CN105566638A - Nonionic modified epoxy curing agent synthesis method - Google Patents
Nonionic modified epoxy curing agent synthesis method Download PDFInfo
- Publication number
- CN105566638A CN105566638A CN201510990616.2A CN201510990616A CN105566638A CN 105566638 A CN105566638 A CN 105566638A CN 201510990616 A CN201510990616 A CN 201510990616A CN 105566638 A CN105566638 A CN 105566638A
- Authority
- CN
- China
- Prior art keywords
- triethylene tetramine
- polyether glycol
- glycol diglycidylether
- ether solution
- propylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C08G59/40—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
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The present invention relates to a nonionic modified epoxy curing agent synthesis method comprising the following steps: under dry nitrogen protection, a propylene glycol monomethyl ether solution of triethylenetetramine is poured into a 500ml four-mouth reaction flask equipped with a reflux condenser, a thermometer and a stirrer; polyether polyol diglycidyl ether is dropped, the molar ratio and the material dropping rate are controlled for reaction to obtain a triethylenetetramine and polyether polyol diglycidyl ether adduct; and liquid epoxy resin is dropped according to stoichiometric ratio into a propylene glycol methyl ether solution of the triethylenetetramine and polyether polyol diglycidyl ether adduct with residue triethylenetetramine being removed by vacuum distillation for synthesis of a waterborne epoxy curing agent. The method is simple, low in cost and easy to control, and the synthesized nonionic waterborne epoxy curing agent has excellent corrosion resistance, chemical resistance, mechanical properties and adhesion.
Description
Technical field
The present invention relates to a kind of synthetic technology of rust proof paint solidifying agent, particularly relate to a kind of non-ionic type modified epoxy solidifying agent synthetic method.
Background technology
Epoxy resin has excellent metal adhesion and corrosion resistance nature, is the most widely used resin in current rust proof paint.But solvent epoxy coatings is because bringing harm containing a large amount of organic solvents to ecotope, and the coating technology reducing or eliminating organic solvent continues to bring out, water-borne coatings is one of most promising technology.The sixties in 20th century, aqueous epoxy coating is used widely at building field.Aqueous epoxy coating has excellent erosion resistance, chemical-resistant, mechanical property and sticking power excellent, lower VOC content, smell is little, can reduce danger of combustion, service tool such as to can wash by water at the advantage, so people start to consider aqueous epoxy coating to be used for metal rust preventing field.
Preliminary Applications research shows, although aqueous epoxy antirust paint also has gap compared with solvent type epoxy rust proof paint, except under water or especially harsh corrosive environment, all solvent type epoxy protective systems part used, aqueous epoxy antirust paint also can be competent at.The research of aqueous epoxy resins rust proof paint is focused on both ways: the Water-borne modification research being resin and solidifying agent on the one hand, is the improvement of rust-stabilising pigment on the other hand.Conventional epoxy-polyamines affixture cationoid aqueous epoxy curing agent brings adverse influence to film performance and environment protection because using VFA salify.
Summary of the invention
It is simple that technical problem to be solved by this invention is to provide a kind of method, with low cost, easy to control, and the nonionic waterborne epoxy curing agent of synthesis has excellent erosion resistance, chemical-resistant, the synthetic method of mechanical property and sticking power.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of non-ionic type modified epoxy solidifying agent synthetic method, comprises the steps:
Under drying nitrogen protection, the propylene glycol monomethyl ether solution of triethylene tetramine is put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator;
Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, be obtained by reacting triethylene tetramine and polyether glycol diglycidylether affixture;
Stoichiometrically drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, synthesis obtains aqueous epoxy curing agent.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described under drying nitrogen protection, the propylene glycol monomethyl ether solution of triethylene tetramine is put into reflux condensing tube is housed, being implemented as follows of step in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator:
Under drying nitrogen protection, be 1:1 ~ 1:1.8 according to volume ratio, the propylene glycol monomethyl ether solution of triethylene tetramine put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator.
Further, described dropping polyether glycol diglycidylether, controls material dropping speed and molar ratio of material, is obtained by reacting being implemented as follows of triethylene tetramine and polyether glycol diglycidylether affixture step:
Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, wherein triethylene tetramine and polyether glycol diglycidylether mol ratio are 2.2:1.0, and reaction 1 ~ 4h, obtains triethylene tetramine and polyether glycol diglycidylether affixture.
Further, the described liquid-state epoxy resin that stoichiometrically drips is in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, and synthesis obtains being implemented as follows of aqueous epoxy curing agent step:
Under temperature of reaction is 50 ~ 70 DEG C of conditions, be stoichiometrically 2:1 ~ 3.6:1, drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, reaction 2 ~ 5h synthesis obtains aqueous epoxy curing agent.
The invention has the beneficial effects as follows: method is simple, with low cost, easy to control, the nonionic waterborne epoxy curing agent of synthesis has excellent erosion resistance, chemical-resistant, mechanical property and sticking power.
Embodiment
Be described principle of the present invention and feature below in conjunction with example, example, only for explaining the present invention, is not intended to limit scope of the present invention.
A kind of non-ionic type modified epoxy solidifying agent synthetic method, comprises the steps:
Under drying nitrogen protection, the propylene glycol monomethyl ether solution of triethylene tetramine is put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator;
Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, be obtained by reacting triethylene tetramine and polyether glycol diglycidylether affixture;
Stoichiometrically drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, synthesis obtains aqueous epoxy curing agent.
Embodiment 1:
Under drying nitrogen protection, be 1:1 according to volume ratio, the propylene glycol monomethyl ether solution of triethylene tetramine put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator; Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, wherein triethylene tetramine and polyether glycol diglycidylether mol ratio are 2.2:1.0, and reaction 1h, obtains triethylene tetramine and polyether glycol diglycidylether affixture; Under temperature of reaction is 50 DEG C of conditions, be stoichiometrically 2:1, drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, reaction 2h synthesis obtains aqueous epoxy curing agent.
Embodiment 2:
Under drying nitrogen protection, be 1:1.5 according to volume ratio, the propylene glycol monomethyl ether solution of triethylene tetramine put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator; Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, wherein triethylene tetramine and polyether glycol diglycidylether mol ratio are 2.2:1.0, and reaction 3h, obtains triethylene tetramine and polyether glycol diglycidylether affixture; Under temperature of reaction is 60 DEG C of conditions, be stoichiometrically 3:1, drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, reaction 4h synthesis obtains aqueous epoxy curing agent.
Embodiment 3:
Under drying nitrogen protection, be 1:1.8 according to volume ratio, the propylene glycol monomethyl ether solution of triethylene tetramine put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator; Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, wherein triethylene tetramine and polyether glycol diglycidylether mol ratio are 2.2:1.0, and reaction 4h, obtains triethylene tetramine and polyether glycol diglycidylether affixture; Under temperature of reaction is 70 DEG C of conditions, be stoichiometrically 3.6:1, drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, reaction 5h synthesis obtains aqueous epoxy curing agent.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. a non-ionic type modified epoxy solidifying agent synthetic method, is characterized in that, comprise the steps:
Under drying nitrogen protection, the propylene glycol monomethyl ether solution of triethylene tetramine is put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator;
Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, be obtained by reacting triethylene tetramine and polyether glycol diglycidylether affixture;
Stoichiometrically drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, synthesis obtains aqueous epoxy curing agent.
2. a kind of non-ionic type modified epoxy solidifying agent synthetic method according to claim 1; it is characterized in that; described under drying nitrogen protection, the propylene glycol monomethyl ether solution of triethylene tetramine is put into reflux condensing tube is housed, being implemented as follows of step in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator:
Under drying nitrogen protection, be 1:1 ~ 1:1.8 according to volume ratio, the propylene glycol monomethyl ether solution of triethylene tetramine put into and reflux condensing tube is housed, in 500ml tetra-mouthfuls of reaction flasks that temperature takes into account agitator.
3. a kind of non-ionic type modified epoxy solidifying agent synthetic method according to claim 1, it is characterized in that, described dropping polyether glycol diglycidylether, control material dropping speed and molar ratio of material, be obtained by reacting being implemented as follows of triethylene tetramine and polyether glycol diglycidylether affixture step:
Drip polyether glycol diglycidylether, control material dropping speed and molar ratio of material, wherein triethylene tetramine and polyether glycol diglycidylether mol ratio are 2.2:1.0, and reaction 1 ~ 4h, obtains triethylene tetramine and polyether glycol diglycidylether affixture.
4. a kind of non-ionic type modified epoxy solidifying agent synthetic method according to claim 1, it is characterized in that, the described liquid-state epoxy resin that stoichiometrically drips is in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, and synthesis obtains being implemented as follows of aqueous epoxy curing agent step:
Under temperature of reaction is 50 ~ 70 DEG C of conditions, be stoichiometrically 2:1 ~ 3.6:1, drip liquid-state epoxy resin in the propylene glycol monomethyl ether solution removing the triethylene tetramine after residual triethylene tetramine and polyether glycol diglycidylether affixture through underpressure distillation, reaction 2 ~ 5h synthesis obtains aqueous epoxy curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510990616.2A CN105566638A (en) | 2015-12-25 | 2015-12-25 | Nonionic modified epoxy curing agent synthesis method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510990616.2A CN105566638A (en) | 2015-12-25 | 2015-12-25 | Nonionic modified epoxy curing agent synthesis method |
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| CN105566638A true CN105566638A (en) | 2016-05-11 |
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| CN201510990616.2A Pending CN105566638A (en) | 2015-12-25 | 2015-12-25 | Nonionic modified epoxy curing agent synthesis method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928433A (en) * | 2017-04-01 | 2017-07-07 | 深圳市深赛尔股份有限公司 | A kind of synthesis of large arch dam self-emulsifying type epoxy hardener and preparation method thereof |
| CN111621002A (en) * | 2020-06-15 | 2020-09-04 | 四川职业技术学院 | Non-ionic waterborne epoxy resin curing agent and preparation method thereof |
| CN115505101A (en) * | 2022-11-03 | 2022-12-23 | 广州境好新材料有限公司 | Water-based amine curing agent and preparation method thereof |
-
2015
- 2015-12-25 CN CN201510990616.2A patent/CN105566638A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928433A (en) * | 2017-04-01 | 2017-07-07 | 深圳市深赛尔股份有限公司 | A kind of synthesis of large arch dam self-emulsifying type epoxy hardener and preparation method thereof |
| CN111621002A (en) * | 2020-06-15 | 2020-09-04 | 四川职业技术学院 | Non-ionic waterborne epoxy resin curing agent and preparation method thereof |
| CN111621002B (en) * | 2020-06-15 | 2022-09-27 | 四川职业技术学院 | Non-ionic waterborne epoxy resin curing agent and preparation method thereof |
| CN115505101A (en) * | 2022-11-03 | 2022-12-23 | 广州境好新材料有限公司 | Water-based amine curing agent and preparation method thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160511 |
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| WD01 | Invention patent application deemed withdrawn after publication |