CN103739828A - Preparation method of cardanol-based high temperature-resistant epoxy resin curing agent - Google Patents
Preparation method of cardanol-based high temperature-resistant epoxy resin curing agent Download PDFInfo
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- CN103739828A CN103739828A CN201310703958.2A CN201310703958A CN103739828A CN 103739828 A CN103739828 A CN 103739828A CN 201310703958 A CN201310703958 A CN 201310703958A CN 103739828 A CN103739828 A CN 103739828A
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Abstract
The invention relates to a preparation method of a cardanol-based high temperature-resistant epoxy resin curing agent. The preparation method comprises the steps of firstly weighing cardanol, a phenolic compound, paraformaldehyde and diamine or polyamine according to weight, adding the cardanol, the phenolic compound and the paraformaldehyde into a reaction container, adding a catalyst, heating at the temperature of 75-100 DEG C for 2-6h to obtain an intermediate, then cooling the intermediate to 60-68 DEG C, adding the diamine or the polyamine, adding the remaining paraformaldehyde at the temperature in a stirring state, then heating till the temperature achieves 65-95 DEG C, reacting for 4-8h, and dehydrating in a vacuum state to obtain the cardanol-based high temperature-resistant epoxy resin curing agent provided by the invention. The synthesized curing agent has the advantages of great surface hardness and Shore hardness, excellent gloss, good high temperature resistance and low-temperature fast curing. According to the preparation method disclosed by the invention, the epoxy resin curing agent with a wide range of curing temperature, high temperature resistance and excellent surface performance is obtained and is suitable for requirements of primer paint and finish paint.
Description
Technical field:
The present invention relates to chemical field, relate in particular to macromolecular material, particularly epoxy curing agent, specifically a kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol.
Background technology:
Cardanol (Cardanol) is that one is refined and formed, can replace or partly replace phenol for the manufacture of epoxy hardener, liquid phenolic resin, liquid or pulverous heat-reactive phenolic resin through modern technique from natural cashew nut shell oil.Cardanol also has following characteristics because of its special chemical structure: 1,, containing benzene ring structure, have resistance to elevated temperatures; 2, the hydroxyl of polarity can provide wetting and active to contact surface of system; 3, a position is containing carbon 15 straight chains of unsaturated double-bond, can provide the good toughness of system, excellent hydrophobic nature and low-permeability and from dryness.
The solidifying agent of general heat resistant type is selected anhydride curing agent, as cis-butenedioic anhydride, Tetra hydro Phthalic anhydride and derivative thereof; Phenyl amines solidifying agent is as diaminodiphenylsulfone(DDS) etc., the curing general thermotolerance of epoxy resin of these solidifying agent is all relatively good, but these solidifying agent are had relatively high expectations to condition of cure, generally need to add catalyzer hot setting, low-temperature curing is not known where to begin, the epoxy hardener toxicity of phenyl amines is larger, easily carcinogenic, poor toughness.Anhydride curing agent is as volatile in cis-butenedioic anhydride, and pungency is strong.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol, the preparation method of the described this high-temperature-resistant epoxy resin solidifying agent based on cardanol will solve that heat resistant type solidifying agent condition of cure of the prior art is had relatively high expectations, toxicity is large, the technical problem of poor toughness.
The preparation method of this high-temperature-resistant epoxy resin solidifying agent based on cardanol of the present invention, comprise the following steps: first according to weight, take cardanol, phenolic compound, paraformaldehyde, amine, described cardanol, phenolic compound, paraformaldehyde, the mol ratio of amine is 1:0～3:0.5～4:0.8～1.5, by cardanol, phenolic compound and part paraformaldehyde add in reaction vessel, and add appropriate zinc acetate as catalyzer, at 75～100 ℃, heat 2～6 hours to obtain intermediate, then described intermediate is cooled to 60～68 ℃, add amine, in this temperature and under whipped state, add remaining paraformaldehyde in batches, then temperature is brought up to 65～95 ℃, react 4～8 hours, under vacuum state, dehydration obtains solidifying agent.
Further, cardanol and phenolic compound are added in the process of reaction vessel, the mol ratio of cardanol and phenolic compound is 1:1～3.
Further, described phenolic compound includes but not limited to cresols or xylenol or nonyl phenol or phenol or p-tert-butylphenol or o-tert-butyl phenol or to phenyl phenol or orthoxenol or p-phenyl phenol or diphenylol propane or to alkylphenol, and the alkyl of described alkylphenol is straight chain or containing side chain.
Further, described amine includes but not limited to quadrol or diethylenetriamine or triethylene tetramine or tetraethylene pentamine or polyethylene polyamine or m-xylene diamine or aminoethyl piperazine or isophorone diamine, m-xylene diamine, 1,3-BAC.
Further, the quality of described zinc acetate is 0.3%～5% of cardanol quality.
Concrete, can divide and add remaining paraformaldehyde for 2-5 time.
When the present invention uses, can use separately, also can be mixed with other solidifying agent, improve the dryness of other solidifying agent, thermotolerance.
The synthetic solidifying agent of the present invention has extraordinary surface hardness (>2H) and shore hardness (>95o), glossiness good (Gao Guang), resistance to elevated temperatures good (at 100 ℃, 30min loss of strength is no more than 30%), can low temperature fast setting.The present invention is the epoxy curing agent that a kind of solidification value scope is wide, high temperature resistant, surface property is good, is applicable to the requirement of priming paint and finish paint.
The present invention and prior art contrast, and its effect is actively with obvious.Modified by cardanol pnenolic aldehyde amine hardener of the present invention, due to the effect of long alkyl chain in cardanol (C15H31-2n, n=0-3), has toughening effect to system, but caused with the thermotolerance of epoxy curing systems, declines.The present invention introduces the phenolic structure between phenyl ring in reaction molecular, greatly improved thermotolerance and the hardness (comprising surface hardness and solid piece hardness) of general epoxy resin, and molecular weight is large, and toxicity is low, good toughness.With respect to other heat resistant type solidifying agent such as anhydrides and phenyl aminess, the advantage of this money solidifying agent is to have improved general cardanol solidifying agent resistance toheat and hardness, has also retained good toughness and curability at low temperatures simultaneously, and over-all properties is outstanding.Being applicable to some has requirement to resistance toheat but is not too high, but keeps low temperature (10 ℃) to solidify, and the occasion of the advantage of traditional cardanol resin such as good toughness, as transformer application.
Embodiment:
Embodiment 1
Dihydroxyphenyl propane (1mol), cardanol (300g, 1mol) and paraformaldehyde (30g, 1mol) are added in the four-hole bottle with heating jacket, and add 3g zinc acetate as catalyzer, heat 2 hours to obtain intermediate SM at 100 ℃.SM is cooled to 65 ℃, add diethylenetriamine (1mol), under this temperature whipped state, add in batches paraformaldehyde (30g, 1mol) then temperature be elevated to 80 ℃ of reactions 5 hours, reaction finishes to slough the water discharging generating in reaction under final vacuum state and obtains this solidifying agent (S1).Viscosity 30000mPa.S, amine value 290mgKOH/g, solid content 95%, surface hardness >2H, shore hardness >95 degree
Resistance toheat comparison
Wherein MD650 is the cardanol pnenolic aldehyde amine hardener that Shanghai Meidong Biological Material Co., Ltd produces, commercialization, and the excellent mid-to high-end product that belongs to of performance performance, is the main product of cardanol solidifying agent.By relatively finding out, use the curing solid piece of the epoxy relative MD650 resistance toheat in same proportioning situation of phenol aldehyde modified cardanol pnenolic aldehyde amine hardener of the present invention's research and development to significantly improve.Have benefited from the one hand the present invention and used dihydroxyphenyl propane that the phenyl ring density of the molecule of solidifying agent is increased, have benefited from the other hand the introducing of phenolic structure, after solidifying agent and epoxy resin cure, with the advantage of obvious resol, hardness and thermotolerance significantly improve.
Embodiment 2
Cardanol (600g, 2mol) and paraformaldehyde (30g, 1mol) are added in the four-hole bottle with heating jacket, and add 3g zinc acetate as catalyzer, heat 2 hours to obtain intermediate SM at 100 ℃.SM is cooled to 65 ℃, add tetraethylene pentamine (1mol), under this temperature whipped state, add in batches paraformaldehyde (1mol) then temperature be elevated to 80 ℃ of reactions 5 hours, reaction finishes to slough the water discharging generating in reaction under final vacuum state and obtains this solidifying agent (S2).Viscosity 100Pa.S, amine value 285mgKOH/g, solid content 98%, surface hardness >2H, shore hardness 90-95 degree
Resistance toheat comparison
Wherein MD650 is the cardanol pnenolic aldehyde amine hardener that Shanghai Meidong Biological Material Co., Ltd produces, commercialization, and the excellent mid-to high-end product that belongs to of performance performance, is the main product of cardanol solidifying agent.By relatively finding out, use the curing solid piece of the epoxy relative MD650 resistance toheat in same proportioning situation of phenol aldehyde modified cardanol pnenolic aldehyde amine hardener of the present invention's research and development to significantly improve.Have benefited from the introducing of phenolic structure, after solidifying agent and epoxy resin cure with the obvious advantage of resol, hardness and thermotolerance significantly improve, but introduce owing to there is no dihydroxyphenyl propane, so this solidifying agent (S2) does not have solidifying agent (S1) good heat resistance, but relatively traditional epoxy curing agent MD650 compares raising also clearly.
Embodiment 3
By phenol A(1mol), cardanol (300g, 1mol) and paraformaldehyde (30g, 1mol) add in the four-hole bottle with heating jacket, and adds 5g zinc acetate as catalyzer, heats 2 hours to obtain intermediate SM at 100 ℃.SM is cooled to 65 ℃, add tetraethylene pentamine (189g, 1mol), under this temperature whipped state, add paraformaldehyde (30g in batches, 1mol) then temperature is elevated to 80 ℃ of reactions 5 hours, and reaction finishes to slough the water discharging generating in reaction under final vacuum state and obtains this solidifying agent (S1).Viscosity 30000mPa.S, amine value 290mgKOH/g, solid content 95%, surface hardness >2H, shore hardness >95 degree
Resistance toheat comparison
Wherein MD650 is the cardanol pnenolic aldehyde amine hardener that Shanghai Meidong Biological Material Co., Ltd produces, commercialization, and the excellent mid-to high-end product that belongs to of performance performance, is the main product of cardanol solidifying agent.By relatively finding out, use the curing solid piece of the epoxy relative MD650 resistance toheat in same proportioning situation of phenol aldehyde modified cardanol pnenolic aldehyde amine hardener of the present invention's research and development to significantly improve.Have benefited from the one hand the present invention and used dihydroxyphenyl propane that the phenyl ring density of the molecule of solidifying agent is increased, have benefited from the other hand the introducing of phenolic structure, after solidifying agent and epoxy resin cure, with the advantage of obvious resol, hardness and thermotolerance significantly improve.
Claims (5)
1. the preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol, it is characterized in that: first according to weight, take cardanol, phenolic compound, paraformaldehyde, amine, described cardanol, phenolic compound, paraformaldehyde, the mol ratio of amine is 1:0～3:0.5～4:0.8～1.5, by cardanol, phenolic compound and part paraformaldehyde add in reaction vessel, and add appropriate zinc acetate as catalyzer, at 75～100 ℃, heat 2～6 hours to obtain intermediate, then described intermediate is cooled to 60～68 ℃, add amine, in this temperature and under whipped state, add remaining paraformaldehyde in batches, then temperature is brought up to 65～95 ℃, react 4～8 hours, under vacuum state, dehydration obtains solidifying agent.
2. the preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol as claimed in claim 1, is characterized in that: cardanol and phenolic compound are added in the process of reaction vessel, the mol ratio of cardanol and phenolic compound is 1:1～3.
3. the preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol as claimed in claim 1, it is characterized in that: described phenolic compound comprises cresols or xylenol or nonyl phenol or phenol or p-tert-butylphenol or o-tert-butyl phenol or to phenyl phenol or orthoxenol or p-phenyl phenol or diphenylol propane or to alkylphenol, the alkyl of described alkylphenol is straight chain or containing side chain.
4. the preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol as claimed in claim 1, it is characterized in that: described amine comprises quadrol or diethylenetriamine or triethylene tetramine or tetraethylene pentamine or polyethylene polyamine or m-xylene diamine or aminoethyl piperazine or isophorone diamine, m-xylene diamine, 1,3-BAC.
5. the preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol as claimed in claim 1, is characterized in that: the quality of described zinc acetate is 0.3%～5% of cardanol quality.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710599A (en) * | 2015-04-13 | 2015-06-17 | 哈尔滨中建璟园科技开发有限公司 | Curing agent for epoxy floor paints and preparation method thereof |
| CN104744653A (en) * | 2015-04-01 | 2015-07-01 | 南通星辰合成材料有限公司 | Method for synthesizing epoxy curing agent from bisphenol propane by-products |
| TWI561503B (en) * | 2015-06-15 | 2016-12-11 | Teng-Ke Lin | Method of promoter, curing agent and thinner formula for eliminating amine blushing and amine blooming. |
| CN107057009A (en) * | 2017-06-01 | 2017-08-18 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of the modified amine of polyphenol containing anacardol epoxy curing agent |
| CN107365410A (en) * | 2016-05-12 | 2017-11-21 | 常州杰美新高分子科技有限公司 | A kind of resources conservation, the plant base catalysis material of efficient green |
| CN107488260A (en) * | 2017-07-10 | 2017-12-19 | 中国林业科学研究院林业新技术研究所 | A kind of epoxy curing agent based on anacardol and furfural and preparation method thereof |
| CN107759755A (en) * | 2017-10-26 | 2018-03-06 | 湖北绿色家园材料技术股份有限公司 | Using the low cost of chemical industry leftover bits and pieces preparation, environment-friendly type stone material dry suspending adhesive curing agent |
| CN106496476B (en) * | 2016-11-14 | 2018-08-31 | 东莞兆舜有机硅科技股份有限公司 | A kind of Effect of Organosilicon-modified Phenol-formaldehyde Resin and its application |
| CN110616057A (en) * | 2019-09-25 | 2019-12-27 | 宜兴市普利泰电子材料有限公司 | Preparation and use methods of sealant for assembly line storage battery |
| CN110746581A (en) * | 2019-09-23 | 2020-02-04 | 辽宁石油化工大学 | Phenolic aldehyde amine epoxy latent curing agent, preparation method and application |
| CN111793195A (en) * | 2020-06-19 | 2020-10-20 | 华南农业大学 | Cardanol modified amine epoxy resin curing agent and preparation method and application thereof |
| CN112341973A (en) * | 2020-11-24 | 2021-02-09 | 南京阿斯孚特新材料科技有限公司 | Two-component normal-temperature cured epoxy resin elastomer composition and preparation method thereof |
| CN115028790A (en) * | 2022-06-22 | 2022-09-09 | 上海稻畑精细化工有限公司 | High-temperature-resistant epoxy resin curing agent and preparation method thereof |
| CN115925591A (en) * | 2022-11-29 | 2023-04-07 | 湖北长海新能源科技有限公司 | Modified diamino diphenyl sulfone and preparation method and application thereof |
| CN116790220A (en) * | 2023-08-21 | 2023-09-22 | 广州布鲁奥申新材料科技有限公司 | Environment-friendly high-toughness epoxy adhesive, preparation method and application thereof |
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| CN104744653A (en) * | 2015-04-01 | 2015-07-01 | 南通星辰合成材料有限公司 | Method for synthesizing epoxy curing agent from bisphenol propane by-products |
| CN104710599A (en) * | 2015-04-13 | 2015-06-17 | 哈尔滨中建璟园科技开发有限公司 | Curing agent for epoxy floor paints and preparation method thereof |
| TWI561503B (en) * | 2015-06-15 | 2016-12-11 | Teng-Ke Lin | Method of promoter, curing agent and thinner formula for eliminating amine blushing and amine blooming. |
| CN107365410A (en) * | 2016-05-12 | 2017-11-21 | 常州杰美新高分子科技有限公司 | A kind of resources conservation, the plant base catalysis material of efficient green |
| CN107365410B (en) * | 2016-05-12 | 2020-11-24 | 常州杰美新高分子科技有限公司 | Resource-saving, efficient and green plant-based catalytic functional material |
| CN106496476B (en) * | 2016-11-14 | 2018-08-31 | 东莞兆舜有机硅科技股份有限公司 | A kind of Effect of Organosilicon-modified Phenol-formaldehyde Resin and its application |
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| CN107057009B (en) * | 2017-06-01 | 2019-06-07 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of the modified amine of polyphenol containing anacardol epoxy curing agent |
| CN107488260A (en) * | 2017-07-10 | 2017-12-19 | 中国林业科学研究院林业新技术研究所 | A kind of epoxy curing agent based on anacardol and furfural and preparation method thereof |
| CN107759755A (en) * | 2017-10-26 | 2018-03-06 | 湖北绿色家园材料技术股份有限公司 | Using the low cost of chemical industry leftover bits and pieces preparation, environment-friendly type stone material dry suspending adhesive curing agent |
| CN110746581A (en) * | 2019-09-23 | 2020-02-04 | 辽宁石油化工大学 | Phenolic aldehyde amine epoxy latent curing agent, preparation method and application |
| CN110616057A (en) * | 2019-09-25 | 2019-12-27 | 宜兴市普利泰电子材料有限公司 | Preparation and use methods of sealant for assembly line storage battery |
| CN110616057B (en) * | 2019-09-25 | 2021-07-23 | 宜兴市普利泰电子材料有限公司 | Preparation and use methods of sealant for assembly line storage battery |
| CN111793195A (en) * | 2020-06-19 | 2020-10-20 | 华南农业大学 | Cardanol modified amine epoxy resin curing agent and preparation method and application thereof |
| CN112341973A (en) * | 2020-11-24 | 2021-02-09 | 南京阿斯孚特新材料科技有限公司 | Two-component normal-temperature cured epoxy resin elastomer composition and preparation method thereof |
| CN115028790A (en) * | 2022-06-22 | 2022-09-09 | 上海稻畑精细化工有限公司 | High-temperature-resistant epoxy resin curing agent and preparation method thereof |
| CN115028790B (en) * | 2022-06-22 | 2024-02-09 | 上海稻畑精细化工有限公司 | High-temperature-resistant epoxy resin curing agent and preparation method thereof |
| CN115925591A (en) * | 2022-11-29 | 2023-04-07 | 湖北长海新能源科技有限公司 | Modified diamino diphenyl sulfone and preparation method and application thereof |
| CN116790220A (en) * | 2023-08-21 | 2023-09-22 | 广州布鲁奥申新材料科技有限公司 | Environment-friendly high-toughness epoxy adhesive, preparation method and application thereof |
| CN116790220B (en) * | 2023-08-21 | 2023-12-08 | 广州布鲁奥申新材料科技有限公司 | Environment-friendly high-toughness epoxy adhesive, preparation method and application thereof |
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