CN108976389A - A kind of microcapsules quick curing agent and preparation method thereof for epoxy resin - Google Patents
A kind of microcapsules quick curing agent and preparation method thereof for epoxy resin Download PDFInfo
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- CN108976389A CN108976389A CN201810820034.3A CN201810820034A CN108976389A CN 108976389 A CN108976389 A CN 108976389A CN 201810820034 A CN201810820034 A CN 201810820034A CN 108976389 A CN108976389 A CN 108976389A
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- Prior art keywords
- curing agent
- microcapsules
- epoxy resin
- thermoplastic resin
- resin
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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
- 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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of microcapsules quick curing agents for epoxy resin, it is wall material by core material, thermoplastic resin of active curing agent, it can make fast epoxy resin curing, solve the problems, such as single component epoxy rapid curing and the raising store materials phase two, suitable for preparing the epoxy prepreg of the fibers such as carbon fiber, glass fibre and its fabric enhancing, it can be applied to the fields such as automobile, sports articles and aerospace.
Description
Technical field
The present invention relates to one kind for microcapsules quick curing agent and preparation method thereof, belongs to curing agent and its technology of preparing
Field.
Background technique
Epoxy resin is the general name in molecule with two or more epoxy group performed polymers, band ether and secondary on main chain
Alcohol radical, two sealing ends are epoxy group, ring-opening reaction can occur with a variety of compounds containing active hydrogen.Curing agent is added in epoxy resin
Afterwards, solidification is cross-linked into reticular structure under certain condition, is a kind of important thermosetting for a kind of widely used high molecular material
Property resin variety.Common high-performance epoxy hardener curing time is longer, in order to improve composite material production efficiency, reduces the people
Product composite material manufacturing cost, under the premise of not improving solidification temperature and not reducing composite property, it is desirable to contract as far as possible
Short curing time.But the shortening of curing time means the raising of curing agent reactivity, makes epoxy resin and its preparation
Prepreg storage period greatly shortens.
Curing agent or promotor are subjected to microencapsulation, it is to solve the above problems that latency is made it have in resin matrix
A kind of scheme.The solidification process of epoxy-resin systems is curing agent or curing accelerator in the continuous action of outside energy or draws
Give generation.The required energy that the curing agent or curing accelerator of greater activity carry out solidification process is lower, and the time is shorter,
But the Storage period of resin system also due to this reason and reduce.After microcapsules technology, by curing agent or curing accelerator
It is isolated with the other compositions of epoxy resin, only under certain temperature or pressure, makes external microcapsules rupture, release inside
Curing agent or curing accelerator, cause curing reaction, this addresses the problem rapid curing and extend the store materials phase two asks
Topic.
Micro capsule curing agent research is more, such as micro- Rubber Capsule curing accelerator of Shioh development, using polymethyl
Acid esters makees the microcapsules that coating agent, imdazole derivatives and triphenylphosphine make core, and the epoxy resin of the stable storing of composition is for half
The sealing of conductor device.Micro- Rubber Capsule curing accelerator of the synthesis such as Cao Ming, using ten alkyl phenyl silicones gradient co-polymers
For shell, ultrasonic disperse adds the imidazoles particle of spray drying to be core, can significantly improve Storage period.The developments such as Bmndys it is micro- encapsulated
Capsule curing accelerator, coating agent also use polymethacrylates, core 3,4- diphenyl-imidazole chlorination copper complex, for double
The curing accelerator of cyanamide and epoxy resin.These curing agent wall materials are mostly that the lower polymer of heat resistance is easily decomposes or wave
Hair, is not suitable for preparing epoxy prepreg.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of microcapsules quick curing agent for epoxy resin and its
Preparation method can make fast epoxy resin curing, solve single component epoxy rapid curing and improve the store materials phase two
A problem can be applied to vapour suitable for preparing the epoxy prepreg of the fibers such as carbon fiber, glass fibre and its fabric enhancing
The fields such as vehicle, sports articles and aerospace.
The present invention is realized by following scheme:
A kind of microcapsules quick curing agent for epoxy resin, which is characterized in that the core material of the microcapsules quick curing agent
For active curing agent, wall material is thermoplastic resin.
Further, the active curing agent is imidazoles or derivatives thereof.
Further, the active curing agent is imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2- phenylimidazole, 2- benzene
Base -4-methylimidazole, 2-ethyl-4-methylimidazole, 1- cyano -2-ethyl-4-methylimidazole or 1- cyano -2- phenylimidazole.
Further, the thermoplastic resin is high-temperature resistant thermoplastic resin.
Further, the thermoplastic resin is poly(aryl ether ketone), polyetherimide or polyethersulfone resin.
A method of preparing the above-mentioned microcapsules quick curing agent for epoxy resin, it is characterised in that: use solution
Spray-on process prepares microcapsule-type curing agent, the specific steps are as follows:
(1) active curing agent and thermoplastic resin are mixed and added into dispersing agent according to a certain ratio, are dissolved in organic solvent, stirring is extremely
Thermoplastic resin is completely dissolved；
(2) solution that step (1) obtains is injected into cold methanol solution；
(3) sediment is filtered, filtered sediment is placed in vacuum oven, obtains microcapsules rapid curing after dry
Agent.
Further, the mass ratio of the active curing agent and thermoplastic resin is 1:1~1:100.
Further, the organic solvent is the organic matter to dissolve each other with thermoplastic resin wall material.
Further, the organic solvent is methylene chloride, chloroform or dimethylformamide.
Further, the dispersing agent in step (1) is silanes dispersing agent, the additional amount of dispersing agent be active curing agent and
The 0.1%-10% of thermoplastic resin mass fraction.
Technical effect of the invention: microcapsule wall material in the prior art is mostly the lower polymer of heat resistance, in epoxy
It is easy to decompose or volatilize in advance during resin storage, epoxy resin Storage period is caused to decline.In addition, existing heat resistance is lower
Microcapsule wall material is easy to rupture in advance in Curing Process of Epoxy, and epoxy resin cure reaction is caused to occur in advance,
Influence the performance of the epoxy resin after solidifying.Microcapsule wall material heat resistant thermoplastic's resin that the present invention uses, can effectively keep away
Exempt from the appearance of the above problem.
Specific embodiment
Combined with specific embodiments below with specification to a kind of microcapsules rapid curing for epoxy resin of the invention
Agent and preparation method thereof is further elaborated, but protection content of the invention is not limited to following embodiment.
A kind of microcapsules quick curing agent for epoxy resin, with active curing agent core material, using thermoplastic resin as wall
Material.Active curing agent is imidazoles or derivatives thereof, such as imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2- phenylimidazole, 2- phenyl-
4-methylimidazole, 2-ethyl-4-methylimidazole, 1- cyano -2-ethyl-4-methylimidazole or 1- cyano -2- phenylimidazole.Thermoplastic
Property resin be high-temperature resistant thermoplastic resin, such as poly(aryl ether ketone), polyetherimide or polyethersulfone resin.The mass ratio of core material and wall material
For 1:(5-6).In preparation, the organic solvent that uses is the organic matter that dissolves each other with thermoplastic resin wall material, such as methylene chloride, trichlorine
Methane or dimethylformamide.Dispersing agent is silanes dispersing agent, and the additional amount of dispersing agent is active curing agent and thermoplastic resin
The 0.1%-10% of rouge mass fraction.
Embodiment 1
It is wall material by core material, poly(aryl ether ketone) of 2-ethyl-4-methylimidazole.By 2-ethyl-4-methylimidazole and poly(aryl ether ketone) 1:5
Proportion is mixed and added into the KH550 dispersing agent that dispersing agent mass ratio is 0.5% (to count on the basis of the gross mass of core material and wall material),
It is dissolved in dichloromethane solvent, solid content 20%.Stirring is completely dissolved to poly(aryl ether ketone), and cold methanol is injected into using spray head
In solution.Sediment is filtered, is placed in vacuum oven, 60 DEG C of drying 24 hours are to get to microcapsules quick curing agent.With ring
After oxygen resin E51 is mixed with mass ratio 1:30, mixture solidifies for 15 minutes under the conditions of 130 DEG C, pour mass vitrifying after solidification
Transition temperature is more than 140 DEG C.
Embodiment 2
It is wall material using 1- cyano -2- phenylimidazole as core material, poly(aryl ether ketone).By 1- cyano -2- phenylimidazole and poly(aryl ether ketone) 1:6
Proportion is mixed and added into the KH550 dispersing agent that dispersing agent mass ratio is 0.5%, is dissolved in dichloromethane solvent, solid content 20%.It stirs
It mixes to poly(aryl ether ketone) and is completely dissolved, be injected into using spray head in cold methanol solution.Sediment is filtered, merging vacuum drying
Case, 60 DEG C of dryings 24 hours are to get arriving microcapsules quick curing agent.After being mixed with epoxy resin AG80 with mass ratio 1:25, mix
It closes object to solidify within 15 minutes under the conditions of 130 DEG C, pour mass glass transition temperature is more than 140 DEG C after solidification.
Embodiment 3
It is wall material using 1- cyano -2- phenylimidazole as core material, polyetherimide.By 1- cyano -2- phenylimidazole and polyetherimide
Amine 1:6 proportion is mixed and added into KH560 points that dispersing agent mass ratio is 0.3% (to count on the basis of the gross mass of core material and wall material)
Powder is dissolved in solvent dimethylformamide, solid content 20%.Stirring is completely dissolved to polyetherimide, is injected into using spray head
Enter in cold methanol solution.Sediment is filtered, vacuum oven is placed in, 60 DEG C of drying 24 hours quick to get microcapsules are arrived
Curing agent.After being mixed with epoxy resin AG80 with mass ratio 1:100, mixture solidifies for 5 minutes under the conditions of 150 DEG C, after solidification
Pour mass glass transition temperature is more than 150 DEG C.
Embodiment 4
It is wall material by core material, polyetherimide of 2-methylimidazole.Simultaneously by 2-methylimidazole and the mixing of polyetherimide 1:6 proportion
The KH560 dispersing agent that dispersing agent mass ratio is 1% (to count on the basis of the gross mass of core material and wall material) is added, is dissolved in dimethyl methyl
Amide solvent, solid content 20%.Stirring is completely dissolved to polyetherimide, is injected into cold methanol solution using spray head.
Sediment is filtered, is placed in vacuum oven, 60 DEG C of drying 24 hours are to get to microcapsules quick curing agent.With epoxy resin
After AG80 is mixed with mass ratio 1:1, mixture solidifies for 5 minutes under the conditions of 150 DEG C, pour mass glass transition temperature after solidification
More than 120 DEG C.
Claims (10)
1. a kind of microcapsules quick curing agent for epoxy resin, which is characterized in that the core of the microcapsules quick curing agent
Material is active curing agent, and wall material is thermoplastic resin.
2. a kind of microcapsules quick curing agent for epoxy resin according to claim 1, it is characterised in that: the work
Property curing agent be imidazoles or derivatives thereof.
3. a kind of microcapsules quick curing agent for epoxy resin according to claim 2, it is characterised in that: the work
Property curing agent be imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2- phenylimidazole, 2- phenyl -4-methylimidazole, 2- ethyl -4- first
Base imidazoles, 1- cyano -2-ethyl-4-methylimidazole or 1- cyano -2- phenylimidazole.
4. a kind of microcapsules quick curing agent for epoxy resin according to claim 1, it is characterised in that: the heat
Plastic resin is high-temperature resistant thermoplastic resin.
5. a kind of quick curing agent for epoxy resin according to claim 4, it is characterised in that: the thermoplastic resin
Rouge is poly(aryl ether ketone), polyetherimide or polyethersulfone resin.
6. a kind of method for preparing a kind of microcapsules quick curing agent for epoxy resin according to claim 1,
It is characterized in that: microcapsule-type curing agent is prepared using solution spray-on process, the specific steps are as follows:
Active curing agent and thermoplastic resin are mixed and added into dispersing agent according to a certain ratio, are dissolved in organic solvent, stirring to heat
Plastic resin is completely dissolved；
The solution that step (1) obtains is injected into cold methanol solution；
Sediment is filtered, filtered sediment is placed in vacuum oven, obtains microcapsules quick curing agent after dry.
7. according to the method described in claim 6, it is characterized by: the mass ratio of the active curing agent and thermoplastic resin is
1:1~1:100.
8. the method according to claim 6, it is characterised in that: the organic solvent is to dissolve each other with thermoplastic resin wall material
Organic matter.
9. according to the method described in claim 8, it is characterized in that, the organic solvent is methylene chloride, chloroform or two
Methylformamide.
10. according to the method described in claim 8, it is characterized by: dispersing agent in step (1) is silanes dispersing agent, point
The additional amount of powder is the 0.1%-10% of active curing agent and thermoplastic resin mass fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810820034.3A CN108976389A (en) | 2018-07-24 | 2018-07-24 | A kind of microcapsules quick curing agent and preparation method thereof for epoxy resin |
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| CN201810820034.3A CN108976389A (en) | 2018-07-24 | 2018-07-24 | A kind of microcapsules quick curing agent and preparation method thereof for epoxy resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746580A (en) * | 2019-11-29 | 2020-02-04 | 肇庆市海特复合材料技术研究院 | PPMA (polypropylene-random-oxide-styrene) coated microcapsule type rapid curing agent for epoxy resin with long storage period and preparation method and application thereof |
| CN110835404A (en) * | 2019-12-02 | 2020-02-25 | 肇庆市海特复合材料技术研究院 | Preparation method of microcapsule rapid curing agent for epoxy resin |
| CN110834444A (en) * | 2019-11-26 | 2020-02-25 | 江苏大学 | Preparation method of interlayer toughening composite material |
| CN111484714A (en) * | 2020-05-13 | 2020-08-04 | 华东理工大学 | Low-temperature forming method of unsaturated bulk molding compound |
| CN116102714A (en) * | 2023-04-11 | 2023-05-12 | 天津爱思达新材料科技有限公司 | Epoxy resin microcapsule rapid curing system and preparation method thereof |
| WO2024183721A1 (en) * | 2023-03-07 | 2024-09-12 | 华为技术有限公司 | Capsule-type imidazole curing agent and manufacturing method therefor, and curable composition comprising capsule-type imidazole curing agent |
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| CN1112142A (en) * | 1994-03-15 | 1995-11-22 | 东丽株式会社 | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
| US20120248639A1 (en) * | 2011-03-31 | 2012-10-04 | Mitsuru Akagawa | Microencapsulated curing agent |
| CN104193965A (en) * | 2014-08-21 | 2014-12-10 | 江汉大学 | Imidazole epoxy curing agent micro capsule and preparation method thereof |
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2018
- 2018-07-24 CN CN201810820034.3A patent/CN108976389A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1112142A (en) * | 1994-03-15 | 1995-11-22 | 东丽株式会社 | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
| US20120248639A1 (en) * | 2011-03-31 | 2012-10-04 | Mitsuru Akagawa | Microencapsulated curing agent |
| CN104193965A (en) * | 2014-08-21 | 2014-12-10 | 江汉大学 | Imidazole epoxy curing agent micro capsule and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110834444A (en) * | 2019-11-26 | 2020-02-25 | 江苏大学 | Preparation method of interlayer toughening composite material |
| CN110834444B (en) * | 2019-11-26 | 2021-11-23 | 江苏大学 | Preparation method of interlayer toughening composite material |
| CN110746580A (en) * | 2019-11-29 | 2020-02-04 | 肇庆市海特复合材料技术研究院 | PPMA (polypropylene-random-oxide-styrene) coated microcapsule type rapid curing agent for epoxy resin with long storage period and preparation method and application thereof |
| CN110835404A (en) * | 2019-12-02 | 2020-02-25 | 肇庆市海特复合材料技术研究院 | Preparation method of microcapsule rapid curing agent for epoxy resin |
| CN111484714A (en) * | 2020-05-13 | 2020-08-04 | 华东理工大学 | Low-temperature forming method of unsaturated bulk molding compound |
| WO2024183721A1 (en) * | 2023-03-07 | 2024-09-12 | 华为技术有限公司 | Capsule-type imidazole curing agent and manufacturing method therefor, and curable composition comprising capsule-type imidazole curing agent |
| CN116102714A (en) * | 2023-04-11 | 2023-05-12 | 天津爱思达新材料科技有限公司 | Epoxy resin microcapsule rapid curing system and preparation method thereof |
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Application publication date: 20181211 |
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