CN105860029B - A kind of preparation method of fire resistant water-based epoxy resin - Google Patents
A kind of preparation method of fire resistant water-based epoxy resin Download PDFInfo
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- CN105860029B CN105860029B CN201610451512.9A CN201610451512A CN105860029B CN 105860029 B CN105860029 B CN 105860029B CN 201610451512 A CN201610451512 A CN 201610451512A CN 105860029 B CN105860029 B CN 105860029B
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- epoxy resin
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- fire resistant
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
Abstract
The invention discloses a kind of preparation methods of fire resistant water-based epoxy resin, are specially to add in solvent in the epoxy resin that (1) is 0.1 0.6mol/100g in epoxide number, being stirred evenly at 60 DEG C~80 DEG C is completely dissolved epoxy resin, obtains product 1；(2) organic amine is added in product 1, is reacted with epoxy resin, the ratio of the epoxy resin and organic amine is 1:0.1~1:0.5, obtain product 2；(3) functional silane monomer is added in product 2, product 3 is obtained after reaction；(4) silane monomer and deionized water are added in into product 3, product 4 is obtained after reaction；(5) strong classes of organic acids is added in into product 4 and is neutralized into salt, obtain product 5；(6) deionized water is added in into product 5, aqueous epoxy resins are obtained after dilution.The aqueous epoxy resins that the present invention obtains, high temperature resistant salt spray resistance is outstanding, has further expanded the application range of epoxy resin.
Description
【Technical field】
The invention belongs to macromolecule synthesising technology fields, and main application fields are coating, ink, and slight changes can also be used
In fields such as adhesives.
【Background technology】
Epoxy resin has excellent adhesive force and antiseptic property, has a wide range of applications in paint field.It is protected in environment
It protects increasingly strict today, the Water-borne modification of epoxy resin is trend of the times.However the performance of epoxy resin at high temperature is poor, limit
Its application range is made.
Existing organic silicon modified aqueous epoxy resin, generally using physical blending and chemical reaction two ways.Physics
Blend method is simple, but poor compatibility, and modified effect is poor.
Chemical reaction is mainly reacted using functional group such as hydroxyl, alkoxy etc. on organosilicon and epoxy resin, generation
Grafting or block copolymer.But reaction process stability is poor, it is understood that there may be a part of organosilicon unreacted.Its Water-borne modification mode
Generally by introducing carboxyl, Water-borne modification after being neutralized with amine belongs to anion-type water-thinned resin.Its under high temperature and hygrothermal environment with
The poor adhesive force of metal substrate is unfavorable for protection of the paint film to ground.
【The content of the invention】
The technical problem to be solved in the present invention is to provide a kind of preparation methods of heat safe aqueous epoxy resins.
The technical scheme is that a kind of preparation method of fire resistant water-based epoxy resin, concretely comprises the following steps,
(1) solvent is added in the epoxy resin for being 0.1-0.6mol/100g in epoxide number, is stirred evenly at 60 DEG C~80 DEG C
Epoxy resin is completely dissolved, obtains product 1；Contain 2 or 2 or more epoxy groups in the epoxy molecule；
(2) organic amine is added in product 1, is reacted with epoxy resin, the ratio of the epoxy resin and organic amine is 1:
0.1~1:0.5, obtain product 2；
(3) functional silane monomer is added in product 2, product 3 is obtained after reaction；
(4) silane monomer and deionized water are added in into product 3, product 4 is obtained after reaction；
(5) strong classes of organic acids is added in into product 4 and is neutralized into salt, obtain product 5；
(6) deionized water is added in into product 5, aqueous epoxy resins are obtained after dilution.
In step (5), organic acid：The mol ratios of organic amine are：0.6:1~1.1:1.
General water-base resin be divided into three types be cation respectively, it is anion, non-ionic, cationic is wherein one
Kind.The invention belongs to cation-type water-thinned resin, cation type refers to the structure type of resin, and hydrogen ion is provided with acid, with
Amino in resin combines so that resin positively charged.
The present invention is to dissolving no particular/special requirement, and solid is 60%-80% after general dissolving.The epoxy resin of addition is in 1-
3mol。
Organic amine is added according to the ratio with epoxy resin, and the amount of being preferably added is 0.3-1.5mol.
Step (3), it is preferred that 60-120 DEG C of functional silane reaction temperature, addition 0.1-0.5mol.
Step (4) silane charge：Binary is 0.5-1.5mol plus ternary total amount.50-100 DEG C of reaction temperature.
Strong acid addition is preferably 0.2-1.5mol, is advisable with that can be neutralized into salt.
The preparation method of a kind of fire resistant water-based epoxy resin according to the present invention, it is preferred that molten described in step (1)
Agent is ether solvent.Preferably, the organic amine described in step (2) is primary amine or secondary amine.
A kind of preparation method of fire resistant water-based epoxy resin of the present invention, further, the organic amine described in step (2)
For the one or several kinds in n-butylamine, di-n-butylamine, diethylamine, ethylenediamine, monoethanolamine, diethanol amine, monoisopropanolamine.
Preferably, the reaction temperature described in step (2) is 60 DEG C of -120 DEG C of it is further preferred that reaction temperature is 70 DEG C
~100 DEG C.
A kind of preparation method of fire resistant water-based epoxy resin of the present invention, it is preferred that the functionality described in step (3)
Silane monomer is the functional silane monomer containing epoxy group either primary amine, secondary amine or isocyanate group；Described in step (4)
Silane monomer is the silane monomer of binary or ternary.The silane monomer of step (4), be binary or ternary silane monomer wherein
One kind, can also binary ternary collocation use, binary ternary collocation performance it is more preferable.
Further, the functional silane monomer described in step (3) is -3 aminopropyl trimethoxysilane of N- aminoethyls, 3-
Aminopropyltriethoxywerene werene, 3- glycydoxies methyldiethoxysilane, 3- glycidol ethers oxygroup third
Base trimethoxy silane, 3- glycydoxies triethoxysilane, 3- isocyanate group propyl trimethoxy silicanes
In one or several kinds.
Further, the silane monomer described in step (4) is methyltrimethoxysilane, methyltriethoxysilane, benzene
Base trimethoxy silane, ethyl orthosilicate, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diphenyl dimethoxy
One or several kinds in base silane.
A kind of preparation method of fire resistant water-based epoxy resin of the present invention, it is preferred that the organic acid described in step (5)
One or several kinds in benzene sulfonic acid, formic acid, acetic acid, ethanedioic acid, succinic acid, citric acid.
Preferably, in step (3), product 2 is 1 with functional silane monomer ratio:0.02~1:0.05；Step (4)
In, the quality of silane monomer accounts for the ratio of product 3 as 5%~25%, and water accounts for the 15%~25% of silane gross mass.Step (4)
Reaction temperature be 60~80 DEG C.
The present invention technical principle be：Using epoxy resin as agent structure, by the chain extension of amine, modification, molecule is controlled
The size and water solubility of amount.The effect that functional silane realizes bridge joint is added in, silane is continuously added and reaches modified host epoxy
The purpose of resin.Finally water-soluble resin is obtained using acid neutralization.
1st, the epoxy resin of suitable molecular weight is dissolved in solvent, it is spare is warming up to certain temperature.Its epoxy resin
2 epoxide groups should at least be contained, to achieve the purpose that chain extension in next step.
2nd, organic amine is added at a certain temperature, with epoxy reaction.Generally using primary amine and secondary amine, such as n-butylamine
And di-n-butyl amine.Primary amine mainly plays the role of chain extension, and secondary amine can both adjust the quantity of N atoms in resin backbone, and also might be used
To introduce some special functional groups.
The amount that primary amine and secondary amine add in is this step emphasis, and primary amine adds in excessive, easy gel in building-up process.Add in number
Amount is inadequate, and the molecular weight of resin is smaller, and final performance is poor.Primary amine is in 0.3-1mol, and secondary amine is in 0.3-1mol.
3rd, functional silane is continuously added.Bridge beam action is played mainly between epoxy resin and silane, is into one
Step introduces silane and prepares.If lacking this part, resin property declines to a great extent.
The reaction being related to is：Amido and the epoxy reaction in function silane, the amido in epoxy group and function silane are anti-
It answers, the isocyanates in hydroxyl and function silane reacts.
The present invention is neutralized with acid by amine and epoxy reaction and realizes Water-borne modification.The invention belongs to cation-type water-thinned resin,
Adhesive force on ground is more preferable, even if adhesive force has almost no change after 300 DEG C of high-temperature bakings；Anionic heat-resisting quantity
Can be relatively poor, and the combination power of ground is weaker.
Epoxy resin has excellent adhesive force, but high temperature resistance is poor.By the modification of silane, organic-nothing is realized
Machine hydridization improves heat resistance.Amine why is selected to be reacted with epoxy resin, then is neutralized with acid and realizes Water-borne modification, is because N is former
Son and ground are because the effect of hydrogen bond, even if the adhesive force of resin is still without significant change at high temperature.
The present invention has synthesized a kind of aqueous epoxy resins of hybrid inorganic-organic by modification of the silane to epoxy resin,
Epoxy resin is original a little outer maintaining, and substantially increases the performances such as the high temperature resistant of epoxy resin, hardness, ageing-resistant, into
One step has expanded the application range of epoxy resin.
Salt spray resistance：
1st, epoxy resin has outstanding salt spray resistance in itself
2nd, the presence of " N " further improves adhesive force between resin and ground in cationic epoxy resin, favorably
In protection of the paint film to ground.
3rd, the volatilization of organic acid makes resin be changed from aqueous to solvent-borne type, is irreversible process, further improves resin
Salt spray resistance.
Resin of the present invention is chemical bond linkage entirely, and the salt spray resistance of physical mixed is excellent than in the prior art.Moreover, this
Invention cation type resin is got well than the salt spray resistance of general resin.Epoxy resin is the significant contributor of salt spray resistance.
Resin of the present invention is silicon-modified epoxy, and epoxy occupies the majority, therefore salt spray resistance is excellent.
High temperature resistance：300 DEG C of paint film appearances are unchanged, adhesive force<1 grade, hardness 2H, when salt spray resistance 240 is small.
【Specific embodiment】
Embodiment 1
1st, 760g (2mol) epoxy resin 618 is dissolved in 100g n-butanols
2nd, 90 DEG C are warming up to, is slowly added to 36g (0.5mol) n-butylamine, until the reaction is complete.
3rd, functional silane KH550 about 22g (0.1mol) are continuously added, until the reaction is complete
4th, methyltriethoxysilane 178g (1mol) is added in, it is spare in 80 DEG C of heat preservations after stirring evenly.
5th, add in 36g (2mol) deionized water, stirring 2 it is small when after cool down.
6th, add in 23g (0.5mol) formic acid and appropriate amount of deionized water obtains required resin.
High temperature resistance：300 DEG C of paint film appearances are unchanged, adhesive force<1 grade, hardness 2H, when salt spray resistance 240 is small.
Embodiment 2
1st, 2000g (2mol) epoxy resin 601 is dissolved in 500g propylene glycol monomethyl ethers
2nd, 100 DEG C are warming up to, is slowly added to ethanolamine 61g (1mol), until the reaction is complete
3rd, diethanol amine 10.5g (0.1mol) is continuously added, until the reaction is complete
4th, 80 DEG C are cooled to, adds in 24.7g (0.1mol) isocyanates propyl-triethoxysilicane, until the reaction is complete
5th, methyltrimethoxysilane, dimethyldimethoxysil,ne difference 100g are added in, is stirred evenly
6th, 70 DEG C addition 54g deionized waters, heat preservation 1 it is small when after cool down.
7th, add in 46g formic acid and appropriate amount of deionized water obtains required resin.
High temperature resistance：300 DEG C of paint film appearances are unchanged, adhesive force<1 grade, hardness 2H, when salt spray resistance 240 is small.
Embodiment 3
1st, 760g (2mol) epoxy resin 618 is dissolved in 100g n-butanols
2nd, 85 DEG C are warming up to, is slowly added to 30.5g (0.5mol) ethanolamine, until the reaction is complete.
3rd, functional silane KH550 about 22g (0.1mol) are continuously added, until the reaction is complete
4th, phenyltrimethoxysila,e 99g (0.5mol) and dimethyldimethoxysil,ne 60g (0.5mol), stirring are added in
It is spare in 80 DEG C of heat preservations after uniformly.
5th, add in 36g (2mol) deionized water, stirring 2 it is small when after cool down.
6th, add in 13.8g (0.3mol) formic acid and appropriate amount of deionized water obtains required resin.
Embodiment 4
1st, 380g (1mol) epoxy resin 618 is dissolved in 50g propylene glycol monomethyl ethers
2nd, 85 DEG C are warming up to, is slowly added to 12.2g (0.2mol) ethanolamines and diethanol amine 63g (0.6mol), until anti-
It should be complete.
3rd, functional silane KH550 about 44g (0.2mol) are continuously added, until the reaction is complete
4th, dimethyldimethoxysil,ne 120g (1mol) is added in, it is spare in 80 DEG C of heat preservations after stirring evenly.
5th, add in 27g (1.5mol) deionized water, stirring 2 it is small when after cool down.
6th, add in 37.6g (0.8mol) formic acid and appropriate amount of deionized water obtains required resin.
The aqueous epoxy resins of the present invention by rationally preparing, substantially increase the high temperature resistant of epoxy resin, hardness, resistance to
The performances such as aging have further expanded the application range of epoxy resin.It has a good application prospect.
Claims (10)
1. a kind of preparation method of fire resistant water-based epoxy resin, which is characterized in that concretely comprise the following steps
(1) solvent is added in the epoxy resin for being 0.1-0.6mol/100g in epoxide number, being stirred evenly at 60 DEG C~80 DEG C makes ring
Oxygen resin is completely dissolved, and obtains product 1；Contain 2 or 2 or more epoxy groups in the epoxy molecule；
(2) organic amine is added in product 1, is reacted with epoxy resin, the ratio of the epoxy resin and organic amine is 1:0.1~
1:0.5, obtain product 2；
(3) functional silane monomer is added in product 2, product 3 is obtained after reaction；Product 2 and functional silane monomer ratio
For 1:0.02~1:0.05；
(4) silane monomer and deionized water are added in into product 3, product 4 is obtained after reaction；
(5) strong classes of organic acids is added in into product 4 and is neutralized into salt, obtain product 5；
(6) deionized water is added in into product 5, aqueous epoxy resins are obtained after dilution.
A kind of 2. preparation method of fire resistant water-based epoxy resin as described in claim 1, which is characterized in that step (1) institute
The solvent stated is ether solvent.
A kind of 3. preparation method of fire resistant water-based epoxy resin as described in claim 1, which is characterized in that step (2) institute
The organic amine stated is primary amine or secondary amine.
A kind of 4. preparation method of fire resistant water-based epoxy resin as claimed in claim 3, which is characterized in that step (2) institute
The organic amine stated is one in n-butylamine, di-n-butylamine, diethylamine, ethylenediamine, monoethanolamine, diethanol amine, monoisopropanolamine
Kind is several.
A kind of 5. preparation method of fire resistant water-based epoxy resin as described in claim 1, which is characterized in that step (2) institute
The reaction temperature stated is 60 DEG C -120 DEG C.
A kind of 6. preparation method of fire resistant water-based epoxy resin as described in claim 1, which is characterized in that step (3) institute
The functional silane monomer stated is the functional silane monomer containing epoxy group either primary amine, secondary amine or isocyanate group；Step
Suddenly the silane monomer described in (4) is the silane monomer of binary or ternary.
A kind of 7. preparation method of fire resistant water-based epoxy resin as described in claim 1 or 6, which is characterized in that step (3)
The functional silane monomer is -3 aminopropyl trimethoxysilane of N- aminoethyls, 3-aminopropyltriethoxysilane, 3-
Glycydoxy methyldiethoxysilane, 3- glycydoxies trimethoxy silane, 3- shrink sweet
One or several kinds in oily ether oxygen base propyl-triethoxysilicane, 3- isocyanate group propyl trimethoxy silicanes.
A kind of 8. preparation method of fire resistant water-based epoxy resin as claimed in claim 6, which is characterized in that step (4) institute
The silane monomer stated for methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysila,e, ethyl orthosilicate,
One or several kinds in dimethyldimethoxysil,ne, dimethyl diethoxysilane, dimethoxydiphenylsilane.
A kind of 9. preparation method of fire resistant water-based epoxy resin as described in claim 1, which is characterized in that step (5) institute
One or several kinds of the organic acid stated in benzene sulfonic acid, formic acid, acetic acid, ethanedioic acid, succinic acid, citric acid.
A kind of 10. preparation method of fire resistant water-based epoxy resin as described in claim 1, which is characterized in that step (4)
In, the quality of silane monomer accounts for the ratio of product 3 as 5%~25%, and water accounts for the 15%~25% of silane gross mass.
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| CN109438674B (en) * | 2018-11-21 | 2021-01-29 | 苏州生益科技有限公司 | Phosphorus-containing epoxy resin composition, and prepreg and laminated board prepared from same |
| CN109608619B (en) * | 2018-11-21 | 2021-01-15 | 苏州生益科技有限公司 | Phosphorus-containing epoxy resin composition, and prepreg and laminated board prepared from same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079810A (en) * | 2010-12-15 | 2011-06-01 | 北京航空航天大学 | Synthesis and application of light-cured polyurethane-acrylic acid-epoxy resin adhesive |
| CN104231231A (en) * | 2014-09-17 | 2014-12-24 | 张会励 | Preparation method of organic-inorganic hybrid water-based resin |
| CN103360575B (en) * | 2013-07-30 | 2015-08-12 | 长沙学院 | A kind of water-based organic salt modified epoxy ester resin and preparation method thereof and application |
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|---|---|---|---|---|
| US6770371B2 (en) * | 2002-07-08 | 2004-08-03 | The Boeing Company | Silane triol capped expoxy-amine adhesion promoter for adhesive-bonded metal substrates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079810A (en) * | 2010-12-15 | 2011-06-01 | 北京航空航天大学 | Synthesis and application of light-cured polyurethane-acrylic acid-epoxy resin adhesive |
| CN103360575B (en) * | 2013-07-30 | 2015-08-12 | 长沙学院 | A kind of water-based organic salt modified epoxy ester resin and preparation method thereof and application |
| CN104231231A (en) * | 2014-09-17 | 2014-12-24 | 张会励 | Preparation method of organic-inorganic hybrid water-based resin |
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