CN108148163A - A kind of preparation method of modified by cardanol amine epoxy curing agent - Google Patents
A kind of preparation method of modified by cardanol amine epoxy curing agent Download PDFInfo
- Publication number
- CN108148163A CN108148163A CN201711428106.1A CN201711428106A CN108148163A CN 108148163 A CN108148163 A CN 108148163A CN 201711428106 A CN201711428106 A CN 201711428106A CN 108148163 A CN108148163 A CN 108148163A
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- China
- Prior art keywords
- amine
- cardanol
- curing agent
- modified
- anacardol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of preparation methods of modified by cardanol amine epoxy curing agent; anacardol, amine will be added in reactor; it heats under nitrogen protection; being no more than 75 DEG C with temperature is advisable; it stirs 1 10 hours; add and then add in aldehyde; temperature is set as 75 ~ 85 DEG C; reaction 3 ~ 8 hours, then vacuumizes at this temperature, except the water of dereaction generation; make into orange-yellow clear oil substance; cardanol glycidyl ether is added, is stirred 0.5 10 hours at 50 ~ 90 DEG C, discharge to obtain modified by cardanol amine epoxy curing agent.The present invention is modified cashew nut phenols epoxy hardener, color becomes partially orange phase lighter from original partially red phase, and hardness has been increased to 2H, has impacted for 50 cm.kg, low temperature by introducing two anacardol segments in agent molecule is cured（‑15℃）Under the conditions of cure seven days coating surface hardness up to H.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of curing agent, specifically a kind of modified by cardanol amine epoxy resin
The preparation method of curing agent.
Background technology
Anacardol is the natural phenolic compound with unsaturation C15 long side chains, and structure is similar to laccol.Anacardol
This unique texture makes it both have the feature of aromatic compound, high temperature resistance；There is the feature of aliphatic compound again,
Good flexibility, excellent hydrophobicity, hypotonicity and white spirit；In addition, the phenolic hydroxyl group on phenyl ring makes it have phenols again
Property.Its typical reaction is as follows：The double bond of anacardol can carry out addition polymerization, oxidation and hydrogenation, can be carried out with aldehydes
Phenolic aldehyde polycondensation reaction, phenolic hydroxyl group can occur esterification, etherification reaction, can synthesize many new compounds using these reactions.
Modified by cardanol epoxy anabolica has the characteristics that low viscosity, low-temperature setting, water-tolerant.Hu Jiapeng etc. is with cashew nut
Phenol, formaldehyde and diethylenetriamine have synthesized anacardol acetal amine hardener for raw material through polycondensation reaction, and the low temperature of curing agent is compatible
Property, the physical and mechanical property of solidfied material, chemical mediator-resitant property all increase.Liu little Ying etc. is using alkene on anacardol side chain
Curing modifier is made in basic ring oxidation, reduces oneself viscosity, improves crosslink density.
Although modified by cardanol curing agent has lot of advantages, still remain some problems needs and overcome, such as face
Color depth, the tough sex chromosome mosaicism caused by hardness deficiency, (- 15 DEG C) curing rate waits cannot similarly neglect slowly at lower temperature
Depending on.
Invention content
The purpose of the present invention is to provide a kind of preparation method of modified by cardanol amine epoxy curing agent, described this
The preparation method of kind modified by cardanol amine epoxy curing agent will solve modified by cardanol curing agent color of the prior art
The technical issues of curing rate is slow under deep, hardness deficiency, low temperature.
The present invention provides a kind of preparation method of modified by cardanol amine epoxy curing agent, including step：
1) weigh anacardol, amine, aldehyde, cardanol glycidyl ether the step of, the anacardol, amine, aldehyde, cashew nut
The molar ratio of phenol glycidol ether is 1:0.1~10：0.1-10：0.1-10；
2) anacardol, amine are added in reactor, heated under nitrogen protection, preferred heating temperature is less than or waits
It in 75 DEG C, stirs 1-10 hours, then adds aldehyde, temperature is set as 75~85 DEG C, reacts 3~8 hours, then in this temperature
Under vacuumize, except dereaction generation water, make into orange-yellow clear oil substance, cardanol glycidyl ether added, 50
It is stirred 0.5-10 hours at~90 DEG C, discharge to obtain modified by cardanol amine epoxy curing agent.
3) further, the amine is ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, Amix1000
Any one in (mixed amine), EA-300, isophorone diamine, hexamethylene diamine, propane diamine or m-xylene diamine.
Further, the aldehyde is any one in formaldehyde, paraformaldehyde or furtural.
The present invention carries out cashew nut phenols epoxy hardener by introducing two anacardol segments in agent molecule is cured
Modified, traditional its shortcoming of modified by cardanol epoxy hardener is being improved to a certain degree.Color is by original partially red phase transformation
For partially orange phase-lighter, hardness has been increased to 2H, has impacted for 50cm.kg, gel time 20min, low temperature (- 15 DEG C)
Under the conditions of cure seven days coating surface hardness up to H.
The present invention react that generate a kind of band that can continue modification active using cardanol glycidyl ether and amine
The intermediate of amine.Molecule fragment containing two anacardols in the molecule of the present invention, increases the toughness after film curing.
The present invention changes synthesizes pnenolic aldehyde amine hardener in color, toughness, hardness and curability at low temperatures with anacardol merely
Limitation, enhance the performance of anacardol base class pnenolic aldehyde amine hardener, widen the use scope of traditional cardanol epoxy curing agent.
The present invention is compared with prior art, is had the technical effect that positive and apparent.The curing agent of the present invention is compared to similar
Curing agent, in the case where being not added with any accelerating agent, low temperature curing properties are good, minimum to cure at -15 DEG C.It is of light color,
Partially orange phase is become from original partially red phase, colour stable, 1 grade of adhesive force, hardness greatly improves, and hardness of paint film is up to 2H.It should
Curing agent can both be used separately as the curing agent of property, can also be with other curing agent particularly cashew nut phenolic cure
Agent shares the low temperature drying performance to improve other anacardol curing agent, hardness, and makes traditional anacardol curing agent lighter.
Specific embodiment
Embodiment 1：
Anacardol (300g) and diethylenetriamine (101g) are added in four-hole bottle, are heated to 60 DEG C, is reacted 2 hours,
Paraformaldehyde (32.6g) is slowly added into, which reacts 6 hours at 80 DEG C and then vacuumize the water and unreacted for removing generation
Amine obtains clear liquid, and cools to 60 DEG C, adds in cardanol glycidyl ether (360g), and the reaction is anti-at 80 DEG C
It answers 6 hours, obtains target curing agent.
First, product basic index：
2nd, measuring mechanical property index：
Embodiment 2：
Anacardol (300g) and m-xylene diamine (400g) are added in four-hole bottle and are heated to 60 DEG C, reacts 2 hours, slowly
Slow to add in paraformaldehyde (32.6g), which reacts 6 hours at 80 DEG C, then vacuumizes the water and unreacted for removing generation
Amine obtains clear liquid and cools to 60 DEG C, adds in cardanol glycidyl ether (360g), which reacts at 80 DEG C
6 hours, obtain target curing agent.
First, product basic index：
2nd, measuring mechanical property index：
Experimental data referred to above is according to following standard testing：Paint film general preparation method is according to national standard GB1727-
79, pencil hardness test method GB/T 6739-1996, paint film adhesion measuring method GB1720-79, paint film flexibility measuring method
(bending) GB1731-1993, paint film impact resistance measuring method GB1732-93.
As can be seen from the above table, we invent bisphenol epoxies curing agent under room temperature (25 DEG C) and low temperature (- 15 DEG C) all
It can cure, and with higher comprehensive performance, and the suitable of cured epoxy hardener commercialization at -15 DEG C can be reached at present
It is few, for traditional cardanol solidifying agent of epoxy resin.
Claims (3)
1. a kind of preparation method of modified by cardanol amine epoxy curing agent, it is characterised in that including step：
1) weigh anacardol, amine, aldehyde, cardanol glycidyl ether the step of, the anacardol, amine, aldehyde, anacardol contracting
The molar ratio of water glycerin ether is 1:0.1~10：0.1-10 ：0.1-10；
2) anacardol, amine are added in reactor, heated under nitrogen protection, temperature is below or equal to 75 DEG C, stirs 1-10
Hour, aldehyde is then added, temperature is set as 75 ~ 85 DEG C, reacts 3 ~ 8 hours, then vacuumizes at this temperature, removes anti-
The water that should be generated makes into orange-yellow clear oil substance, adds cardanol glycidyl ether, 0.5- is stirred at 50 ~ 90 DEG C
10 hours, discharged to obtain modified by cardanol amine epoxy curing agent.
2. a kind of preparation method of modified by cardanol amine epoxy curing agent according to claim 1, it is characterised in that：
The amine is ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, Amix1000（Mixed amine）, EA-300, different Buddhist
Any one in your ketone diamines, hexamethylene diamine, propane diamine or m-xylene diamine.
3. a kind of preparation method of modified by cardanol amine epoxy curing agent according to claim 1, it is characterised in that：
The aldehyde is any one in formaldehyde, paraformaldehyde or furtural.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711428106.1A CN108148163A (en) | 2017-12-26 | 2017-12-26 | A kind of preparation method of modified by cardanol amine epoxy curing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711428106.1A CN108148163A (en) | 2017-12-26 | 2017-12-26 | A kind of preparation method of modified by cardanol amine epoxy curing agent |
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| CN108148163A true CN108148163A (en) | 2018-06-12 |
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| CN201711428106.1A Pending CN108148163A (en) | 2017-12-26 | 2017-12-26 | A kind of preparation method of modified by cardanol amine epoxy curing agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134829A (en) * | 2018-08-17 | 2019-01-04 | 重庆南方漆业有限公司 | One kind is anti-to after-tack epoxy hardener and its preparation method and application |
| CN113462261A (en) * | 2021-07-28 | 2021-10-01 | 绵阳惠利环氧工程有限公司 | Semitransparent closed solvent-free epoxy primer coating compound |
| 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 |
| CN116854852A (en) * | 2023-09-05 | 2023-10-10 | 山东天一化学股份有限公司 | Preparation method and application of modified brominated polystyrene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508856A (en) * | 2008-02-13 | 2009-08-19 | 上海涂料有限公司上海长风化工厂 | Cashew pnenolic aldehyde amine epoxide resin paint solidifying agent and method for producing the same |
| CN103214657A (en) * | 2013-04-01 | 2013-07-24 | 四川东材科技集团股份有限公司 | Preparation method of anacardol glycidyl ether modified polyamine epoxy hardener |
| 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 |
-
2017
- 2017-12-26 CN CN201711428106.1A patent/CN108148163A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508856A (en) * | 2008-02-13 | 2009-08-19 | 上海涂料有限公司上海长风化工厂 | Cashew pnenolic aldehyde amine epoxide resin paint solidifying agent and method for producing the same |
| CN103214657A (en) * | 2013-04-01 | 2013-07-24 | 四川东材科技集团股份有限公司 | Preparation method of anacardol glycidyl ether modified polyamine epoxy hardener |
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134829A (en) * | 2018-08-17 | 2019-01-04 | 重庆南方漆业有限公司 | One kind is anti-to after-tack epoxy hardener and its preparation method and application |
| CN113462261A (en) * | 2021-07-28 | 2021-10-01 | 绵阳惠利环氧工程有限公司 | Semitransparent closed solvent-free epoxy primer coating compound |
| 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 |
| CN116854852A (en) * | 2023-09-05 | 2023-10-10 | 山东天一化学股份有限公司 | Preparation method and application of modified brominated polystyrene |
| CN116854852B (en) * | 2023-09-05 | 2023-11-10 | 山东天一化学股份有限公司 | Preparation method and application of modified brominated polystyrene |
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Application publication date: 20180612 |