CN103739828B - A kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol - Google Patents
A kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol Download PDFInfo
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- CN103739828B CN103739828B CN201310703958.2A CN201310703958A CN103739828B CN 103739828 B CN103739828 B CN 103739828B CN 201310703958 A CN201310703958 A CN 201310703958A CN 103739828 B CN103739828 B CN 103739828B
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Abstract
A kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol, first cardanol, phenolic compound, paraformaldehyde, diamines or polyamines is taken according to weight, cardanol, phenols and paraformaldehyde are added in reaction vessel, and add catalyzer, intermediate is heated 2 ~ 6 hours to obtain at 75 ~ 100 DEG C, then described intermediate is cooled to 60 ~ 68 DEG C, add diamines or polyamines, remaining paraformaldehyde is added under this temperature whipped state, then temperature is elevated to 65 ~ 95 DEG C, react 4 ~ 8 hours, under vacuum state, dehydration obtains the present invention.The solidifying agent of the present invention's synthesis has extraordinary surface hardness and shore hardness, and glossiness is good, resistance to elevated temperatures is good, low-temperature fast-curing.The present invention is the epoxy curing agent that a kind of solidification value scope is wide, high temperature resistant, surface property is excellent, is applicable to the requirement of priming paint and finish paint.
Description
Technical field:
The present invention relates to chemical field, particularly relate 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 a kind of refinement through modern technique from natural cashew nut shell oil forms, can replace or partly replace phenol for the manufacture of epoxy hardener, liquid phenolic resin, liquid or pulverous heat-reactive phenolic resin.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 chain of unsaturated double-bond, the toughness that system can be provided good, excellent hydrophobic nature and low-permeability and from dryness.
Anhydride curing agent selected by the solidifying agent of general heat resistant type, as cis-butenedioic anhydride, Tetra hydro Phthalic anhydride and derivative thereof; Phenyl amines solidifying agent is as diaminodiphenylsulfone(DDS) etc., the general thermotolerance of epoxy resin of these solidifying agent solidification is all relatively good, but these solidifying agent require higher 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 comparatively large, 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 to solve heat resistant type solidifying agent condition of cure of the prior art require higher, toxicity is comparatively 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 take cardanol according to weight, 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 proper amount of acetic acid zinc as catalyzer, intermediate is heated 2 ~ 6 hours to obtain at 75 ~ 100 DEG C, then described intermediate is cooled to 60 ~ 68 DEG C, add amine, under whipped state, add remaining paraformaldehyde in this temperature in batches, then temperature is brought up to 65 ~ 95 DEG C, react 4 ~ 8 hours, under vacuum state, dehydration obtains solidifying agent.
Further, adding in the process of reaction vessel by cardanol and phenolic compound, 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 be used alone, also can be mixed with other solidifying agent, improve the dryness of other solidifying agent, thermotolerance.
The solidifying agent of the present invention's synthesis has extraordinary surface hardness (>2H) and shore hardness (>95o), glossiness good (Gao Guang), resistance to elevated temperatures good (at 100 DEG C, 30min loss of strength is no more than 30%), can be low-temperature fast-curing.The present invention is the epoxy curing agent that a kind of solidification value scope is wide, high temperature resistant, surface property is excellent, 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 causes and decline with the thermotolerance of epoxy curing systems.The present invention introduces the phenolic structure between phenyl ring in reaction molecular, and substantially increase thermotolerance and the hardness (comprising surface hardness and solid block hardness) of general epoxy resin, and molecular weight is large, toxicity is low, good toughness.Relative to other heat resistant type solidifying agent such as anhydrides and phenyl amines, the advantage of this money solidifying agent is to improve general cardanol solidifying agent resistance toheat and hardness, also remains good toughness and curability at low temperatures simultaneously, and over-all properties is given prominence to.Be applicable to some have requirement to resistance toheat but be not too high, but keep low temperature (-10 DEG C) solidification, 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 of band heating jacket, and add 3g zinc acetate as catalyzer, at 100 DEG C, heat 2 hours to obtain intermediate SM.SM is cooled to 65 DEG C, add diethylenetriamine (1mol), add under this temperature whipped state in batches paraformaldehyde (30g, 1mol) then temperature be elevated to 80 DEG C of reactions 5 hours, reaction is sloughed the water discharging generated in reaction under terminating final vacuum state and is obtained this solidifying agent (S1).Viscosity 30000mPa.S, amine value 290mgKOH/g, solid content 95%, surface hardness >2H, shore hardness >95 degree
Resistance toheat compares
Wherein MD650 is the cardanol pnenolic aldehyde amine hardener that Shanghai Meidong Biological Material Co., Ltd produces, commercialization, and performance excellence belongs to mid-to high-end product, is the main product of cardanol solidifying agent.By relatively finding out, the solid block relative MD650 resistance toheat in same proportioning situation of epoxy of the phenol aldehyde modified cardanol pnenolic aldehyde amine hardener solidification of the present invention's research and development is used to significantly improve.On the one hand having benefited from present invention uses dihydroxyphenyl propane makes the phenyl ring density of the molecule of solidifying agent increase, and another aspect has benefited from the introducing of phenolic structure, and with the advantage of obvious resol after solidifying agent and epoxy resin cure, hardness and thermotolerance significantly improve.
Embodiment 2
Cardanol (600g, 2mol) and paraformaldehyde (30g, 1mol) are added in the four-hole bottle of band heating jacket, and add 3g zinc acetate as catalyzer, at 100 DEG C, heat 2 hours to obtain intermediate SM.SM is cooled to 65 DEG C, add tetraethylene pentamine (1mol), add under this temperature whipped state in batches paraformaldehyde (1mol) then temperature be elevated to 80 DEG C of reactions 5 hours, reaction is sloughed the water discharging generated in reaction under terminating final vacuum state and is obtained this solidifying agent (S2).Viscosity 100Pa.S, amine value 285mgKOH/g, solid content 98%, surface hardness >2H, shore hardness 90-95 degree
Resistance toheat compares
Wherein MD650 is the cardanol pnenolic aldehyde amine hardener that Shanghai Meidong Biological Material Co., Ltd produces, commercialization, and performance excellence belongs to mid-to high-end product, is the main product of cardanol solidifying agent.By relatively finding out, the solid block relative MD650 resistance toheat in same proportioning situation of epoxy of the phenol aldehyde modified cardanol pnenolic aldehyde amine hardener solidification of the present invention's research and development is used to significantly improve.Have benefited from the introducing of phenolic structure, with the advantage of obvious resol after solidifying agent and epoxy resin cure, 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 of band heating jacket, and add 5g zinc acetate as catalyzer, heats 2 hours to obtain intermediate SM at 100 DEG C.SM is cooled to 65 DEG C, add tetraethylene pentamine (189g, 1mol), add paraformaldehyde (30g under this temperature whipped state in batches, 1mol) then temperature is elevated to 80 DEG C of reactions 5 hours, and reaction is sloughed the water discharging generated in reaction under terminating final vacuum state and obtained this solidifying agent (S1).Viscosity 30000mPa.S, amine value 290mgKOH/g, solid content 95%, surface hardness >2H, shore hardness >95 degree
Resistance toheat compares
Wherein MD650 is the cardanol pnenolic aldehyde amine hardener that Shanghai Meidong Biological Material Co., Ltd produces, commercialization, and performance excellence belongs to mid-to high-end product, is the main product of cardanol solidifying agent.By relatively finding out, the solid block relative MD650 resistance toheat in same proportioning situation of epoxy of the phenol aldehyde modified cardanol pnenolic aldehyde amine hardener solidification of the present invention's research and development is used to significantly improve.On the one hand having benefited from present invention uses dihydroxyphenyl propane makes the phenyl ring density of the molecule of solidifying agent increase, and another aspect has benefited from the introducing of phenolic structure, and with the advantage of obvious resol after solidifying agent and epoxy resin cure, hardness and thermotolerance significantly improve.
Claims (1)
1., based on a preparation method for the high-temperature-resistant epoxy resin solidifying agent of cardanol, it is characterized in that: first take cardanol according to weight, phenolic compound, paraformaldehyde, amine, described cardanol, phenolic compound, paraformaldehyde, the mol ratio of amine is 1:1 ~ 3:0.5 ~ 4:0.8 ~ 1.5, by cardanol, phenolic compound and part paraformaldehyde add in reaction vessel, and add proper amount of acetic acid zinc as catalyzer, intermediate is heated 2 ~ 6 hours to obtain at 75 ~ 100 DEG C, then described intermediate is cooled to 60 ~ 68 DEG C, adds amine, under whipped state, add remaining paraformaldehyde in this temperature in batches, then temperature is brought up to 65 ~ 95 DEG C, react 4 ~ 8 hours, under vacuum state, dehydration obtains solidifying agent, and described phenolic compound is cresols, or xylenol, or nonyl phenol, or phenol, or o-tert-butyl phenol, or orthoxenol, or p-phenyl phenol, or diphenylol propane, or to alkylphenol, the described alkyl to alkylphenol is straight chain or contains side chain, and described amine is quadrol, or diethylenetriamine, or triethylene tetramine, or tetraethylene pentamine, or polyethylene polyamine, or m-xylene diamine, or aminoethyl piperazine, or isophorone diamine, or 1,3-BAC, the quality of described zinc acetate is 0.3% ~ 5% of cardanol quality.
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| CN201310703958.2A CN103739828B (en) | 2013-12-19 | 2013-12-19 | A kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol |
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| CN201310703958.2A CN103739828B (en) | 2013-12-19 | 2013-12-19 | A kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol |
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| CN103739828B true CN103739828B (en) | 2015-10-28 |
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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. |
| 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 |
| 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 |
| CN107488260B (en) * | 2017-07-10 | 2020-11-17 | 中国林业科学研究院林业新技术研究所 | Epoxy resin curing agent based on cardanol 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 |
| 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 |
| CN112341973B (en) * | 2020-11-24 | 2023-01-10 | 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 |
| 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 |
| 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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