CN105646848B - Epoxy resin/amine-type cure system water resistance can be improved contains fluorine catalyst and preparation method thereof - Google Patents
Epoxy resin/amine-type cure system water resistance can be improved contains fluorine catalyst and preparation method thereof Download PDFInfo
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- CN105646848B CN105646848B CN201610156612.9A CN201610156612A CN105646848B CN 105646848 B CN105646848 B CN 105646848B CN 201610156612 A CN201610156612 A CN 201610156612A CN 105646848 B CN105646848 B CN 105646848B
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- Prior art keywords
- amine
- epoxy resin
- water resistance
- preparation
- catalyst
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Classifications
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing 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
- C08G59/50—Amines
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
Abstract
The present invention relates to it is a kind of improve epoxy resin/amine-type cure system water resistance containing fluorine catalyst and preparation method thereof, a kind of fluorine-containing ammonium salt is generated using fluorinated, acid and polyetheramine, it is brown liquid at room temperature, it is soluble in water, pH value is 4~7, has fabulous catalytic for epoxy resin/amine curing agent.The fluorine-containing catalyst preparation for improving epoxy resin/amine-type cure system water resistance of the present invention is simple to operate, easy, due to containing fluorine atom, the system of institute's catalytic curing has low surface energy, preferable water resistance so that it has potential application prospect in terms of coating, electronic encapsulating material, composite.
Description
Technical field
The invention belongs to the special addition agent of high polymer material, belongs to containing fluorine catalyst and preparation method thereof, and in particular to one
Kind can improve epoxy resin/amine-type cure system water resistance containing fluorine catalyst and preparation method thereof.It is that epoxy resin/amine is solid
The special excellent rapid curing catalyst of change system, the water resistance of curing system can be improved, reduce surface tension.
Background technology
Amine curing agent is the important curing agent of epoxy resin, and because species is different, solidification temperature is from room temperature to high temperature.One
As, in gentle high-temperature curing agent need catalyst just to meet to be actually needed, the epoxy-resin systems after solidification due to containing
Hydroxyl isopolarity group easily absorbs water, and reduces the water resistance of curing system.Fluorinated polymer is generally used for double thin property materials,
Anti-fouling material, low friction and non-adhesive material field.Therefore, surface energy can be reduced by fluorine being introduced in curing system, and it is resistance to improve its
It is water-based.This patent contains fluorine catalyst using prepared by fluorinated, acid and polyetheramine, and it is anti-can to significantly improve epoxy resin/amine-type cure
Answer speed, meanwhile, the surface energy of curing system can be reduced by being introduced containing fluorine atom in fluorine catalyst, influence system wellability,
Adhesion and solvent resistance.The bond energy of C-F keys is higher than C-C bond energys, and the change of polymer can be improved by introducing C-F keys in the polymer
The property learned and heat endurance.If fluorine atom, in surface enrichment, curing system can be applied to the coating of low-surface-energy.If fluorine atom
In polymer network, the water proofing property of curing system can be improved.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that one kind can improve epoxy resin/amine-type cure system
The reaction speed for containing fluorine catalyst and preparation method thereof, accelerating amine-type cure epoxy resin of water resistance, improves curing system
Water resistance.
Technical scheme
It is a kind of improve epoxy resin/amine-type cure system water resistance contain fluorine catalyst, it is characterised in that component is to rub
You are than being 1:2~2.5 polyetheramine and fluorinated, acid.
The fluorinated, acid is trifluoroacetic acid, perfluoro-heptanoic acid or fluorination n-nonanoic acid.
The polyetheramine is that 2 degrees of functionality contain Amino End Group PPOX ether or Amino End Group polyethylene glycol oxide ether, amine value 440
~500mg KOH/g.
A kind of to prepare the method containing fluorine catalyst that improve epoxy resin/amine-type cure system water resistance, it is special
Sign is that step is as follows：
Step 1：It is 1 in molar ratio by polyetheramine and fluorinated, acid:2~2.5 ratio is mixed；
Step 2：40~60 minutes under 40 DEG C of reactions, obtain that epoxy resin/amine-type cure system water resistance can be improved
Contain fluorine catalyst.
Beneficial effect
It is proposed by the present invention it is a kind of improve epoxy resin/amine-type cure system water resistance contain fluorine catalyst and its preparation
Method, a kind of fluorine-containing ammonium salt is generated using fluorinated, acid and polyetheramine, is at room temperature brown liquid, it is soluble in water, pH value is 4~
7, there is fabulous catalytic for epoxy resin/amine curing agent.The present invention's improves epoxy resin/amine-type cure system
The fluorine-containing catalyst preparation of water resistance is simple to operate, easy, and due to containing fluorine atom, the system of institute's catalytic curing has low table
Face energy, preferable water resistance so that it has potential application prospect in terms of coating, electronic encapsulating material, composite.
The catalyst available ontologies polymerization production of the present invention, products therefrom are pure.The main performance of catalyst of the present invention：
Outward appearance：Brown liquid, pH value：4~7, effective content：More than 99%, dissolubility：It is soluble in water.This catalyst compares DMP-
30 activity are big, good with amine curing agent compatibility, can improve the water resistance of curing system, reduce surface energy, the ring solidified
Oxygen tree fat/amine-type cure system has broader practice field and bigger application value.
The present invention have developed one kind and contain fluorine catalyst, and good with amine curing agent compatibility, catalytic effect is better than existing market
Three-(dimethylamino methyl) phenol (DMP-30) of sale, can make fast epoxy resin curing, can meet epoxy resin/amine
The quick-setting requirement of curing system, the water-resistance, wellability and surface energy of curing system can be improved containing fluorine atom.
The present invention compared with prior art the advantages of be：Rational formula and processing technology, increasing substantially catalyst
In the case of catalytic activity, the introducing of fluorine atom, the water resistance of curing system can be improved, reduces surface energy, improves wellability.
And catalyst of the present invention can be produced with substance law, simple production process, products pure, narrow molecular weight distribution, all using state
Raw material are produced, cost is low.
Embodiment
In conjunction with embodiment, the invention will be further described：
The present invention technological thought be：By polyetheramine (D-230) and fluoric-containing acid (trifluoroacetic acid, perfluoro-heptanoic acid, perfluor nonyl
Acid) a kind of fluorine-containing ammonium salt in catalysis agent of reaction synthesis.There occurs anti-for hydroxyl in Amino End Group and trifluoroacetic acid in D230 on carboxyl
Should, ammonium salt is generated, epoxy radicals can be opened, so as to catalyzed epoxies and amine-type cure system.Because itself being poly-
Ether amines modified structure, therefore catalyst is used as, it is good with amine curing agent compatibility, containing fluorine atom, curing system can be improved
Water-resistance, reduce the surface energy of solidfied material.
Embodiment 1：
1 mole of polyetheramine and 2 molar trifluoroacetic acids are thrown in reactor, are warming up to 40 DEG C, stirs 40 minutes, is cooled to
25 DEG C, discharging, cool down and produce catalyst of the present invention.
Embodiment 2：
1 mole of polyetheramine and 2.5 moles of perfluoro-heptanoic acids are thrown in reactor, are warming up to 50 DEG C, is stirred 60 minutes, cooling
To 25 DEG C, discharging, cool down and produce catalyst of the present invention.
Embodiment 3：
1 mole of polyetheramine and 2.2 moles of perfluoro-pelargonic acids are thrown in reactor, are warming up to 65 DEG C, is stirred 60 minutes, cooling
To 25 DEG C, discharging, cool down and produce catalyst of the present invention.
Claims (2)
- A kind of 1. preparation method containing fluorine catalyst for improving epoxy resin/amine-type cure system water resistance, it is characterised in that： Component is that mol ratio is 1:2~2.5 polyetheramine and fluorinated, acid；The fluorinated, acid is trifluoroacetic acid, perfluoro-heptanoic acid or fluorination nonyl Acid；The step of preparation method, is as follows：Step 1：It is 1 in molar ratio by polyetheramine and fluorinated, acid:2~2.5 ratio is mixed；Step 2：40~60 minutes under 40 DEG C of reactions, obtain that containing for epoxy resin/amine-type cure system water resistance can be improved Fluorine catalyst.
- 2. the preparation side containing fluorine catalyst of epoxy resin/amine-type cure system water resistance can be improved according to claim 1 Method, it is characterised in that：The polyetheramine is that 2 degrees of functionality contain Amino End Group PPOX ether or Amino End Group polyethylene glycol oxide ether, 440~500mg of amine value KOH/g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610156612.9A CN105646848B (en) | 2016-03-18 | 2016-03-18 | Epoxy resin/amine-type cure system water resistance can be improved contains fluorine catalyst and preparation method thereof |
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| CN201610156612.9A CN105646848B (en) | 2016-03-18 | 2016-03-18 | Epoxy resin/amine-type cure system water resistance can be improved contains fluorine catalyst and preparation method thereof |
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| CN105646848A CN105646848A (en) | 2016-06-08 |
| CN105646848B true CN105646848B (en) | 2018-03-13 |
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| CN105885564B (en) * | 2016-06-23 | 2018-07-24 | 中国人民解放军国防科学技术大学 | Super-hydrophobic composite coating of the multiple fluorinated epoxy of full stress-strain and preparation method thereof and application method |
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| JPS6147730A (en) * | 1984-08-14 | 1986-03-08 | Toshiba Corp | Photo-setting composition |
| CN102637891A (en) * | 2012-04-27 | 2012-08-15 | 东方电气集团东方汽轮机有限公司 | Vanadium cell nafion proton membrane and preparation method thereof |
| CN104448714B (en) * | 2014-12-24 | 2017-01-25 | 中科院广州化学有限公司 | Organic fluorine random copolymer modified epoxy material for packaging LEDs and preparation method of organic fluorine random copolymer modified epoxy material |
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Effective date of registration: 20210401 Address after: No. 169, Wenxing Road, Xianyang equipment manufacturing industrial park, Qindu District, Xianyang City, Shaanxi Province, 712000 Patentee after: Xianyang xinweihua insulating material Co.,Ltd. Address before: 712021 No.7, Licai Industrial Park, Baoquan Road, Xianyang City, Shaanxi Province Patentee before: XIANYANG WEIHUA INSULATION MATERIALS Co.,Ltd. |