115321959A (en) * | 2022-08-22 | 2022-11-11 | 广东环波新材料有限责任公司 | Environment-friendly LTCC ceramic slurry and substrate preparation method |
| CN116217433A (en) * | 2023-05-10 | 2023-06-06 | 潍坊德高新材料有限公司 | Preparation method of cyanoacrylate monomer |
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Application publication date: 20150311 |