CN108373533B - Preparation method of self-emulsifying water-based epoxy curing agent - Google Patents
Preparation method of self-emulsifying water-based epoxy curing agent Download PDFInfo
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- CN108373533B CN108373533B CN201810175669.2A CN201810175669A CN108373533B CN 108373533 B CN108373533 B CN 108373533B CN 201810175669 A CN201810175669 A CN 201810175669A CN 108373533 B CN108373533 B CN 108373533B
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims 7
- 238000004945 emulsification Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000012875 nonionic emulsifier Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
-
- 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
-
- 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 preparation method of a self-emulsifying water-based epoxy curing agent. The problems that the storage stability is poor, the performance of a paint film is influenced by adding acid and salifying and the like in the conventional preparation of the water-based epoxy curing agent are solved; the invention firstly prepares the macromolecular non-ionic emulsifier which can participate in system crosslinking, and the emulsifier is used for preparing the waterborne epoxy curing agent, and the curing agent has good storage stability, simple preparation method, wide applicable range and great industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical coatings, and particularly relates to a preparation method of a self-emulsifying water-based epoxy curing agent.
Background
The epoxy resin has the advantages of good adhesive force, low curing shrinkage, excellent mechanical property, chemical resistance, good corrosion resistance and the like, and has important application in the industrial coating, particularly in the field of corrosion resistance. However, in the preparation and construction processes, a large amount of thinner is needed for dilution, so that the defects of high VOC content, harm to the health of operators, serious environmental pollution and the like are caused. In recent years, with the demand for environmental protection, water-based epoxy resins have been gradually replaced with conventional solvent-based epoxy resins. The water-based epoxy resin takes water as a solvent, is safe and convenient to construct and meets the environmental protection requirement, so that the rapid development of water-based epoxy resin is the key point of the next research and development of the coating industry.
However, the existing preparation of waterborne epoxy curing agents has the disadvantages of instability, poor performance and the like, for example, patent CN1752163A discloses a preparation method of waterborne epoxy curing agents, and waterborne amine curing agents are finally prepared by salifying organic acids. CN1958639A is also prepared by a method of neutralizing with acid to form salt. However, a significant disadvantage of this method is that the addition of organic acids leads to unstable storage of the product and also easily causes rust on the treated metal surface, which leads to a reduction in the properties of the coating.
How to develop a new preparation method of the self-emulsifying water-based epoxy curing agent and prepare the self-emulsifying water-based epoxy curing agent with stability and better performance is the technical problem to be solved by the invention.
Disclosure of Invention
The invention provides a preparation method of self-emulsifying water-based epoxy curing agent aiming at the defects, which comprises the steps of firstly utilizing polyamine to react with methyl allyl alcohol polyoxyethylene ether with hydrophilic chain segments, then carrying out chain extension reaction with epoxy resin, and finally emulsifying to prepare the water-based epoxy curing agent. The problems that the storage stability is poor, the performance of a paint film is influenced by adding acid and salifying and the like in the conventional preparation of the water-based epoxy curing agent are solved; the invention firstly prepares a macromolecular non-ionic emulsifier which can participate in system crosslinking, and the emulsifier is used for preparing the waterborne epoxy curing agent, and the curing agent has good storage stability, simple preparation method, wide applicable range and great industrial application prospect.
The invention discloses a preparation method of a self-emulsifying water-based epoxy curing agent.
The method comprises the following steps:
(1) preparing a macromolecular emulsifier: firstly, polyamine reacts with methylallyl alcohol polyoxyethylene ether with large molecular weight to prepare a macromolecular reactive emulsifier with an amino group at the tail end; the reaction formula is as follows:
(2) then reacting the emulsifier prepared in the step (1) with a mixture of epoxy resin and monofunctional epoxy diluent;
(3) and (3) stirring the product obtained in the step (2), and dropwise adding deionized water to prepare the waterborne epoxy curing agent. In the step (1), the step (c),
the polyamine is ethylenediamine or polyether amine.
The molecular weight of the methallyl alcohol polyoxyethylene ether is 900-1300.
The addition amount of the polyamine and the methallyl alcohol polyoxyethylene ether is 5 to 15 percent by weight percentage. In the step (1), polyamine and high molecular weight methallyl alcohol polyoxyethylene ether are mixed and stirred uniformly, the temperature is increased to 80-90 ℃, catalyst triphenylphosphine is added dropwise, after the dropwise addition is finished, the temperature is increased to 100-120 ℃, the reaction is maintained for 2-4 h, and the reaction is stopped after the temperature is reduced.
The addition mass percentage of the triphenylphosphine in the mixture of the polyamine and the high molecular weight methallyl alcohol polyoxyethylene ether is 10-20%.
In the step (2), the addition amount of the diluent and the epoxy resin is 20-50% by mass.
In the step (2), epoxy resin and epoxy diluent are mixed, then the mixture is dripped into the product preheated to 40-50 ℃ in the step (1), stirring is carried out while dripping, the stirring speed is 500r/s-1000r/s, after dripping is finished, the temperature is raised to 70-80 ℃, heat preservation reaction is carried out for 2h-4h, and the temperature is reduced to 40-50 ℃ until all epoxy reactions are finished.
In the step (3), the addition amount of the deionized water in the product of the step (2) is 40-50%.
In the step (3), slowly dropwise adding deionized water into the product in the step (2), keeping high-speed stirring (the stirring speed is 1500r/s-2000r/s), and stirring for 40-60min to prepare the milky water-based epoxy curing agent.
The invention has the beneficial effects that: the invention provides a simple, easy-to-operate and wide-source method for preparing the VOC-free waterborne epoxy curing agent, and the product has good performance and great industrial application prospect due to simple production.
The waterborne epoxy curing agent prepared by the invention has good storage stability, can self-emulsify epoxy resin, is convenient to apply, has good compatibility with the epoxy resin, and has good performance hardness and chemical resistance of a prepared paint film.
Description of the drawings:
FIG. 1 shows a process flow diagram of the present invention.
The specific implementation mode is as follows:
for better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1:
the first step is as follows: putting 200g of methallyl alcohol polyoxyethylene ether (VPEG, molecular weight of 1000, industrial product, Qingdao Tianxin) and 12g of ethylenediamine (Dow, industrial product) into a reaction bottle, stirring and mixing uniformly, heating to 80 ℃, dropwise adding a catalyst triphenylphosphine, heating to 100 ℃ after dropwise adding, maintaining reaction for 2 hours, cooling to stop reaction, and preparing an emulsifier with an amino functional group at the tail end
The second step is that: mixing 12g E51 epoxy resin (Yueyangyanpetrochemical) and 6g butyl glycidyl ether (BGE, industrial product, Hexion), dropwise adding into the product obtained in the first step preheated to 40-50 ℃, stirring while dropwise adding, heating to 80 ℃ after dropwise adding, preserving heat, reacting for 2 hours, and cooling to 50 ℃ until all epoxy reactions are finished;
a third step; and slowly dripping 230g of deionized water into the curing agent, keeping high-speed stirring, and stirring for 40-60min to prepare the milky water-based epoxy curing agent.
The detection performance of the product prepared in this example is shown in table 1:
TABLE 1
Example 2:
the first step is as follows: 100g of methallyl alcohol polyoxyethylene ether (VPEG, molecular weight of 1000, industrial product, Qingdao Tianxin) and 23g of polyetheramine D230 (industrial product, Huntsman) are put into a reaction bottle, stirred and mixed uniformly, the temperature is increased to 80 ℃, catalyst triphenylphosphine is added dropwise, after the dropwise addition is finished, the temperature is increased to 100 ℃, reaction is maintained for 2 hours, the temperature is reduced, the reaction is stopped, and the emulsifier with the amino functional group at the tail end is prepared
The second step is that: mixing 6g E51 epoxy resin (Yueyangyanpetrochemical) and 3g phenyl glycidyl ether (692, industrial product, Hexion), dropwise adding into the product obtained in the first step preheated to 40-50 ℃, stirring while dropwise adding, heating to 80 ℃ after dropwise adding, preserving heat for reaction for 2 hours until all epoxy reaction is finished, and cooling to 50 ℃;
a third step; and (3) slowly dropwise adding 132g of deionized water into the curing agent, keeping high-speed stirring, and stirring for 40-60min to prepare the milky water-based epoxy curing agent.
The detection performance of the product prepared in this example is shown in table 2:
TABLE 2
Claims (8)
1. A preparation method of a self-emulsifying water-based epoxy curing agent is characterized in that polyamine is reacted with methyl allyl alcohol polyoxyethylene ether, then the reaction is carried out with chain extension reaction with epoxy resin, and finally emulsification is carried out to prepare the water-based epoxy curing agent;
the method comprises the following steps:
(1) preparing a macromolecular emulsifier: firstly, polyamine reacts with methyl allyl alcohol polyoxyethylene ether with large molecular weight, triphenylphosphine is taken as a catalyst, and a macromolecular emulsifier with an amino group at the tail end is prepared;
the molecular weight of the methallyl alcohol polyoxyethylene ether is 900-1300;
(2) then reacting the emulsifier prepared in the step (1) with a mixture of epoxy resin and monofunctional epoxy diluent;
(3) and (3) stirring the product obtained in the step (2), and dropwise adding deionized water to prepare the waterborne epoxy curing agent.
2. The method for preparing a self-emulsifying aqueous epoxy hardener as claimed in claim 1, wherein in the step (1), the polyamine is ethylenediamine or polyetheramine.
3. The method for preparing a self-emulsifying aqueous epoxy hardener as claimed in claim 1, wherein in step (1), the amount of polyamine and methallyl alcohol polyoxyethylene ether added is 5-15% by weight.
4. The preparation method of the self-emulsifying aqueous epoxy hardener as claimed in claim 1, wherein in step (1), the polyamine and the high molecular weight methallyl alcohol polyoxyethylene ether are mixed and stirred uniformly, the temperature is raised to 80 ℃ to 90 ℃, the catalyst triphenylphosphine is added dropwise, after the dropwise addition is finished, the temperature is raised to 100 ℃ to 120 ℃, the reaction is maintained for 2h to 4h, and the reaction is stopped after the temperature is lowered.
5. The method for preparing self-emulsifying waterborne epoxy hardener as claimed in claim 4, wherein the triphenylphosphine is added to the mixture of polyamine and high molecular weight methallyl alcohol polyoxyethylene ether in an amount of 10% -20% by weight.
6. The preparation method of the self-emulsifying water-based epoxy hardener as claimed in claim 1, wherein in the step (2), the addition amount of the diluent and the epoxy resin is 20-50% by mass.
7. The method for preparing a self-emulsifying aqueous epoxy hardener as claimed in claim 1, wherein in step (2), the epoxy resin and the epoxy diluent are mixed, and then added dropwise to the product of step (1) preheated to 40-50 ℃ with stirring, after the dropwise addition, the temperature is raised to 70-80 ℃ for reaction for 2-4 h, and then the temperature is reduced to 40-50 ℃ until all epoxy reaction is finished.
8. The method for preparing a self-emulsifying aqueous epoxy hardener as claimed in claim 1, wherein in step (3), the amount of deionized water added to the product of step (2) is 40% -50%.
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| CN112321803B (en) * | 2020-10-19 | 2022-11-04 | 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5032629A (en) * | 1989-03-13 | 1991-07-16 | Rutgerswerke Ag | Epoxy hardening agents |
| CN101007863A (en) * | 2007-01-12 | 2007-08-01 | 华南理工大学 | Preparation method of non-ionic room temperature-cured aqueous epoxy curing agent |
| CN101050300A (en) * | 2007-04-18 | 2007-10-10 | 广州秀珀化工有限公司 | Self-emulsifying type aqueous latex of epoxy hardener, and preparation method |
| 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 |
| CN106883379A (en) * | 2017-02-27 | 2017-06-23 | 江苏中路工程技术研究院有限公司 | A kind of aqueous epoxy resin curing agent, its preparation method and the water-base epoxy pitch containing the curing agent, its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE102005029143A1 (en) * | 2005-06-23 | 2006-12-28 | Cognis Ip Management Gmbh | Hardener for water-based epoxy resin, e.g. floor coating material, obtained by reacting epoxides and phenolic compounds together, reacting with polyamine and then with unsaturated carbonyl compound or nitrile |
-
2018
- 2018-03-02 CN CN201810175669.2A patent/CN108373533B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5032629A (en) * | 1989-03-13 | 1991-07-16 | Rutgerswerke Ag | Epoxy hardening agents |
| CN101007863A (en) * | 2007-01-12 | 2007-08-01 | 华南理工大学 | Preparation method of non-ionic room temperature-cured aqueous epoxy curing agent |
| CN101050300A (en) * | 2007-04-18 | 2007-10-10 | 广州秀珀化工有限公司 | Self-emulsifying type aqueous latex of epoxy hardener, and preparation method |
| 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 |
| CN106883379A (en) * | 2017-02-27 | 2017-06-23 | 江苏中路工程技术研究院有限公司 | A kind of aqueous epoxy resin curing agent, its preparation method and the water-base epoxy pitch containing the curing agent, its preparation method and application |
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