CN114957590B - Water-based isocyanate derivative cross-linking agent and preparation method thereof - Google Patents
Water-based isocyanate derivative cross-linking agent and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
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Abstract
The invention belongs to the field of cross-linking agents, and particularly relates to a water-based isocyanate derivative cross-linking agent, which has the following structure:
Description
Technical Field
The invention belongs to the field of cross-linking agents, and particularly relates to a water-based isocyanate derivative cross-linking agent and a preparation method thereof.
Background
The water-based epoxy resin maintains the excellent performance of the traditional epoxy resin, has a plurality of irreplaceable excellent performances, such as no toxicity and harm, does not pollute the environment, has high safety performance compared with the inflammable and explosive performance of an organic solvent, takes water as the solvent, has low cost and low environmental requirement, and can be constructed in a wet environment.
The isocyanate group has very high reactivity to the compound containing active hydrogen atoms, and the isocyanate is used as a cross-linking agent, so that the coating has the excellent characteristics of high cross-linking speed, high efficiency, capability of remarkably enhancing the water resistance, solvent resistance, mechanical property and the like of the coating. However, conventional polyisocyanates are oleophilic and hydrophobic, are difficult to mix homogeneously with aqueous systems, and are subject to phase separation in aqueous systems.
Disclosure of Invention
In order to solve the problems, the invention provides the aqueous isocyanate derivative cross-linking agent which has dissociable brominated polystyrene fragments, so that the cross-linking agent has good water solubility, and the defects of poor mechanical strength, water resistance, solvent resistance and the like caused by insufficient cross-linking of aqueous epoxy resin can be remarkably overcome.
The invention provides the following technical scheme:
an aqueous isocyanate derivative cross-linking agent characterized by having the following structure:
the range of n1, n2 and n3 is 2-10, R is isocyanate, and the isocyanate is diisocyanate or triisocyanate.
Preferably, the diisocyanate comprises toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
Preferably, the triisocyanate is triphenylmethane triisocyanate.
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving hydroxypropyl methacrylate in tetrahydrofuran, adding azo-diisoheptonitrile, heating to react under a nitrogen atmosphere, adding dimethylaminoethyl methacrylate, and continuing to react by heating to obtain a copolymer;
s2, dissolving brominated polystyrene in one part of tetrahydrofuran, dissolving a copolymer in the other part of tetrahydrofuran, and mixing and stirring the two to react to obtain a quaternized copolymer;
s3, mixing the quaternized copolymer, isocyanate, stannous octoate and tetrahydrofuran, and heating for reaction in a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
Preferably, in the S1, the molar ratio of hydroxypropyl methacrylate, dimethylaminoethyl methacrylate and azobisisoheptonitrile is (2-10): (2-10): 1.
preferably, in S2, the brominated polystyrene has a bromination degree of 60% to 70%.
Preferably, in S2, the polymerization degree of the brominated polystyrene is 2 to 10.
The beneficial effects of the invention are as follows:
1. the invention provides a water-based isocyanate derivative cross-linking agent, which has dissociable brominated polystyrene fragments, so that the cross-linking agent has good water solubility, and the defects of poor mechanical strength, water resistance, solvent resistance and the like caused by insufficient cross-linking of water-based epoxy resin can be remarkably overcome.
2. The cross-linking agent disclosed by the invention has excellent hydrophilicity, relatively high-NCO content, high cross-linking speed, no stickiness of a cross-linked waterborne epoxy coating and high cross-linking degree, and enhances the molecular acting force among epoxy resin molecular chains, so that the cross-linked epoxy resin has strong mechanical strength and good comprehensive properties of water resistance, solvent resistance, resistance and the like.
Detailed Description
The present invention will be specifically described with reference to the following examples.
Example 1
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving 0.1mol of hydroxypropyl methacrylate in 200ml of tetrahydrofuran, adding 0.01mol of azodiisoheptonitrile, heating at 60 ℃ for 24 hours under a nitrogen atmosphere, then adding 0.1mol of dimethylaminoethyl methacrylate, heating at 60 ℃ for 24 hours, performing rotary evaporation at 50 ℃ after the reaction is finished, purifying and precipitating by normal hexane, and vacuum drying at 60 ℃ for 24 hours to obtain a copolymer;
s2, 20g of brominated polystyrene (the bromination degree is 60 percent, the polymerization degree is 5) is dissolved in 100ml of one part of tetrahydrofuran, 30g of copolymer is dissolved in 100ml of the other part of tetrahydrofuran, the two parts of tetrahydrofuran are mixed and stirred for reaction for 24 hours, after the reaction is finished, the mixture is distilled at 50 ℃ in a rotary way, purified and precipitated by normal hexane, and vacuum-dried at 60 ℃ for 24 hours to obtain quaternized copolymer;
s3, mixing 45g of quaternized copolymer, 0.1mol of toluene diisocyanate, 0.005mol of stannous octoate and 200ml of tetrahydrofuran, and heating at 60 ℃ for 3 hours under a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
Example 2
This example is identical to example 1 except that "0.02 mol of azobisisoheptonitrile was added" is used.
Example 3
This example is identical to example 1 except that "0.05 mol of azobisisoheptonitrile was added" is used.
Example 4
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving 0.1mol of hydroxypropyl methacrylate in 200ml of tetrahydrofuran, adding 0.01mol of azodiisoheptonitrile, heating at 60 ℃ for 24 hours under a nitrogen atmosphere, then adding 0.1mol of dimethylaminoethyl methacrylate, heating at 60 ℃ for 24 hours, performing rotary evaporation at 50 ℃ after the reaction is finished, purifying and precipitating by normal hexane, and vacuum drying at 60 ℃ for 24 hours to obtain a copolymer;
s2, 20g of brominated polystyrene (the bromination degree is 60 percent, the polymerization degree is 5) is dissolved in 100ml of one part of tetrahydrofuran, 30g of copolymer is dissolved in 100ml of the other part of tetrahydrofuran, the two parts of tetrahydrofuran are mixed and stirred for reaction for 24 hours, after the reaction is finished, the mixture is distilled at 50 ℃ in a rotary way, purified and precipitated by normal hexane, and vacuum-dried at 60 ℃ for 24 hours to obtain quaternized copolymer;
s3, mixing 45g of quaternized copolymer, 0.1mol of isophorone diisocyanate, 0.005mol of stannous octoate and 200ml of tetrahydrofuran, and heating at 60 ℃ for 3 hours under a nitrogen atmosphere to obtain the aqueous isocyanate derivative cross-linking agent.
Example 5
This example is different from example 4 in that "0.02 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 4.
Example 6
This example is identical to example 4 except that "0.05 mol of azobisisoheptonitrile was added" is used.
Example 7
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving 0.1mol of hydroxypropyl methacrylate in 200ml of tetrahydrofuran, adding 0.01mol of azodiisoheptonitrile, heating at 60 ℃ for 24 hours under a nitrogen atmosphere, then adding 0.1mol of dimethylaminoethyl methacrylate, heating at 60 ℃ for 24 hours, performing rotary evaporation at 50 ℃ after the reaction is finished, purifying and precipitating by normal hexane, and vacuum drying at 60 ℃ for 24 hours to obtain a copolymer;
s2, 20g of brominated polystyrene (the bromination degree is 60 percent, the polymerization degree is 5) is dissolved in 100ml of one part of tetrahydrofuran, 30g of copolymer is dissolved in 100ml of the other part of tetrahydrofuran, the two parts of tetrahydrofuran are mixed and stirred for reaction for 24 hours, after the reaction is finished, the mixture is distilled at 50 ℃ in a rotary way, purified and precipitated by normal hexane, and vacuum-dried at 60 ℃ for 24 hours to obtain quaternized copolymer;
s3, mixing 45g of quaternized copolymer, 0.1mol of diphenylmethane diisocyanate, 0.005mol of stannous octoate and 200ml of tetrahydrofuran, and heating at 60 ℃ for 3 hours in a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
Example 8
This example is different from example 7 in that "0.2 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 7.
Example 9
This example is different from example 7 in that "0.05 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 7.
Example 10
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving 0.1mol of hydroxypropyl methacrylate in 200ml of tetrahydrofuran, adding 0.01mol of azodiisoheptonitrile, heating at 60 ℃ for 24 hours under a nitrogen atmosphere, then adding 0.1mol of dimethylaminoethyl methacrylate, heating at 60 ℃ for 24 hours, performing rotary evaporation at 50 ℃ after the reaction is finished, purifying and precipitating by normal hexane, and vacuum drying at 60 ℃ for 24 hours to obtain a copolymer;
s2, 20g of brominated polystyrene (the bromination degree is 60 percent, the polymerization degree is 5) is dissolved in 100ml of one part of tetrahydrofuran, 30g of copolymer is dissolved in 100ml of the other part of tetrahydrofuran, the two parts of tetrahydrofuran are mixed and stirred for reaction for 24 hours, after the reaction is finished, the mixture is distilled at 50 ℃ in a rotary way, purified and precipitated by normal hexane, and vacuum-dried at 60 ℃ for 24 hours to obtain quaternized copolymer;
s3, mixing 45g of quaternized copolymer, 0.1mol of dicyclohexylmethane diisocyanate, 0.005mol of stannous octoate and 200ml of tetrahydrofuran, and heating at 60 ℃ for 3 hours in a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
Example 11
This example is different from example 10 in that "0.02 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 10.
Example 12
This example is different from example 10 in that "0.05 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 10.
Example 13
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving 0.1mol of hydroxypropyl methacrylate in 200ml of tetrahydrofuran, adding 0.01mol of azodiisoheptonitrile, heating at 60 ℃ for 24 hours under a nitrogen atmosphere, then adding 0.1mol of dimethylaminoethyl methacrylate, heating at 60 ℃ for 24 hours, performing rotary evaporation at 50 ℃ after the reaction is finished, purifying and precipitating by normal hexane, and vacuum drying at 60 ℃ for 24 hours to obtain a copolymer;
s2, 20g of brominated polystyrene (the bromination degree is 60 percent, the polymerization degree is 5) is dissolved in 100ml of one part of tetrahydrofuran, 30g of copolymer is dissolved in 100ml of the other part of tetrahydrofuran, the two parts of tetrahydrofuran are mixed and stirred for reaction for 24 hours, after the reaction is finished, the mixture is distilled at 50 ℃ in a rotary way, purified and precipitated by normal hexane, and vacuum-dried at 60 ℃ for 24 hours to obtain quaternized copolymer;
s3, mixing 45g of quaternized copolymer, 0.1mol of hexamethylene diisocyanate, 0.005mol of stannous octoate and 200ml of tetrahydrofuran, and heating at 60 ℃ for 3 hours under a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
Example 14
This example is different from example 13 in that "0.02 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 13.
Example 15
This example is different from example 13 in that "0.05 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 13.
Example 16
A preparation method of an aqueous isocyanate derivative cross-linking agent comprises the following steps:
s1, dissolving 0.1mol of hydroxypropyl methacrylate in 200ml of tetrahydrofuran, adding 0.01mol of azodiisoheptonitrile, heating at 60 ℃ for 24 hours under a nitrogen atmosphere, then adding 0.1mol of dimethylaminoethyl methacrylate, heating at 60 ℃ for 24 hours, performing rotary evaporation at 50 ℃ after the reaction is finished, purifying and precipitating by normal hexane, and vacuum drying at 60 ℃ for 24 hours to obtain a copolymer;
s2, 20g of brominated polystyrene (the bromination degree is 60 percent, the polymerization degree is 5) is dissolved in 100ml of one part of tetrahydrofuran, 30g of copolymer is dissolved in 100ml of the other part of tetrahydrofuran, the two parts of tetrahydrofuran are mixed and stirred for reaction for 24 hours, after the reaction is finished, the mixture is distilled at 50 ℃ in a rotary way, purified and precipitated by normal hexane, and vacuum-dried at 60 ℃ for 24 hours to obtain quaternized copolymer;
s3, mixing 45g of quaternized copolymer, 0.1mol of triphenylmethane triisocyanate, 0.005mol of stannous octoate and 200ml of tetrahydrofuran, and heating at 60 ℃ for 3 hours in a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
Example 17
This example is different from example 15 in that "0.02 mol of azobisisoheptonitrile was added", and the other is exactly the same as example 15.
Example 18
This example is identical to example 15 except that "0.05 mol of azobisisoheptonitrile was added" is used.
Results and detection
And (3) adding a crosslinking agent accounting for 1%, 3% and 5% of the mass of the water-based epoxy resin into the water-based epoxy resin sold in the market, uniformly stirring, curing for 48 hours, and then starting the test.
1. Tensile strength test: the CTM6005 microcomputer controlled electronic tension tester manufactured by a cooperative strength instrument is used for detecting the mechanical properties of the crosslinked waterborne epoxy resin;
2. and (3) water resistance test: square samples with the side length of 2cm are taken and placed in a vacuum drying oven to be dried to constant weight, and are weighed to obtain m 1 Placing the dried sample into distilled water to absorb water for 24 hours, wiping off water stains on the surface, and weighing to obtain m 2 ，
Water absorption= (m) 2 -m 1 )/m 1 *100％
3. Toluene resistance test: square samples with the side length of 2cm are taken and placed in a vacuum drying oven to be dried to constant weight, and are weighed to obtain m 1 Placing the dried sample into distilled water to absorb water for 24 hours, wiping off water stains on the surface, and weighing to obtain m 2 ，
Toluene absorption= (m 2 -m 1 )/m 1 *100％
TABLE 1 Property of waterborne epoxy after curing
As is clear from Table 1, the tensile strength of each sample was more than 7.5MPa, the tensile strength was the maximum for the sample having an addition of 5% corresponding to example 9, the tensile strength was 9.5MPa, the water absorption of each sample was 15.3% or less, the water absorption was the minimum for the sample having an addition of 5% corresponding to example 1, the water absorption was only 2.7%, and the toluene absorption difference was not large for each sample and was 100% or more.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An aqueous isocyanate derivative cross-linking agent characterized by having the following structure:
the range of n1, n2 and n3 is 2-10, R is isocyanate, and the isocyanate is diisocyanate or triisocyanate.
2. An aqueous isocyanate-derived crosslinker according to claim 1, wherein the diisocyanate comprises toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
3. An aqueous isocyanate-derived crosslinker according to claim 1, wherein the triisocyanate is triphenylmethane triisocyanate.
4. The preparation method of the aqueous isocyanate derivative cross-linking agent is characterized by comprising the following steps:
s1, dissolving hydroxypropyl methacrylate in tetrahydrofuran, adding azo-diisoheptonitrile, heating to react under a nitrogen atmosphere, adding dimethylaminoethyl methacrylate, and continuing to react by heating to obtain a copolymer;
s2, dissolving brominated polystyrene in one part of tetrahydrofuran, dissolving a copolymer in the other part of tetrahydrofuran, and mixing and stirring the two to react to obtain a quaternized copolymer;
s3, mixing the quaternized copolymer, isocyanate, stannous octoate and tetrahydrofuran, and heating for reaction in a nitrogen atmosphere to obtain the water-based isocyanate derivative cross-linking agent.
5. The method for producing an aqueous isocyanate derivative cross-linking agent according to claim 4, wherein in S1, the molar ratio of hydroxypropyl methacrylate, dimethylaminoethyl methacrylate and azobisisoheptonitrile is (2-10): (2-10): 1.
6. the method for preparing an aqueous isocyanate derivative cross-linking agent according to claim 4, wherein in S2, the brominated polystyrene has a bromination degree of 60% to 70%.
7. The method for producing an aqueous isocyanate derivative cross-linking agent according to claim 4, wherein in S2, the polymerization degree of the brominated polystyrene is 2 to 10.
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| CN110551134A (en) * | 2019-08-29 | 2019-12-10 | 武汉纺织大学 | Preparation method of cross-linking agent, multiple-stimulus-response color-changing self-repairing coating and preparation method thereof |
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| CN105849131B (en) * | 2013-12-29 | 2018-11-09 | 陶氏环球技术有限责任公司 | The method for recycling brominated styrene-butadiene copolymer from organic solvent |
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| GB1001458A (en) * | 1962-12-03 | 1965-08-18 | Ici Ltd | Catalysts for isocyanate reactions |
| JPH02304056A (en) * | 1989-05-18 | 1990-12-17 | Asahi Chem Ind Co Ltd | Aqueous blocked polyisocyanate compound |
| CN102633990A (en) * | 2012-04-05 | 2012-08-15 | 广东生益科技股份有限公司 | Epoxy resin composition, prepreg made of epoxy resin composition and copper-coated laminate made of epoxy resin composition |
| CN107207631A (en) * | 2015-01-30 | 2017-09-26 | 陶氏环球技术有限责任公司 | Generate bromination and the method for halogenation hydrated polymer |
| CN110551134A (en) * | 2019-08-29 | 2019-12-10 | 武汉纺织大学 | Preparation method of cross-linking agent, multiple-stimulus-response color-changing self-repairing coating and preparation method thereof |
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