CN101096580A - Method for improving storage stability of alpha-cyanacrylate adhesive - Google Patents
Method for improving storage stability of alpha-cyanacrylate adhesive Download PDFInfo
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Abstract
The invention discloses an improving method of storage stability of alpha-cyano acrylate adhesive in the alpha-cyano acrylate adhesive domain, which comprises the following steps: adopting cyanoacetate and formagene or formaldehyde solution as raw material; using low-boiling point organic solvent to coboil with water as dehydrant under alkaline catalyst; doing condensing reaction at 80-100 deg. c under normal pressure or 60+-5deg. c without vacuum degree at 0.5-50mmHg without dehydrant; adding alcohol removing agent after dehydrating completely to stir sufficiently; refluxing stably for 0.5-2h; recycling (dehydrant)alcohol removing agent to add inhibitor to do cracking distilling with vacuum degree at 0.5-25mmHg under 160-220 deg. c; rectifying; obtaining the product; obtaining the product with alcohol content less than 50ppm to keep biological property over normal temperature.
Description
Technical field
The invention belongs to the alpha-cyanacrylate adhesive field, particularly improve the method for storage stability of alpha-cyanacrylate adhesive.
Background technology
With α-Qing Jibingxisuanzhi is that monomer is that the poor storage stability of the instant drying adhesive of main component is its main shortcoming, the major cause of its poor stability is to contain in the monomer alcohols material of trace and the water and the monomer of trace had an effect, and easily anionic polymerisation takes place and solidifies.In order to improve its stability, this has been carried out a large amount of research over 30 years both at home and abroad, existent method is to add stopper or adopt physical method to come the encapsulating adhesive monomer with paraffin oil or rare gas element at present, but all there is defective in these methods, such as in product, adding stopper, performances such as set time of tackiness agent and bonding strength are affected, and these methods are not fundamentally got rid of the alcohols material that directly causes its poor stability, so that must add a large amount of stoppers.Like this, though improved monomeric stability in storage, greatly reduce monomeric reactive behavior curing speed is reduced.The synthesis technique or the method for preparation α-Qing Jibingxisuanzhi (mainly being α-Qing Jibingxisuanwanjizhi) are disclosed as CN1047077.The main method of known this technology is at present: alkyl cyanoacetates (is looked different product line ethyl cyanacetate commonly used, cyanoacetic acid butyl ester or the like) (is being generally pyridine with Paraformaldehyde 96 or formalin at basic catalyst, sodium hydroxide, sodium alkoxide or the like) and under the dewatering agent existence carry out condensation reaction, after the dehydration fully, reclaim dewatering agent, under certain temperature and stopper, carry out the cracking distillation after adding stopper, obtain α-Qing Jibingxisuanzhi (as ethyl, alpha-cyanoacrylate butyl ester or the like) crude monomer, rectifying feed the product that can obtain stable storing behind the sulfurous gas.
The shortcoming of above-mentioned known technology is easily to produce alcohols material in the reaction process, and when rectifying, alcohols material and product are not easily separated, causes product purity not high (generally can contain the above alcohols material of 500ppm), poor storage stability.In order to increase the stability in storage of product, generally need to add the sulfurous gas of 150～200ppm.Yet behind the sulfurous gas that adds 150～200ppm, the curing speed of α-Qing Jibingxisuanzhi is with more than the decline twice.
Summary of the invention
The object of the present invention is to provide and a kind ofly improve storage stability of alpha-cyanacrylate adhesive and do not reduce the method for its curing speed, can be in producing the α-Qing Jibingxisuanzhi process, to cause the alcohols material of poor stability thoroughly to be removed, thereby obtain that a kind of productive rate and purity can both be improved, and the good α-Qing Jibingxisuanzhi (purity can reach more than 99.5%) of stability in storage.
The method of raising storage stability of alpha-cyanacrylate adhesive of the present invention may further comprise the steps:
(1). cyan-acetic ester is mixed in reactor with formalin or Paraformaldehyde 96, in the presence of basic catalyst, in temperature is 80～100 ℃, under the normal pressure doing to carry out condensation reaction under the condition of dewatering agent with water azeotropic lower boiling (60～100 ℃) organic solvent; Dehydration back fully adds except that pure agent, the stable backflow 0.5～2 hour under fully stirring, adding negatively charged ion stopper, free radical polymerization inhibitor or their mixture after reclaiming dewatering agent and removing pure agent, is that (preferred 0.5～20mmHg) vacuum and temperature are to carry out the crude monomer that the cracking distillation obtains corresponding α-Qing Jibingxisuanzhi under the condition of 160～220 ℃ (preferred 165～210 ℃) to 0.5～25mmHg in vacuum tightness again; Or
Cyan-acetic ester is mixed in reactor with formalin or Paraformaldehyde 96, in the presence of basic catalyst, in temperature is 60 ± 5 ℃, and vacuum tightness is (preferred 0.5～30mmHg), and do not have under the condition of any and water azeotropic dewatering agent and carry out condensation reaction under the vacuum of 0.5～50mmHg; Dehydration back fully adds except that pure agent, the stable backflow 0.5～2 hour under fully stirring, add negatively charged ion stopper, free radical polymerization inhibitor or their mixture after reclaim removing pure agent, and then be that (preferred 0.5～20mmHg) vacuum and temperature are to carry out the crude monomer that the cracking distillation obtains corresponding α-Qing Jibingxisuanzhi under the condition of 160～220 ℃ (preferred 165～210 ℃) to 0.5～25mmHg in vacuum tightness;
Wherein, the molar ratio of cyan-acetic ester and formaldehyde or Paraformaldehyde 96 is 1.00～1.25: 1.00; The add-on of dewatering agent is 30～60ml/mol formaldehyde or Paraformaldehyde 96; The add-on of removing pure agent is 5～30ml/mol formaldehyde or Paraformaldehyde 96; The add-on of negatively charged ion stopper is 4～8g/mol formaldehyde or Paraformaldehyde 96, and the add-on of free radical polymerization inhibitor is 1～3g/mol formaldehyde or Paraformaldehyde 96;
(2). the crude monomer of the α-Qing Jibingxisuanzhi that step (1) is obtained can obtain the smart monomer (pure content is less than 50ppm) of the higher relatively α-Qing Jibingxisuanzhi of purity again through rectifying, its stability in storage for keeping at normal temperatures the rerum natura change did not take place more than half a year.
Described cyanoacetate compound is including, but not limited to methyl-cyanacetate, ethyl cyanacetate, cyanoacetic acid isopropyl ester, the cyanoacetic acid butyl ester, cyanoacetic acid isobutyl ester, cyanoacetic acid n-octyl, the different monooctyl ester of cyanoacetic acid, cyanoacetic acid methoxyl group ethyl ester or cyanoacetic acid ethoxy ethyl ester etc.
Described catalyzer is selected from a kind of in sodium hydroxide, potassium hydroxide, pyridine (as hexahydropyridine), thanomin (as diethanolamine) or the triethylamine etc., and add-on is 0.3～5ml/mol formaldehyde or Paraformaldehyde 96.
Described dewatering agent is lower boiling organic solvents such as methyl alcohol, ethanol, toluene, normal hexane, hexanaphthene, sherwood oil or ethylene dichloride.
Describedly remove pure agent and be selected from a kind of in Acetyl Chloride 98Min., diacetyl oxide, trimethylchlorosilane, the hexamethyldisilazane etc., input amount is 5～30ml/mol formaldehyde or Paraformaldehyde 96.
Described negatively charged ion stopper is a Vanadium Pentoxide in FLAKES; Described free radical polymerization inhibitor is Resorcinol, pyrocatechol, p-tert-butylphenol or their mixture.
Feature of the present invention is exactly in reaction process to remove pure agent and thoroughly remove alcohols material by selecting for use, thereby obtains that a kind of purity is very high, the good α-Qing Jibingxisuanzhi of stability in storage is a monomer.The problem that it is the stability in storage of glue that the method that the present invention adopts adding to remove pure agent has fundamentally solved long-term indeterminable α-Qing Jibingxisuanzhi is operated also very easy.Also obtained simultaneously purity very high, contain alcohol amount (＜50ppm) very low α-Qing Jibingxisuanzhidanti.The present invention has application prospect and significantly economic benefit widely in each series product of preparation α-Qing Jibingxisuanzhi.
Embodiment
Further specify the present invention below in conjunction with representational embodiment, but these embodiment do not limit essential scope of the present invention.
The preparation of embodiment 1. ethyl
Ethyl cyanacetate and formalin are made starting raw material to be mixed in reactor, in the presence of hexahydropyridine, making dewatering agent with water azeotropic ethylene dichloride, its add-on is a 60ml/mol formaldehyde, carries out condensation reaction under temperature is 80 ± 5 ℃, non-pressurized condition; Dehydration back fully adds Acetyl Chloride 98Min., the stable backflow 2 hours under fully stirring, reclaim the dewatering agent ethylene dichloride and remove pure agent Acetyl Chloride 98Min., add Vanadium Pentoxide in FLAKES, the Resorcinol stopper, under the condition of 0.5～25mmHg vacuum and 160～190 ℃, carry out the cracking distillation again, can obtain pure content through rectifying again is ethyl essence monomer 99.2% or more less than the purity of 50ppm, productive rate is 65%, wherein the molar ratio of ethyl cyanacetate and formaldehyde is 1.05: 1.00, the input amount of hexahydropyridine is a 3ml/mol formaldehyde, the add-on of Acetyl Chloride 98Min. is a 5ml/mol formaldehyde, the add-on of Vanadium Pentoxide in FLAKES is a 5g/mol formaldehyde, the add-on of Resorcinol is a 2g/mol formaldehyde, and it is above and keep rerum natura and do not change that the ethyl tackiness agent of producing at room temperature can be preserved half a year.
20 gram products are put into the 50ml Erlenmeyer flask, carry out the stability in storage test after with grinding port plug bottleneck being covered gently.Curing speed test is that product is dropped between the two sheet glass slide glasss with dropper, then with two slide glasss each other parallel sliding to can not slide suddenly the time till, calculate the corresponding time.Its result is as follows:
| Sample type | 3 days | 12 days | Final viscosity | Curing speed |
| Embodiment 1 | Gel-free | Gel-free | 300 centipoises | 15 seconds/glass-glass |
| There is not the pure agent of removing | Gel | 15 seconds/glass-glass |
Annotate: probe temperature is 70 ℃.
The preparation of embodiment 2. alpha-cyanoacrylate methoxyl group ethyl esters
Cyanoacetic acid methoxyl group ethyl ester is made starting raw material with Paraformaldehyde 96 to be mixed in reactor, in the presence of hexahydropyridine, in temperature is 60 ± 5 ℃, vacuum tightness is 30mmHg when initial, be to carry out condensation reaction under the condition of 2mmHg during end, dehydration back fully adds trimethylchlorosilane, the stable backflow 2 hours under fully stirring, reclaim and remove pure agent trimethylchlorosilane, add Vanadium Pentoxide in FLAKES, the Resorcinol stopper, under the condition of 0.5～25mmHg vacuum and 160～200 ℃, carry out the cracking distillation again, can obtain pure content through rectifying again is alpha-cyanoacrylate methoxyl group ethyl ester essence monomer 99.2% or more less than the purity of 50ppm, productive rate is 60%, wherein the molar ratio of cyanoacetic acid methoxyl group ethyl ester and Paraformaldehyde 96 was generally 1.07: 1.00, the throwing amount of hexahydropyridine is the 3ml/mol Paraformaldehyde 96, the add-on of trimethylchlorosilane is the 5ml/mol Paraformaldehyde 96, the add-on of Vanadium Pentoxide in FLAKES is the 6g/mol Paraformaldehyde 96, the add-on of Resorcinol is the 2g/mol Paraformaldehyde 96, and it is above and keep rerum natura and do not change that the alpha-cyanoacrylate methoxyl group ethyl ester tackiness agent of producing at room temperature can be preserved half a year.
20 gram products are put into the 50ml Erlenmeyer flask, carry out the stability in storage test after with grinding port plug bottleneck being covered gently.Curing speed test is that product is dropped between the two sheet glass slide glasss with dropper, then with two slide glasss each other parallel sliding to can not slide suddenly the time till, calculate the corresponding time.Its result is as follows:
| Sample type | 3 days | 14 days | Final viscosity | Curing speed |
| Embodiment 2 | Gel-free | Gel-free | 500 centipoises | 30 seconds/glass-glass |
| There is not the pure agent of removing | Gel | 30 seconds/glass-glass |
Annotate: probe temperature is 70 ℃.
The preparation of embodiment 3. methyls
Methyl-cyanacetate is mixed in reactor with Paraformaldehyde 96 (granularity is 40～120 orders), in the presence of sodium hydroxide catalyst, is 100 ℃ in temperature, carries out condensation reaction with toluene as dewatering agent under the normal pressure, and its add-on is the 60ml/mol Paraformaldehyde 96; Dehydration back fully adds diacetyl oxide, the stable backflow 1 hour under fully stirring, reclaim dewatering agent toluene and remove pure agent diacetyl oxide, adding behind Vanadium Pentoxide in FLAKES, pyrocatechol and the p-tert-butylphenol stopper in vacuum tightness is to carry out the cracking distillation under the vacuum of 0.5～25mmHg and the condition that temperature is 160～190 ℃ again, pass through rectifying again, can obtain pure content and be the smart monomer of 99.2% methyl less than the yield 65% of 50ppm and purity; Wherein, the molar ratio of methyl-cyanacetate and Paraformaldehyde 96 is 1.05: 1.00; The add-on of Vanadium Pentoxide in FLAKES is the 4g/mol Paraformaldehyde 96, and the add-on of diacetyl oxide is the 5ml/mol Paraformaldehyde 96, and the add-on of pyrocatechol and p-tert-butylphenol is respectively the 1g/mol Paraformaldehyde 96; The add-on of sodium hydroxide is 1.0～1.5g/mol Paraformaldehyde 96, and it is above and keep rerum natura and do not change that the methyl tackiness agent of producing at room temperature can be preserved half a year.
20 gram products are put into the 50ml Erlenmeyer flask, carry out the stability in storage test after with grinding port plug bottleneck being covered gently.Curing speed test is that product is dropped between the two sheet glass slide glasss with dropper, then with two slide glasss each other parallel sliding to can not slide suddenly the time till, calculate the corresponding time.Its result is as follows:
| Sample type | 3 days | 12 days | Final viscosity | Curing speed |
| Embodiment 3 | Gel-free | Gel-free | 250 centipoises | 15 seconds/glass-glass |
| There is not the pure agent of removing | Gel | 15 seconds/glass-glass |
Annotate: probe temperature is 70 ℃.
Claims (10)
1. a method that improves storage stability of alpha-cyanacrylate adhesive is characterized in that, this method may further comprise the steps:
(1). cyan-acetic ester is mixed in reactor with formalin or Paraformaldehyde 96, in the presence of basic catalyst, is 80～100 ℃ in temperature, under the normal pressure doing to carry out condensation reaction under the condition of dewatering agent with water azeotropic low boiling point organic solvent; Dehydration back fully adds except that pure agent, the stable backflow under fully stirring, adding negatively charged ion stopper, free radical polymerization inhibitor or their mixture after reclaiming dewatering agent and removing pure agent, is to carry out the crude monomer that the cracking distillation obtains corresponding α-Qing Jibingxisuanzhi under the vacuum of 0.5～25mmHg and the condition that temperature is 160～220 ℃ in vacuum tightness again; Described lower boiling is meant that temperature is 60～100 ℃; Or
Cyan-acetic ester is mixed in reactor with formalin or Paraformaldehyde 96, in the presence of basic catalyst, is 60 ± 5 ℃ in temperature, and vacuum tightness is under the vacuum of 0.5～50mmHg, and does not have under the condition of any and water azeotropic dewatering agent and carry out condensation reaction; Dehydration back fully adds except that pure agent, the stable backflow under fully stirring, add negatively charged ion stopper, free radical polymerization inhibitor or their mixture after reclaim removing pure agent, and then be to carry out the crude monomer that the cracking distillation obtains corresponding α-Qing Jibingxisuanzhi under the vacuum of 0.5～25mmHg and the condition that temperature is 160～220 ℃ in vacuum tightness;
Wherein, the molar ratio of cyan-acetic ester and formaldehyde or Paraformaldehyde 96 is 1.00～1.25: 1.00; The add-on of dewatering agent is 30～60ml/mol formaldehyde or Paraformaldehyde 96; The add-on of removing pure agent is 5～30ml/mol formaldehyde or Paraformaldehyde 96; The add-on of negatively charged ion stopper is 4～8g/mol formaldehyde or Paraformaldehyde 96, and the add-on of free radical polymerization inhibitor is 1～3g/mol formaldehyde or Paraformaldehyde 96;
(2). the crude monomer of the α-Qing Jibingxisuanzhi that step (1) is obtained passes through rectifying again, can obtain the smart monomer of pure content less than the α-Qing Jibingxisuanzhi of 50ppm.
2. method according to claim 1 is characterized in that: described cracking distillatory vacuum tightness is 0.5～20mmHg, and temperature is 165～210 ℃.
3. method according to claim 1 is characterized in that: described vacuum tightness of carrying out condensation reaction under the condition of no any dewatering agent is 0.5～30mmHg.
4. method according to claim 1, it is characterized in that: described cyan-acetic ester is a methyl-cyanacetate, ethyl cyanacetate, the cyanoacetic acid isopropyl ester, the cyanoacetic acid butyl ester, cyanoacetic acid isobutyl ester, cyanoacetic acid n-octyl, the different monooctyl ester of cyanoacetic acid, cyanoacetic acid methoxyl group ethyl ester or cyanoacetic acid ethoxy ethyl ester.
5. method according to claim 1 is characterized in that: described catalyzer add-on is 0.3～5ml/mol formaldehyde or Paraformaldehyde 96.
6. method according to claim 1 or 5 is characterized in that: described catalyzer is selected from a kind of in sodium hydroxide, potassium hydroxide, pyridine, thanomin or the triethylamine.
7. method according to claim 6 is characterized in that: described pyridine is a hexahydropyridine; Described thanomin is a diethanolamine.
8. method according to claim 1 is characterized in that: described dewatering agent is methyl alcohol, ethanol, toluene, normal hexane, hexanaphthene, sherwood oil or ethylene dichloride.
9. method according to claim 1 is characterized in that: describedly remove pure agent and be selected from a kind of in Acetyl Chloride 98Min., diacetyl oxide, trimethylchlorosilane, the hexamethyldisilazane.
10. method according to claim 1 is characterized in that: described negatively charged ion stopper is a Vanadium Pentoxide in FLAKES; Described free radical polymerization inhibitor is Resorcinol, pyrocatechol, p-tert-butylphenol or their mixture.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102030681A (en) * | 2010-11-18 | 2011-04-27 | 山东禹王实业有限公司化工分公司 | Preparation method of halohydrocarbon-free alpha-cyanoacrylate |
| CN103205206A (en) * | 2012-01-16 | 2013-07-17 | 浙江久而久化学有限公司 | Magnetic material adhesive and preparation method thereof |
| CN103232366A (en) * | 2013-04-25 | 2013-08-07 | 华南理工大学 | Preparation method of alpha-cyano propenoic acid-2-methoxy ethyl ester |
| CN105218509A (en) * | 2015-07-12 | 2016-01-06 | 九江学院 | The minimizing technology of ethylene glycol in a kind of NSC 11801 |
| CN107954901A (en) * | 2017-12-07 | 2018-04-24 | 邓立新 | A kind of synthetic method of a-cyanoacrylate |
| CN108689881A (en) * | 2018-07-12 | 2018-10-23 | 广州白云医用胶有限公司 | The synthetic method of α-n-octylcyanoacrylate |
| WO2020085334A1 (en) * | 2018-10-23 | 2020-04-30 | 東亞合成株式会社 | Photocurable adhesive composition |
| CN115611772A (en) * | 2022-11-07 | 2023-01-17 | 湖南浩森胶业有限公司 | Synthesis method of alpha-n-octyl cyanoacrylate |
| CN115678441A (en) * | 2022-11-14 | 2023-02-03 | 广东粤港澳大湾区黄埔材料研究院 | Cyanoacrylate adhesive and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030681A (en) * | 2010-11-18 | 2011-04-27 | 山东禹王实业有限公司化工分公司 | Preparation method of halohydrocarbon-free alpha-cyanoacrylate |
| CN103205206A (en) * | 2012-01-16 | 2013-07-17 | 浙江久而久化学有限公司 | Magnetic material adhesive and preparation method thereof |
| CN103232366A (en) * | 2013-04-25 | 2013-08-07 | 华南理工大学 | Preparation method of alpha-cyano propenoic acid-2-methoxy ethyl ester |
| CN105218509A (en) * | 2015-07-12 | 2016-01-06 | 九江学院 | The minimizing technology of ethylene glycol in a kind of NSC 11801 |
| CN105218509B (en) * | 2015-07-12 | 2017-11-10 | 九江学院 | The minimizing technology of ethylene glycol in a kind of ethylene carbonate |
| CN107954901B (en) * | 2017-12-07 | 2020-07-17 | 新昌县勤勉生物医药科技有限公司 | Synthesis method of α -cyanoacrylate |
| CN107954901A (en) * | 2017-12-07 | 2018-04-24 | 邓立新 | A kind of synthetic method of a-cyanoacrylate |
| CN108689881A (en) * | 2018-07-12 | 2018-10-23 | 广州白云医用胶有限公司 | The synthetic method of α-n-octylcyanoacrylate |
| CN108689881B (en) * | 2018-07-12 | 2021-09-17 | 广州白云医用胶有限公司 | Synthesis method of alpha-n-octyl cyanoacrylate |
| WO2020085334A1 (en) * | 2018-10-23 | 2020-04-30 | 東亞合成株式会社 | Photocurable adhesive composition |
| JPWO2020085334A1 (en) * | 2018-10-23 | 2021-09-24 | 東亞合成株式会社 | Photocurable adhesive composition |
| CN115611772A (en) * | 2022-11-07 | 2023-01-17 | 湖南浩森胶业有限公司 | Synthesis method of alpha-n-octyl cyanoacrylate |
| CN115678441A (en) * | 2022-11-14 | 2023-02-03 | 广东粤港澳大湾区黄埔材料研究院 | Cyanoacrylate adhesive and preparation method thereof |
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