CN102161749B - Self-toughening epoxy resin curing agent and preparation method thereof - Google Patents
Self-toughening epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN102161749B CN102161749B CN2011100588560A CN201110058856A CN102161749B CN 102161749 B CN102161749 B CN 102161749B CN 2011100588560 A CN2011100588560 A CN 2011100588560A CN 201110058856 A CN201110058856 A CN 201110058856A CN 102161749 B CN102161749 B CN 102161749B
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Abstract
The invention belongs to the technical field of chemical new materials or building adhesive curing agents and provides a self-toughening epoxy resin curing agent, which consists of 1.2 to 1.8 moles of nonyl phenol, 1.5 to 2.2 moles of ethanediamine and 0.6 to 1.2 moles of paraformaldehyde. The invention also provides a method for preparing the self-toughening epoxy resin curing agent, which comprises the following steps: a), adding nonyl phenol in a molar ratio into a reaction kettle; b) adding ethanediamine in a molar ratio, and stirring at room temperature for 4 to 6 minutes; and c) adding paraformaldehyde in a molar ratio with heating, heating to 75 to 85 DEG C, keeping the temperature for about 1.5 to 2.5 hours, and cooling to 20 to 25 DEG C to obtain the self-toughening epoxy resin curing agent. The self-toughening epoxy resin curing agent is improved in shearing and adhesive strengths, tensile strength and impact strength, dehydration operation is not needed, the self-toughening epoxy resin curing agent is prepared by one-step reaction, and the process is simple.
Description
Technical field
The invention belongs to new chemical materials or architecture adhesion agent solidifying agent technical field, be specifically related to a kind of preparation of Mannich modified firming agent of epoxy-resin systems.
Background technology
At present, amine and modified amine curing agent are the most practical to epoxy-resin systems, and the prescription of modified amine curing agent is that modification is come on the basis with aliphatics and cycloaliphatic amines mainly.The epoxy resin cured product elongation at break is low, and fragility is big, and bond is antifatigue not, needs it is carried out toughening modifying for this reason.It is toughness reinforcing toughness reinforcing with physics to be divided into chemistry by toughening mechanism.The more toughner of Recent study mainly contains: rubber-like elastomerics, thermoplastic resin, nano material, liquid crystalline polymers and flexible solidifying agent, and flexible solidifying agent mainly contains chain alkyl amine, phenol aldehyde modified amine hardener.Existing existing phenol aldehyde modified amine hardener shortcoming is that cured product is too crisp, and is water-fast undesirable with performance humidity.Cashew pnenolic aldehyde and nonyl phenolic aldehyde modified amine curing agent are the phenol aldehyde modified amine hardeners that has from toughness reinforcing.Existing document of cashew pnenolic aldehyde modified amine and publication, and nonyl phenolic aldehyde modified amine is not seen public reported temporarily.
Summary of the invention
To the defective of prior art, the invention provides a kind of from epoxy resin toughened solidifying agent, should enhancing all be arranged from epoxy resin toughened solidifying agent shear bond strength, tensile strength and impact strength, and need not dehydration operation, a step accomplishes, technology is simple.
The invention provides a kind ofly from epoxy resin toughened solidifying agent, be made up of NP, Paraformaldehyde 96 and quadrol, the shared molar ratio of each component is:
NP: 1.2 mol～1.8mol
Quadrol: 1.5 mol～2.2 mol
Paraformaldehyde 96: 0.6 mol～1.2 mol.
The present invention also provides and has prepared above-mentioned method from epoxy resin toughened solidifying agent, and concrete steps are:
A) by above-mentioned mol ratio NP is added reaction kettle;
B) quadrol of the above-mentioned mol ratio of adding, stirring at room 4-6 minute;
C) intensification limit in limit adds the Paraformaldehyde 96 of above-mentioned mol ratio in batches then, is warmed up to 40-80 ℃, is incubated then about 1.5-2.5 hour, cools 20-25 ℃, derives from epoxy resin toughened solidifying agent.
Should be light yellow viscous liquid from epoxy resin toughened solidifying agent, record amine value and viscosity, be respectively about 340～450mgKOH/g, 235～2200mPa.s.
Advantage of the present invention is:
1 has introduced the long-chain NP in the tough-increased phenolic modified amine curing agent, increased toughness, water tolerance and the moisture resistance of curing system.
The solid polyformaldehyde of 2 employings when the tough-increased phenolic modified amine curing agent is synthetic, water in products content is less, has simplified aftertreatment technology.
3 decompression after the tough-increased phenolic modified amine curing agent need not polycondensation (vacuum) dehydration operation that the present invention relates to, technology is simple, and is easy to operate, not high to equipment requirements, is easy to suitability for industrialized production.
4 solidifying agent are applied to cured epoxy tackiness agent in self-vulcanizing or the water, solidify during preparation that the dry state shear bond strength is 21.91MPa after 24 hours, and tensile strength is 12.5MPa, and shock strength is 9.41kJ/m
2Solidifying the 7d shear bond strength in the hygrometric state cementing is 5-7MPa.And the wet bonding intensity of 810 underwater curing agent of prior art is 1.50 ~ 2.60MPa, and tensile strength is 18.4 ~ 26.1MPa.
Embodiment
For a better understanding of the present invention, the present invention is done detailed description further, but the scope of the present invention's protection is not limited to the represented scope of embodiment below in conjunction with embodiment.
Embodiment 1:
Weighing NP 110g, quadrol 30g, Paraformaldehyde 96 10g.In the thermostatical oil bath, in 250 milliliters the there-necked flask that whisking appliance, thermopair, prolong are housed, add the 110g NP, add the 30g quadrol again; At room temperature stirred 4 minutes, begin the heating, be warmed up to 40 ℃ after; Beginning repeatedly adds Paraformaldehyde 96 in batches, and (temperature adds 40% of Paraformaldehyde 96 quality total amount when 40 ℃ are raised to 50 ℃; Temperature add when adding 20%, 70 ℃ to 80 ℃ of Paraformaldehyde 96 total amount when adding 30%, 60 ℃ to 70 ℃ of Paraformaldehyde 96 total amount when 50 ℃ are raised to 60 ℃ the Paraformaldehyde 96 total amount 10%); After being warming up to 80 ℃, be incubated 2 hours.Be cooled to 20 ℃ and obtain flaxen viscous liquid, amine value and viscosity are measured in discharging, are respectively 340.50KOH/g, 1387.5mPa.s.
Embodiment 2:
Weighing NP 110g, quadrol 30g, Paraformaldehyde 96 6g.In the thermostatical oil bath, in 250 milliliters the there-necked flask that whisking appliance, thermopair, prolong are housed, add the 110g NP, add the 30g quadrol again; At room temperature stirred 5 minutes, begin the heating, be warmed up to 40 ℃ after; Beginning repeatedly adds Paraformaldehyde 96 in batches, and (temperature adds 40% of Paraformaldehyde 96 quality total amount when 40 ℃ are raised to 50 ℃; Temperature add when adding 20%, 70 ℃ to 80 ℃ of Paraformaldehyde 96 total amount when adding 30%, 60 ℃ to 70 ℃ of Paraformaldehyde 96 total amount when 50 ℃ are raised to 60 ℃ the Paraformaldehyde 96 total amount 10%); After being warming up to 80 ℃, be incubated 2 hours.Be cooled to 20 ℃ and obtain flaxen viscous liquid, amine value and viscosity are measured in discharging, are respectively 348.52KOH/g, 485mPa.s.
Embodiment 3:
Weighing NP 110g, quadrol 44g, Paraformaldehyde 96 10g.In the thermostatical oil bath, in 250 milliliters the there-necked flask that whisking appliance, thermopair, prolong are housed, add the 110g NP, add the 44g quadrol again; At room temperature stirred 6 minutes, begin the heating, be warmed up to 40 ℃ after; Beginning repeatedly adds Paraformaldehyde 96 in batches, and (temperature adds 40% of Paraformaldehyde 96 quality total amount when 40 ℃ are raised to 50 ℃; Temperature add when adding 20%, 70 ℃ to 80 ℃ of Paraformaldehyde 96 total amount when adding 30%, 60 ℃ to 70 ℃ of Paraformaldehyde 96 total amount when 50 ℃ are raised to 60 ℃ the Paraformaldehyde 96 total amount 10%); After being warming up to 80 ℃, be incubated 2 hours.Be cooled to 20 ℃ and obtain flaxen viscous liquid, amine value and viscosity are measured in discharging, are respectively 442.67KOH/g, 239.5mPa.s.
Embodiment 4:
Weighing NP 110g, quadrol 12g, Paraformaldehyde 96 10g.In the thermostatical oil bath, in 250 milliliters the there-necked flask that whisking appliance, thermopair, prolong are housed, add the 110g NP, add the 12g quadrol again; At room temperature stirred 5 minutes, begin the heating, be warmed up to 40 ℃ after; Beginning repeatedly adds Paraformaldehyde 96 in batches, and (temperature adds 40% of Paraformaldehyde 96 quality total amount when 40 ℃ are raised to 50 ℃; Temperature add when adding 20%, 70 ℃ to 80 ℃ of Paraformaldehyde 96 total amount when adding 30%, 60 ℃ to 70 ℃ of Paraformaldehyde 96 total amount when 50 ℃ are raised to 60 ℃ the Paraformaldehyde 96 total amount 10%); After being warming up to 80 ℃, be incubated 2 hours.Be cooled to 22 ℃ and obtain flaxen viscous liquid, amine value and viscosity are measured in discharging, are respectively 112.11KOH/g, 24750 mPa.s.This routine viscosity is too high, difficult operation when joining glue.
Embodiment 5:
Weighing NP 110g, quadrol 10g, Paraformaldehyde 96 5g.In the thermostatical oil bath, in 250 milliliters the there-necked flask that whisking appliance, thermopair, prolong are housed, add the 110g NP, add the 10g quadrol again; At room temperature stirred 5 minutes, begin the heating, be warmed up to 40 ℃ after; Beginning repeatedly adds Paraformaldehyde 96 in batches, and (temperature adds 40% of Paraformaldehyde 96 quality total amount when 40 ℃ are raised to 50 ℃; Temperature add when adding 20%, 70 ℃ to 80 ℃ of Paraformaldehyde 96 total amount when adding 30%, 60 ℃ to 70 ℃ of Paraformaldehyde 96 total amount when 50 ℃ are raised to 60 ℃ the Paraformaldehyde 96 total amount 10%); After being warming up to 80 ℃, be incubated 2 hours.Be cooled to 25 ℃ and obtain flaxen viscous liquid, amine value and viscosity are measured in discharging, are respectively 135.51KOH/g, 11000 mPa.s.This routine viscosity is too high, difficult operation when joining glue.
Embodiment 6:
Weighing NP 110g, quadrol 18g, Paraformaldehyde 96 5g.In the thermostatical oil bath, in 250 milliliters the there-necked flask that whisking appliance, thermopair, prolong are housed, add the 110g NP, add the 18g quadrol again; At room temperature stirred 5 minutes, begin the heating, be warmed up to 40 ℃ after; Beginning repeatedly adds Paraformaldehyde 96 in batches, and (temperature adds 40% of Paraformaldehyde 96 quality total amount when 40 ℃ are raised to 50 ℃; Temperature add when adding 20%, 70 ℃ to 80 ℃ of Paraformaldehyde 96 total amount when adding 30%, 60 ℃ to 70 ℃ of Paraformaldehyde 96 total amount when 50 ℃ are raised to 60 ℃ the Paraformaldehyde 96 total amount 10%); After being warming up to 80 ℃, be incubated 2 hours.Be cooled to 22 ℃ and obtain flaxen viscous liquid, amine value and viscosity are measured in discharging, are respectively 367.72KOH/g, 690 mPa.s.
Claims (2)
1. one kind from epoxy resin toughened solidifying agent, it is characterized in that be made up of NP, Paraformaldehyde 96 and quadrol, the shared molar ratio of each component is:
NP: 1.2 mol～1.8mol
Quadrol: 1.5 mol～2.2 mol
Paraformaldehyde 96: 0.6 mol～1.2 mol.
2. prepare the said method of claim 1, it is characterized in that concrete steps are from epoxy resin toughened solidifying agent:
By above-mentioned mol ratio NP is added reaction kettle;
The quadrol that adds above-mentioned mol ratio, stirring at room 4-6 minute;
Intensification limit in limit adds the Paraformaldehyde 96 of above-mentioned mol ratio in batches then, heats up by 40-80 ℃, is incubated then about 1.5-2.5 hour, cools 20-25 ℃, derives from epoxy resin toughened solidifying agent.
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| CN2011100588560A CN102161749B (en) | 2011-03-11 | 2011-03-11 | Self-toughening epoxy resin curing agent and preparation method thereof |
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| CN2011100588560A CN102161749B (en) | 2011-03-11 | 2011-03-11 | Self-toughening epoxy resin curing agent and preparation method thereof |
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| CN102161749B true CN102161749B (en) | 2012-11-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665985A (en) * | 2013-12-05 | 2014-03-26 | 江苏金波新材料科技有限公司 | External anticorrosive coating for tubular products |
| CN103665986A (en) * | 2013-12-05 | 2014-03-26 | 江苏金波新材料科技有限公司 | External anticorrosive coating for tubular products and preparation method thereof |
| CN110204690A (en) * | 2019-06-06 | 2019-09-06 | 广州百云宝能源科技有限公司 | A kind of epoxy dry-hang glue curing agent and preparation method thereof |
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2011
- 2011-03-11 CN CN2011100588560A patent/CN102161749B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 杨洋等.一种活性环氧增韧固化剂性能分析.《北京航空航天大学学报》.2007,第33卷(第1期),119-122. * |
| 鹿桂芳等.酚醛改性胺环氧树脂固化剂研究进展.《化学与黏合》.2005,第27卷(第4期),233-236. * |
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