CN108373533A - A kind of preparation method of self-emulsifying aqueous epoxy hardener - Google Patents
A kind of preparation method of self-emulsifying aqueous epoxy hardener Download PDFInfo
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- CN108373533A CN108373533A CN201810175669.2A CN201810175669A CN108373533A CN 108373533 A CN108373533 A CN 108373533A CN 201810175669 A CN201810175669 A CN 201810175669A CN 108373533 A CN108373533 A CN 108373533A
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- aqueous epoxy
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- self
- epoxy hardener
- curing agent
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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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of preparation methods of self-emulsifying aqueous epoxy hardener, are reacted with the methyl allyl alcohol polyoxyethylene ether with hydrophilic segment first with polyamine, then carry out chain extending reaction with epoxy resin, aqueous epoxy curing agent is made in final emulsion.It solves current aqueous epoxy curing agent and prepares the problems such as existing storage stability is bad, and acid adding influences paint film property at salt；The method comprises the steps of firstly, preparing the crosslinked macromolecular nonionic emulsifier of the system that may participate in, and aqueous epoxy curing agent is prepared with this emulsifier, this curing agent storage stability is good, and preparation method is simple, can have a wide range of application, and have great prospects for commercial application.
Description
Technical field
The invention belongs to chemistry painting industry fields, and in particular to a kind of preparation method of self-emulsifying aqueous epoxy hardener.
Background technology
Epoxy resin is with adhesive force is good, cure shrinkage is low, good mechanical performance, chemical-resistance, corrosion resistance
The advantages that good, has important application in industrial coating especially corrosion-resistant field.But because in its preparation and work progress, needing
A large amount of solvent or diluent dilutes, and causes VOC content big, the shortcomings of endangering operator's health, cause environmental pollution serious.In recent years
Come, with the requirement of environmental protection, aqueous epoxy resins are increasingly becoming the trend instead of traditional solvent epoxy varnish.Water-base epoxy
Resin is using water as solvent, and construction safety is convenient, while meeting environmental requirement, and therefore, it is coating industry to greatly develop water-base epoxy
Next step research and development emphasis.
However, preparing aqueous epoxy curing agent at present, there are the shortcomings of unstable, performance is bad, such as patent
A kind of preparation method of aqueous epoxy curing agent is disclosed in CN1752163A, aqueous amine curing agent is finally by organic acid at salt
It is made.CN1958639A is also prepared using the method that acid is neutralized into salt.But this one apparent disadvantage of method is exactly organic
The addition of acid causes product storage unstable, and is easy to cause rusty stain in processed metal surface, causes coating property
Decline.
A kind of preparation method of new self-emulsifying aqueous epoxy hardener how is researched and developed, is prepared stable and better performances
Self-emulsifying aqueous epoxy hardener is the technical problem to be solved in the invention.
Invention content
The present invention provides a kind of preparation method of self-emulsifying aqueous epoxy hardener aiming at above-mentioned defect,
It reacts with the methyl allyl alcohol polyoxyethylene ether with hydrophilic segment first with polyamine, is then expanded with epoxy resin
Aqueous epoxy curing agent is made in chain reaction, final emulsion.It solves current aqueous epoxy curing agent and prepares existing storage stability
It is bad, acid adding at salt influence paint film property the problems such as；The present invention first prepares one kind and may participate in the crosslinked macromolecular nonionic of system
Type emulsifier prepares aqueous epoxy curing agent with this emulsifier, this curing agent storage stability is good, and preparation method is simple, can answer
It is wide with range, there is great prospects for commercial application.
A kind of preparation method technical solution of self-emulsifying aqueous epoxy hardener of the present invention is, with polyamine and methyl alkene
Propyl alcohol polyoxyethylene ether is reacted, and then carries out chain extending reaction with epoxy resin, and aqueous epoxy curing agent is made in final emulsion.
Step includes：
(1) preparation of macromole emulsifying agent：It is first that the methyl allyl alcohol polyoxyethylene ether of polyamine and macromolecule is anti-
It answers, preparing macromolecular of the end with amino group can reactive emulsifier；Reaction equation is as follows：
(2) and then by the emulsifier prepared in step (1) and epoxy resin and single functionality epoxide diluent mixture
Reaction；
(3) product of step (2) is stirred, deionized water is added dropwise, prepares aqueous epoxy curing agent.In step (1),
Polyamine is ethylenediamine or polyetheramine.
Methyl allyl alcohol polyoxyethylene ether molecular weight is 900-1300.
The additive amount of polyamine and methyl allyl alcohol polyoxyethylene ether is 5%-15% by weight percentage.In step (1),
The methyl allyl alcohol polyoxyethylene ether of polyamine and macromolecule is mixed evenly, 80 DEG C -90 DEG C is warming up to and catalysis is added dropwise
Agent triphenylphosphine after being added dropwise, is warming up to 100 DEG C -120 DEG C, and reaction 2h-4h, cooling is maintained to stop reaction.
Addition quality hundred of the triphenylphosphine in the methyl allyl alcohol polyoxyethylene ether mixture of polyamine and macromolecule
Divide than being 10%-20%.
In step (2), diluent is 20%-50% with epoxy resin additive amount mass percent.
In step (2), epoxy resin and epoxide diluent are mixed, the step of being preheating to 40-50 DEG C is then added drop-wise to
(1) it in product, is stirred when being added dropwise, stir speed (S.S.) 500r/s-1000r/s after being added dropwise, is warming up to 70-80 DEG C of guarantor
After temperature reaction 2h-4h, until all epoxy reactions finish, 40-50 DEG C is cooled to.
In step (3), additive amount 40%-50% of the deionized water in step (2) product.
In step (3), deionized water is slowly dropped in step (2) product, and keep high-speed stirred (stir speed (S.S.)
1500r/s-2000r/s), after stirring 40-60min, milky aqueous epoxy curing agent is prepared.
Beneficial effects of the present invention are：The present invention provides a kind of simple, easily operated, raw material sources widely to prepare not
The method of aqueous epoxy curing agent containing VOC, since its production is simple, properties of product are preferable, have great commercial Application
Foreground.
Aqueous epoxy curing agent storage stability prepared by the present invention is good, can self-emulsifying epoxy resin, convenient for application, and
And it is good with epoxy resin compatibility, the paint film property hardness and chemical-resistance of preparation are preferable.
Description of the drawings:
Fig. 1 show the process flow chart of the present invention.
Specific implementation mode：
For a better understanding of the present invention, below with specific example come the technical solution that the present invention will be described in detail, but this
Invention is not limited thereto.
Embodiment 1：
The first step：By 200g methyl allyl alcohol polyoxyethylene ethers (VPEG, molecular weight 1000, industrial goods, Qingdao day are prosperous)
It puts into reaction bulb, is uniformly mixed with the ethylenediamine (Dow, industrial goods) of 12g, be warming up to 80 DEG C of dropwise addition catalyst triphens
Base phosphine after being added dropwise, is warming up to 100 DEG C, and reaction 2h, cooling is maintained to stop reaction, prepares end and contains amidine functional group
Emulsifier
Second step：By 12g E51 epoxy resin (Yueyang petrochemical industry) and 6g butyl glycidyl ethers (BGE, industrial goods,
Hexion it) mixes, is then added drop-wise in the product in the above-mentioned first step for being preheating to 40-50 DEG C, stir, drip when being added dropwise
Bi Hou after being warming up to 80 DEG C of insulation reaction 2h, until all epoxy reactions finish, cools to 50 DEG C；
Third walks；230g deionized waters are slowly dropped in curing agent, and keep high-speed stirred, stir 40-60min
Afterwards, milky aqueous epoxy curing agent is prepared.
Product testing performance manufactured in the present embodiment is as shown in table 1：
Table 1
Embodiment 2：
The first step：By 100g methyl allyl alcohol polyoxyethylene ethers (VPEG, molecular weight 1000, industrial goods, Qingdao day are prosperous)
It puts into reaction bulb, is uniformly mixed with the polyetheramine D230 (industrial goods, Huntsman) of 23g, be warming up to 80 DEG C of dropwise additions
Catalyst triphenylphosphine after being added dropwise, is warming up to 100 DEG C, and reaction 2h, cooling is maintained to stop reaction, prepares end and contains amine
The emulsifier of base functional group
Second step：By 6g E51 epoxy resin (Yueyang petrochemical industry) and 3g phenyl glycidyl ethers (692, industrial goods,
Hexion it) mixes, is then added drop-wise in the product in the above-mentioned first step for being preheating to 40-50 DEG C, stir, drip when being added dropwise
Bi Hou after being warming up to 80 DEG C of insulation reaction 2h, until all epoxy reactions finish, cools to 50 DEG C；
Third walks；132g deionized waters are slowly dropped in curing agent, and keep high-speed stirred, stir 40-60min
Afterwards, milky aqueous epoxy curing agent is prepared.
Product testing performance manufactured in the present embodiment is as shown in table 2：
Table 2
Claims (11)
1. a kind of preparation method of self-emulsifying aqueous epoxy hardener, which is characterized in that with polyamine and methallyl alcohol polyoxy
Vinethene reacts, and then carries out chain extending reaction with epoxy resin, and aqueous epoxy curing agent is made in final emulsion.
2. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step packet
It includes：
(1) preparation of macromole emulsifying agent：Polyamine is reacted with the methyl allyl alcohol polyoxyethylene ether of macromolecule first, is made
Standby macromolecular of the end with amino group can reactive emulsifier；
(2) and then it is the emulsifier prepared in step (1) and epoxy resin and single functionality epoxide diluent mixture is anti-
It answers；
(3) product of step (2) is stirred, deionized water is added dropwise, prepares aqueous epoxy curing agent.
3. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step
（1）In, polyamine is ethylenediamine or polyetheramine；Methyl allyl alcohol polyoxyethylene ether molecular weight is 900-1300.
4. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 2, which is characterized in that step
（1）In, the additive amount of polyamine and methyl allyl alcohol polyoxyethylene ether is 5 %-15% by weight percentage.
5. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step
（1）In, the methyl allyl alcohol polyoxyethylene ether of polyamine and macromolecule is mixed evenly, 80 DEG C of -90 DEG C of drops are warming up to
Add catalyst triphenylphosphine, after being added dropwise, be warming up to 100 DEG C -120 DEG C, reaction 2h-4h, cooling is maintained to stop reaction.
6. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 4, which is characterized in that triphenyl
Addition mass percent of the phosphine in the methyl allyl alcohol polyoxyethylene ether mixture of polyamine and macromolecule is 10%-20%.
7. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step
（2）In, diluent is 20%-50% with epoxy resin additive amount mass percent.
8. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step
（2）In, epoxy resin and epoxide diluent are mixed, the step of being preheating to 40-50 DEG C is then added drop-wise to（1）Product in,
Stir when being added dropwise, after being added dropwise, after being warming up to 70-80 DEG C of insulation reaction 2h-4h, until all epoxy reactions finish, drops
Temperature arrives 40-50 DEG C.
9. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 7, which is characterized in that stirring speed
Rate is 500r/s-1000r/s.
10. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step
（3）In, deionized water is in step（2）Additive amount 40%-50% in product.
11. a kind of preparation method of self-emulsifying aqueous epoxy hardener according to claim 1, which is characterized in that step
（3）In, deionized water is slowly dropped to step（2）In product, and high-speed stirred is kept, stir speed (S.S.) 1500r/s-
2000r/s prepares milky aqueous epoxy curing agent after stirring 40-60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810175669.2A CN108373533B (en) | 2018-03-02 | 2018-03-02 | Preparation method of self-emulsifying water-based epoxy curing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810175669.2A CN108373533B (en) | 2018-03-02 | 2018-03-02 | Preparation method of self-emulsifying water-based epoxy curing agent |
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| CN108373533B CN108373533B (en) | 2021-04-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321803A (en) * | 2020-10-19 | 2021-02-05 | 惠州市惠阳区嘉泰涂料有限公司 | Low-foam-stability water-based epoxy 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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|---|---|---|---|---|
| US5032629A (en) * | 1989-03-13 | 1991-07-16 | Rutgerswerke Ag | Epoxy hardening agents |
| JPH05339189A (en) * | 1992-06-05 | 1993-12-21 | Seiko Epson Corp | Tolan derivative and liquid crystal composition containing the same and liquid crystal display device using the composition |
| US20070066789A1 (en) * | 2005-06-23 | 2007-03-22 | Giorgio Sabbadini | Hardeners for coating compositions (I) |
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| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
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2018
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|---|---|---|---|---|
| US5032629A (en) * | 1989-03-13 | 1991-07-16 | Rutgerswerke Ag | Epoxy hardening agents |
| JPH05339189A (en) * | 1992-06-05 | 1993-12-21 | Seiko Epson Corp | Tolan derivative and liquid crystal composition containing the same and liquid crystal display device using the composition |
| US20070066789A1 (en) * | 2005-06-23 | 2007-03-22 | Giorgio Sabbadini | Hardeners for coating compositions (I) |
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Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321803A (en) * | 2020-10-19 | 2021-02-05 | 惠州市惠阳区嘉泰涂料有限公司 | Low-foam-stability water-based epoxy 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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| CN108373533B (en) | 2021-04-27 |
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Denomination of invention: Preparation method of a self-emulsifying water-based epoxy curing agent Effective date of registration: 20230627 Granted publication date: 20210427 Pledgee: Anqiu Qingyunshan road sub branch of Weifang Bank Co.,Ltd. Pledgor: SHANDONG QIWEI NEW MATERIALS Co.,Ltd. Registration number: Y2023980045681 |
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