CN113502033A - Preparation method of graphene modified waterborne epoxy resin - Google Patents
Preparation method of graphene modified waterborne epoxy resin Download PDFInfo
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- CN113502033A CN113502033A CN202110810577.9A CN202110810577A CN113502033A CN 113502033 A CN113502033 A CN 113502033A CN 202110810577 A CN202110810577 A CN 202110810577A CN 113502033 A CN113502033 A CN 113502033A
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- epoxy resin
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- waterborne epoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
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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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
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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)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of epoxy resin preparation, and discloses a preparation method of graphene modified waterborne epoxy resin, which comprises the following steps: step 1, dissolving epoxy resin and fatty acid in a solvent, placing the solution in a reaction device, adding a catalyst, filling nitrogen, heating and stirring for reaction; step 2, adding a neutralizer into the reaction device, and heating for reaction; step 3, standing and layering, and removing unreacted fatty acid, the catalyst I and the solvent; step 4, adding a cross-linking agent and a catalyst II into a reaction device, and heating for reaction; step 5, placing the graphene oxide in deionized water, and stirring to obtain a graphene oxide solution; and 6, placing the graphene oxide solution into a reaction device, heating for reaction, placing and cooling. The preparation method of the graphene modified waterborne epoxy resin has the advantages of simple process route, no generation of any toxic gas, and good reaction performance of the epoxy resin after curing through graphene oxide.
Description
Technical Field
The invention relates to the technical field of epoxy resin preparation, in particular to a preparation method of graphene modified waterborne epoxy resin.
Background
Epoxy resin (EP) has excellent cohesiveness, good thermal property and mechanical property, and composite materials taking the epoxy resin as a matrix are widely applied to the fields of aerospace and the like, however, pure epoxy resin has large brittleness and cannot completely meet the requirements of high-performance materials on thermal property, electrical property and the like.
Graphene is a single-layer graphite sheet stripped from graphite, has a two-dimensional honeycomb knot, has excellent thermal conductivity, heat resistance and gas barrier effect, and the existing epoxy resin has poor thermal conductivity, temperature resistance and gas barrier property.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of graphene modified waterborne epoxy resin, which has the advantages of simple process route, no generation of any toxic gas, good reaction performance of the epoxy resin after curing and the like, and solves the problems in the background art mentioned above.
(II) technical scheme
In order to realize the purposes that the process route is simple, no toxic gas is generated, and the graphene oxide is introduced to ensure that the epoxy resin still has good reaction performance after being cured, the invention provides the following technical scheme: a preparation method of graphene modified waterborne epoxy resin comprises the following steps:
step 1, firstly, dissolving 40-50 parts of epoxy resin and 10-30 parts of fatty acid in 5-15 parts of solvent, placing the mixture in a reaction device, adding 0.1-1 part of first catalyst, filling nitrogen into the reaction device, heating to 20-80 ℃, and stirring for reacting for 6-24 hours;
step 2, adding 10-20 parts of neutralizing agent into the reaction device, heating to 10-70 ℃, and reacting for 1-8 hours;
step 3, removing unreacted fatty acid, the catalyst I and the solvent by standing and layering;
step 4, adding 0.1-10 parts of cross-linking agent and 0.1-1 part of catalyst II into a reaction device, heating to 100-170 ℃, and reacting for 9-36 hours;
step 5, placing 2-5 parts of graphene oxide in 5-10 parts of deionized water, stirring at the rotating speed of 4000-8000 r/min to obtain a graphene oxide solution, and removing undissolved graphene oxide in a filtering mode;
and 6, placing the graphene oxide solution obtained in the step 5 into a reaction device, heating to 50-100 ℃, reacting for 18-72 hours, and standing to cool to room temperature to obtain a target product.
Preferably, the waterborne epoxy resin comprises epoxy resin E-12, E-20, E-44, E-51, E-54 or a combination thereof.
Preferably, the fatty acid includes brassylic acid, and lauric acid.
Preferably, the solvent comprises butyl acetate, butyl acetate.
Preferably, the first catalyst comprises N, N-dipropyl-1-propylamine, N-dimethylaniline and tetraethylammonium hydroxide.
Preferably, the neutralizing agent comprises a saturated sodium bicarbonate solution, a saturated potassium carbonate solution and a saturated sodium carbonate solution.
Preferably, the crosslinking agent comprises TDI, HDI, IPDI or two or more components.
Preferably, the second catalyst comprises tetrahydrofuran, span 80 and DMF.
Compared with the epoxy resin, the modified epoxy resin has the advantages that a large amount of hydroxyl, carboxyl and ester groups are introduced, so that the hydrophilicity is enhanced; for the introduction of graphene, the graphene has good heat resistance and toughness, and the introduction of graphene molecules can toughen and resist heat of epoxy resin.
For 1000g of water, the dissolution molar quantity of the modified epoxy resin is increased by 30 percent compared with that of the original epoxy resin;
the glass transition temperature Tc of the modified epoxy resin is 10% higher than that of the original epoxy resin.
Compared with the prior art, the invention provides a preparation method of graphene modified waterborne epoxy resin, which has the following beneficial effects:
the preparation method of the graphene modified waterborne epoxy resin is simple in process route and free of any toxic gas, the epoxy resin still has good reaction performance after being cured through the graphene oxide, compared with the epoxy resin, the modified epoxy resin is enhanced in hydrophilicity by introducing a large number of hydroxyl groups, carboxyl groups and ester groups, the graphene has good heat resistance and toughness, and the epoxy resin is toughened and heat-resistant by introducing graphene molecules.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of graphene modified waterborne epoxy resin comprises the following steps:
step 1, firstly, dissolving 40-50 parts of epoxy resin and 10-30 parts of fatty acid in 5-15 parts of solvent, placing the mixture in a reaction device, adding 0.1-1 part of first catalyst, filling nitrogen into the reaction device, heating to 20-80 ℃, and stirring for reacting for 6-24 hours;
step 2, adding 10-20 parts of neutralizing agent into the reaction device, heating to 10-70 ℃, and reacting for 1-8 hours;
step 3, removing unreacted fatty acid, the catalyst I and the solvent by standing and layering;
step 4, adding 0.1-10 parts of cross-linking agent and 0.1-1 part of catalyst II into a reaction device, heating to 100-170 ℃, and reacting for 9-36 hours;
step 5, placing 2-5 parts of graphene oxide in 5-10 parts of deionized water, stirring at the rotating speed of 4000-8000 r/min to obtain a graphene oxide solution, and removing undissolved graphene oxide in a filtering mode;
and 6, placing the graphene oxide solution obtained in the step 5 into a reaction device, heating to 50-100 ℃, reacting for 18-72 hours, and standing to cool to room temperature to obtain a target product.
Further, the water-based epoxy resin comprises epoxy resin E-12, E-20, E-44, E-51, E-54 or a plurality of resins.
Further, the fatty acid includes brassylic acid, and lauric acid.
Further, the solvent includes butyl acetate, butyl acetate.
Further, the first catalyst comprises N, N-dipropyl-1-propylamine, N-dimethylaniline and tetraethylammonium hydroxide.
Further, the neutralizing agent includes a saturated sodium bicarbonate solution, a saturated potassium carbonate solution, and a saturated sodium carbonate solution.
Further, the cross-linking agent comprises TDI, HDI, IPDI or two or more components.
Further, the catalyst II comprises tetrahydrofuran, span 80 and DMF.
Experimental example 1
S1, firstly, 40 parts of epoxy resin E-44 and 25 parts of lauric acid are dissolved in 15 parts of butyl acetate and placed in a reaction device, 0.5 part of N, N-dimethylaniline is added, nitrogen is filled into the reaction device, the mixture is heated to 75 ℃, the mixture is continuously stirred, and the reaction lasts for 18 hours.
S2, adding 5 parts of saturated potassium carbonate solution into the reaction device, heating to 50 ℃, continuously stirring, and reacting for 6 hours.
And S3, standing and layering through a liquid separating funnel to remove unreacted lauric acid, N-dimethylaniline and butyl acetate.
S4, adding 2 parts of TDI and 0.5 part of DMF into the reaction device, heating to 160 ℃, and reacting for 24 hours.
S5, placing 2 parts of graphene oxide into 10 parts of deionized water, stirring at the rotating speed of 6000r/min to obtain a graphene oxide solution, and removing undissolved graphene oxide in a filtering mode.
And S6, placing the graphene oxide solution obtained in the S5 into a reaction device, and heating to 80 ℃ for reaction for 48 hours. And standing to reduce the temperature to room temperature to obtain the target product.
Example 2
S1, firstly, 50 parts of epoxy resin E-20 and 30 parts of brassylic acid are dissolved in 8 parts of butyl acetate and placed in a reaction device, 0.1 part of N, N-dipropyl-1-propylamine is added, nitrogen is filled into the reaction device, the mixture is heated to 60 ℃, and the mixture is continuously stirred and reacts for 22 hours.
S2, adding 10 parts of saturated sodium carbonate solution into the reaction device, heating to 65 ℃, reacting for 4 hours,
s3, and removing unreacted brassylic acid, N-dipropyl-1-propylamine and butyl acetate by standing and layering.
S4, 0.7 part of IPDI and 0.2 part of DMF are added into the reaction device, heated to 110 ℃ and reacted for 12 hours.
S5, placing 1 part of graphene oxide in 10 parts of deionized water, stirring at the rotating speed of 7000r/min to obtain a graphene oxide solution, and removing undissolved graphene oxide in a filtering manner.
And S6, placing the graphene oxide solution obtained in the S5 into a reaction device, heating to 60 ℃, reacting for 24 hours, and standing to cool to room temperature to obtain a target product.
Claims (8)
1. A preparation method of graphene modified waterborne epoxy resin is characterized by comprising the following steps:
step 1, firstly, dissolving 40-50 parts of epoxy resin and 10-30 parts of fatty acid in 5-15 parts of solvent, placing the mixture in a reaction device, adding 0.1-1 part of first catalyst, filling nitrogen into the reaction device, heating to 20-80 ℃, and stirring for reacting for 6-24 hours;
step 2, adding 10-20 parts of neutralizing agent into the reaction device, heating to 10-70 ℃, and reacting for 1-8 hours;
step 3, removing unreacted fatty acid, the catalyst I and the solvent by standing and layering;
step 4, adding 0.1-10 parts of cross-linking agent and 0.1-1 part of catalyst II into a reaction device, heating to 100-170 ℃, and reacting for 9-36 hours;
step 5, placing 2-5 parts of graphene oxide in 5-10 parts of deionized water, stirring at the rotating speed of 4000-8000 r/min to obtain a graphene oxide solution, and removing undissolved graphene oxide in a filtering mode;
and 6, placing the graphene oxide solution obtained in the step 5 into a reaction device, heating to 50-100 ℃, reacting for 18-72 hours, and standing to cool to room temperature to obtain a target product.
2. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the waterborne epoxy resin comprises epoxy resin E-12, E-20, E-44, E-51, E-54 or a plurality of resins.
3. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the fatty acid comprises brassylic acid and laurylic acid.
4. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the solvent comprises butyl acetate and butyl acetate.
5. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the first catalyst comprises N, N-dipropyl-1-propylamine, N-dimethylaniline and tetraethylammonium hydroxide.
6. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the neutralizer comprises a saturated sodium bicarbonate solution, a saturated potassium carbonate solution and a saturated sodium carbonate solution.
7. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the cross-linking agent comprises TDI, HDI, IPDI or two or more components.
8. The preparation method of the graphene-modified waterborne epoxy resin according to claim 1, wherein the preparation method comprises the following steps: the second catalyst comprises tetrahydrofuran, span 80 and DMF.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110810577.9A CN113502033A (en) | 2021-07-16 | 2021-07-16 | Preparation method of graphene modified waterborne epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110810577.9A CN113502033A (en) | 2021-07-16 | 2021-07-16 | Preparation method of graphene modified waterborne epoxy resin |
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| Publication Number | Publication Date |
|---|---|
| CN113502033A true CN113502033A (en) | 2021-10-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110810577.9A Withdrawn CN113502033A (en) | 2021-07-16 | 2021-07-16 | Preparation method of graphene modified waterborne epoxy resin |
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| CN (1) | CN113502033A (en) |
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2021
- 2021-07-16 CN CN202110810577.9A patent/CN113502033A/en not_active Withdrawn
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Application publication date: 20211015 |
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