CN106943969A - A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate - Google Patents
A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate Download PDFInfo
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- CN106943969A CN106943969A CN201710222692.8A CN201710222692A CN106943969A CN 106943969 A CN106943969 A CN 106943969A CN 201710222692 A CN201710222692 A CN 201710222692A CN 106943969 A CN106943969 A CN 106943969A
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- polyvinyl alcohol
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- microcapsules
- liquid isocyanate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
Abstract
A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate is will to add to be constituted core shell material mixing oil phase by polyisocyanates shell material and low activity liquid isocyanate core and emulsified in polyvinyl alcohol water solution, form stabilized oil-in-water emulsion, amine cross-linking agent is divided into 6 parts to be added separately in deionized water, the 6 equal portions amine aqueous solutions for preparing it, and from low concentration to high concentration successively dropwise in emulsion, heating response, emulsion is cooled to after room temperature and washed, microcapsules are obtained by decantation, finally the microcapsules after separation are dried at room temperature for, obtain self-repairing microcapsule.The present invention has the advantages that synthesis step simplicity, low cost, clad ratio are high, capsule size is controllable, composite shell intensity is high.
Description
Art
The invention belongs to a kind of preparation field of self-repairing microcapsule, a kind of composite shell cladding liquid isocyanide is related in particular to
The preparation method of the self-repairing microcapsule of acid esters.
Background technology
Self-repairing microcapsule technology be it is a kind of by selfreparing reagent be coated on it is small and seal capsule in method.Review one's lessons by oneself
Multiple microcapsules are widely used in the reparation of the micro-crack defect of coating and structural polymer.In all self-repairing microcapsules
In, because isocyanates easily can react with the moisture in surrounding environment, thus it is coated with the microcapsules of liquid isocyanate
As a kind of self-healing system that is quick, effective, just can triggering selfreparing reaction without catalyst.
Prior art CN201210218226.X is a large amount of to use capsule-core diluent and cosolvent etc. when coating isocyanates
Toxic solvent.This will cause that active ingredient isocyanates clad ratio is substantially reduced in microcapsules core liquid and the feature of environmental protection is poor.It is existing
Technology CN201410101557.4, CN201410004130.2, CN201210215007.6, CN201410427058.4 etc. on
The preparation of self-repairing microcapsule is all cumbersome as shell, the synthesis step complexity of this microcapsules using Lauxite.Prez
Professor and related researcher（L.-T.T. Nguyen, X.K.D. Hillewaere, R.F.A. Teixeira, O. van
Den Berg, F.E. Du Prez, Polym. Chem., 2015,6 (7), 1159-1170）Using low viscosity isocyanates
As shell material and core, in room temperature and capsule-core diluent and cosolvent can not be needed, shell material and core just can form stable equal
One oil phase, but to be due to that oil phase viscosity is low result in the need for substantial amounts of gum arabic and carry out stabilized oil-in-water emulsion as emulsifying agent.
This raising for not only resulting in production cost also causes difficulty to the separating, washing of follow-up microcapsules.In addition, micro- glue of single layer enclosure
Capsule intensity is poor, and outflow, the inactivation of high activity core liquid are being caused with being easily broken in resin base material mixed process.
The content of the invention
The technical problems to be solved by the invention are to overcome existing technological deficiency, and its goal of the invention is to provide a kind of synthesis
The composite shell cladding liquid isocyanide that step simplicity, low cost, clad ratio are high, capsule size is controllable, composite shell intensity is high
The preparation method of the self-repairing microcapsule of acid esters.
The microcapsules of liquid isocyanate are coated in building-up process, the dissolving each other of shell material and core need to use solvent or
Heating could form uniform oil phase, and building-up process rate-determining steps are cumbersome.These problems limit the extensive of microcapsules
Safety in production.For these problems our preferred low values, low viscosity polyisocyanates as shell material, polyamines is used as crosslinking
Agent.The polyisocyanates shell material of low viscosity and small molecule monomer isocyanates core are in room temperature and need not be under conditions of auxiliary agent just
The oil phase of stable homogeneous can be mixed to form.But this, which generally requires higher rotation speed and the emulsifying agent of higher concentration, effectively to control
The stability of size of the oil droplet in aqueous phase and maintenance oil droplet in aqueous phase.Therefore, we are using higher alcoholysis degree, higher molecular
The polyvinyl alcohol of amount is used as emulsifying agent.The composite shell of the microcapsules formed is polyvinyl alcohol by being crosslinked and by polyisocyanic acid
Ester is constituted with the polyureas of amine cross-linking agent formation, and it has more preferable pliability and hardness, solves current selfreparing micro-
Capsule is embedded into the problem of breakage rate during matrix material is high.And the Microcapsules Size obtained is controllable, surface topography is more
It is smooth and core liquid clad ratio is higher.
The preparation method of the present invention, comprises the following steps：
（1）Polyvinyl alcohol is added in deionized water and stirs 10-30min, 70-90 DEG C of stirring 1.5-5h is then warming up to, most
The polyvinyl alcohol water solution cooling that concentration is 2-12wt% will be obtained afterwards standby；
（2）Utilize step（1）The polyvinyl alcohol water solution of gained is simultaneously stirred in 400-1600rpm, is 1 by mass ratio：2-4's is more
Isocyanates shell material and low activity liquid isocyanate core are well mixed, obtain core shell material mixing oil phase, then will mixing
Oil phase is poured slowly into polyvinyl alcohol water solution and emulsifies 3-5 min formation stabilized oil-in-water emulsions, and wherein core shell material is mixed
Oil phase is 1 with polyvinyl alcohol water solution mass ratio：3-5；
（3）Amine cross-linking agent is divided into 6 parts to be added separately in deionized water, makes the concentration point of its 6 equal portions amine aqueous solution prepared
Not Wei 0.0015-0.0030 g/ml, 0.003-0.006 g/ml, 0.006-0.012 g/ml, 0.012-0.024 g/ml,
0.024-0.048 g/ml, 0.048-0.096 g/ml, and 6 parts of amine aqueous solution concentration are different, and from low concentration to high concentration
Step is added dropwise successively（2）In emulsion in, every part of amine aqueous solution is added at intervals of 5-15 min, after completion of dropping, in 5-15
Emulsion is heated to 45-75 DEG C by oil bath in min, reaction 1-7h terminates, wherein, the mass ratio of shell material and amine cross-linking agent is
1：0.15-0.56, amine aqueous solution is 0.5-1.5 with polyvinyl alcohol water solution volume ratio：1；
（5）Emulsion is cooled to after room temperature and is washed with deionized 5-7 times, microcapsules are obtained by decantation, after finally separating
Microcapsules be dried at room temperature for 20-48 h, that is, obtain self-repairing microcapsule, wherein, the deionized water and quilt of each washing
The female slurry volume ratio of washing is 1-4：1.
The relatively low polyphenyl polymethylene polyisocyanates of shell material preferred viscosities as described above, toluene di-isocyanate(TDI) three
One or more in aggressiveness, '-diphenylmethane diisocyanate tripolymer, hexamethylene diisocyanate trimer.
One in the preferred ethylenediamine of amine cross-linking agent as described above, diethylenetriamine, triethylene tetramine, TEPA
Plant or a variety of.
The preferred IPDI of low activity liquid isocyanate as described above, hexamethylene diisocyanate,
One or more in dicyclohexyl methyl hydride diisocyanate.
The preferred 85-98% alcoholysis degrees of polyvinyl alcohol as described above, molecular weight 20000-180000g/mol polyvinyl alcohol.
In step (2) due to the easy poly- second for occurring self-polymeric reaction at oil-water interfaces and foring microcapsules of polyvinyl alcohol
Enol outer shell.
Shell material reacts and formd the polyureas hypostracum of microcapsules in step (3) is due to amine aqueous solution and oil phase.
It is of the invention compared with existing technology of preparing, with advantages below：
（1）The preparation method of the present invention is simple to operate, with low cost.Prepared microcapsules smooth in appearance, size tunable is good,
During by controlling emulsifying rate from 400 rpm to 1600rpm or emulsifying agent PVA concentration from 2wt% to 12wt%, microcapsules are averaged
Particle size is also down to 9.7 μm by 160 μm.
（2）Microcapsules core liquid clad ratio is in 78-85wt%.
（3）Microcapsules have the composite shell of high intensity, can be with being answered in resin-based materials mixed process by the external world
Power remains to keep microcapsules complete.
（4）This preparation method is applied to the shell material liquid and core liquid of low viscosity, solves low viscosity in the prior art
The problem of shell material and core can not form stable oil phase drop under low-concentration emulsifier, the slow-speed of revolution in aqueous phase.
Brief description of the drawings
Fig. 1 is the microscopic appearance figure of isocyanates microcapsules prepared by embodiment 1.Wherein b figures be a figure amplification one it is micro-
Capsule figure.
Fig. 2 is isocyanates microcapsules and the mixed section microscopic appearance figure of resin base material prepared by embodiment 1.Wherein
A2 figures are A1 figure enlarged drawings.
Fig. 3 is the qualitative of isocyanates microcapsules core liquid prepared by embodiment 1 and quantitative nuclear magnetic spectrogram.
Embodiment
Technical scheme and effect are described in detail with reference to specific embodiment and accompanying drawing, but the present invention
Protection domain should not be limited to following embodiments.
Embodiment 1:
At room temperature, 95% alcoholysis degree, molecular weight are added in deionized water for 70000-80000g/mol polyvinyl alcohol and stirred
30min, is subsequently heated to 80 DEG C of stirring 3h.Finally cooling obtains 5wt% polyvinyl alcohol water solution.The poly- second for taking 60ml to prepare
The enol aqueous solution is stirred at 1600 rpm, then by 12g IPDIs and 4 g polyphenyl polymethylene polyisocyanates
Cyanate, which is mixed into homogeneous oil phase and is poured slowly into polyvinyl alcohol water solution, emulsifies 4min formation stabilized oil-in-water emulsions.Will
0.025g, 0.050 g, 0.100 g, 0.200g, 0.400g, 0.800g diethylenetriamines are dissolved in 10ml deionized waters respectively matches somebody with somebody
Into 6 equal portions diethylenetriamine solution.6 parts of diethylenetriamine solution are added dropwise to stable water bag successively from low concentration high concentration
In fat liquor, every part of diethylenetriamine solution adds 10 min of interval.Completion of dropping, is added emulsion by oil bath in 10 min
Heat is to 65 DEG C.React after 130 min, stop reaction.Room temperature is cooled to, the microcapsules of synthesis are washed with deionized 6 times, and lead to
Cross decantation separation.Microcapsules after separation are dried at room temperature for 48h, from Fig. 1 from spherical microcapsule granule size it is relative
Uniformly, surface is smooth, from Fig. 2 from IPDI successfully coated.With light microscope and nuclear-magnetism point
Division thing, obtains microcapsule granule average-size for 9.7 μm, clad ratio is 78.1wt%, and microcapsules can be mixed with resin material
During keep complete.
Embodiment 2.
At room temperature, 98% alcoholysis degree, molecular weight are added in deionized water for 170000-180000g/mol polyvinyl alcohol and stirred
30min, is subsequently heated to 95 DEG C of stirring 1.5h.Finally cooling obtains 2wt% polyvinyl alcohol water solution.Take the poly- of 60ml preparations
Vinyl alcohol aqueous solution is stirred at 600 rpm, then by 12 g IPDIs and 4g polyphenyl polymethylene polyisocyanates
Cyanate, which is mixed into homogeneous oil phase and is poured slowly into polyvinyl alcohol water solution, emulsifies 4 min formation stabilized oil-in-water emulsions.Will
0.030 g, 0.060g, 0.120g, 0.240g, 0.480g, 0.960g diethylenetriamine are dissolved in 10 ml deionized waters respectively matches somebody with somebody
Into 6 equal portions diethylenetriamine solution.Emulsion, every part of diethyl is added dropwise in 6 parts of diethylenetriamine solution successively after emulsification
Alkene triamine solution adds 10 min of interval.Completion of dropping, 45 DEG C are heated in 10 min by oil bath by emulsion.Reaction 420
After min, stop reaction.Room temperature is cooled to, the microcapsules of synthesis are washed with deionized 6 times, and is separated by being decanted.After separation
Microcapsules be dried at room temperature for 20h, then with light microscope and nmr analysis product, obtain microcapsule granule average-size
For 91.3 μm, clad ratio is 79.8 wt%, and microcapsules can be with keeping complete in resin material mixed process.
Embodiment 3.
At room temperature, 85% alcoholysis degree, molecular weight are added in deionized water for 20000-30000g/mol polyvinyl alcohol and stirred
30min, is subsequently heated to 70 DEG C of stirring 5h.Finally cooling obtains 12wt% polyvinyl alcohol water solution.Take the poly- of 60 ml preparations
Vinyl alcohol aqueous solution is stirred under 400rpm, then by 12g IPDIs and 4g polyphenyl polymethylene polyisocyanates
Cyanate, which is mixed into homogeneous oil phase and is poured slowly into polyvinyl alcohol water solution, emulsifies 4 min formation stabilized oil-in-water emulsions.Will
0.015g, 0.030g, 0.060g, 0.120 g, 0.240g, 0.480g diethylenetriamine are dissolved in 10 ml deionized waters respectively matches somebody with somebody
Into 6 equal portions diethylenetriamine solution.Emulsion, every part of diethyl is added dropwise in 6 parts of diethylenetriamine solution successively after emulsification
Alkene triamine solution adds 10 min of interval.Completion of dropping, 75 DEG C are heated in 10 min by oil bath by emulsion.Reaction
After 82min, stop reaction.Room temperature is cooled to, the microcapsules of synthesis are washed with deionized 6 times, and is separated by being decanted.Separation
Microcapsules afterwards are dried at room temperature for 48h, then with light microscope and nmr analysis product, obtain the average chi of microcapsule granule
Very little is 97.7 μm, and clad ratio is 81.7wt%, and microcapsules can be with keeping complete in resin material mixed process.
Embodiment 4.
At room temperature, 95% alcoholysis degree, molecular weight are added in deionized water for 70000-80000 g/mol polyvinyl alcohol and stirred
30min, is subsequently heated to 80 DEG C of 3 h of stirring.Finally cooling obtains 5 wt% polyvinyl alcohol water solution.Take the poly- of 60ml preparations
Vinyl alcohol aqueous solution is stirred at 600 rpm, then by 16g IPDIs and 4g polyphenyl polymethylene polyisocyanates
Cyanate, which is mixed into homogeneous oil phase and is poured slowly into polyvinyl alcohol water solution, emulsifies 4 min formation stabilized oil-in-water emulsions.Will
0.025 g, 0.050 g, 0.100 g, 0.200g, 0.400g, 0.800g diethylenetriamines are dissolved in 10ml deionized waters respectively
It is made into 6 parts of diethylenetriamine solution.Emulsion, every part of diethyl is added dropwise in 6 parts of diethylenetriamine solution successively after emulsification
Alkene triamine solution adds interval 5min.Completion of dropping, 65 DEG C are heated in 10min by oil bath by emulsion.React 125 min
Afterwards, reaction is stopped.Room temperature is cooled to, the microcapsules of synthesis are washed with deionized 6 times, and is separated by being decanted.After separation
Microcapsules are dried at room temperature for 48h.With light microscope and nmr analysis product, it is 97.6 to obtain microcapsule granule average-size
μm, clad ratio is 82.4wt%, and microcapsules can be with keeping complete in resin material mixed process.
Embodiment 5.
At room temperature, 95% alcoholysis degree, molecular weight are added in deionized water for 70000-80000g/mol polyvinyl alcohol and stirred
30min, is subsequently heated to 80 DEG C of stirring 3h.Finally cooling obtains 5wt% polyvinyl alcohol water solution.The poly- second for taking 60ml to prepare
The enol aqueous solution is stirred under 400 rpm, then by 16g IPDIs and 4 g polyphenyl polymethylene polyisocyanates
Cyanate, which is mixed into homogeneous oil phase and is poured slowly into polyvinyl alcohol water solution, emulsifies 3 min formation stabilized oil-in-water emulsions.Will
The g diethylenetriamines of 0.010 g, 0.030 g, 0.070 g, 0.150 g, 0.300 g, 0.900 are dissolved in 15 ml deionizations respectively
6 equal portions diethylenetriamine solution are made into water.Emulsion is added dropwise in 6 parts of diethylenetriamine solution successively after emulsification, often
Part diethylenetriamine solution adds 10 min of interval.Completion of dropping, 65 DEG C are heated in 10 min by oil bath by emulsion.
React after 140min, stop reaction.Room temperature is cooled to, the microcapsules of synthesis are washed with deionized 5 times, and passes through decantation point
From.Microcapsules after separation are dried at room temperature for 36h.With light microscope and nmr analysis product, obtain microcapsule granule and put down
Equal size is 160 μm, and clad ratio is 85wt%, and microcapsules can be with keeping complete in resin material mixed process.
Embodiment 6.
At room temperature, 95% alcoholysis degree, molecular weight are added in deionized water for 70000-80000 g/mol polyvinyl alcohol and stirred
30 min, are subsequently heated to 80 DEG C of 3 h of stirring.Finally cooling obtains 12 wt% polyvinyl alcohol water solution.60 ml are taken to prepare
Polyvinyl alcohol water solution stirred under 600 rpm, then by 8 g IPDIs and 4g polyphenyl polymethylenes
Polyisocyanates, which is mixed into homogeneous oil phase and is poured slowly into polyvinyl alcohol water solution, emulsifies 5 min formation stabilized oil-in-water breasts
Liquid.The g diethylenetriamines of 0.025 g, 0.045 g, 0.075 g, 0.155 g, 0.365 g, 0.885 are dissolved in 5 ml respectively
6 equal portions diethylenetriamine solution are made into ionized water.Breast is added dropwise in 6 parts of diethylenetriamine solution successively after emulsification
Liquid, every part of diethylenetriamine solution adds 15 min of interval.Completion of dropping, 65 are heated in 10 min by oil bath by emulsion
℃.React after 120 min, stop reaction.Room temperature is cooled to, the microcapsules of synthesis are washed with deionized 7 times, and passes through decantation
Separation.Microcapsules after separation are dried at room temperature for 36 h.With light microscope and nmr analysis product, microcapsule granule is obtained
Average-size is 34.2 μm, and clad ratio is 80.3wt%, and microcapsules can be with keeping complete in resin material mixed process.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent and improvement made within refreshing and principle etc., should be included within the scope of the present invention.
Claims (5)
1. a kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate, it is characterised in that including following
Step：
（1）Polyvinyl alcohol is added in deionized water and stirs 10-30min, 70-90 DEG C of stirring 1.5-5h is then warming up to, most
The polyvinyl alcohol water solution cooling that concentration is 2-12wt% will be obtained afterwards standby；
（2）Utilize step（1）The polyvinyl alcohol water solution of gained is simultaneously stirred in 400-1600rpm, is 1 by mass ratio：2-4's is more
Isocyanates shell material and low activity liquid isocyanate core are well mixed, obtain core shell material mixing oil phase, then will mixing
Oil phase is poured slowly into polyvinyl alcohol water solution and emulsifies 3-5 min formation stabilized oil-in-water emulsions, and is formed outside polyvinyl alcohol
It is 1 that shell, wherein core shell material, which mix oil phase with polyvinyl alcohol water solution mass ratio,：3-5；
（3）Amine cross-linking agent is divided into 6 parts to be added separately in deionized water, makes the concentration point of its 6 equal portions amine aqueous solution prepared
Not Wei 0.0015-0.0030 g/ml, 0.003-0.006g/ml, 0.006-0.012 g/ml, 0.012-0.024 g/ml,
0.024-0.048 g/ml, 0.048-0.096 g/ml, and 6 parts of amine aqueous solution concentration are different, and from low concentration to high concentration
Step is added dropwise successively（2）In emulsion in, every part of amine aqueous solution is added at intervals of 5-15 min, after completion of dropping, in 5-15
Emulsion is heated to 45-75 DEG C by oil bath in min, reaction 1-7h terminates, and forms polyureas hypostracum, wherein, shell material and amine
The mass ratio of crosslinking agent is 1：0.15-0.56, amine aqueous solution is 0.5-1.5 with polyvinyl alcohol water solution volume ratio：1；
（4）Emulsion is cooled to after room temperature and is washed with deionized 5-7 times, microcapsules are obtained by decantation, after finally separating
Microcapsules be dried at room temperature for 20-48 h, that is, obtain self-repairing microcapsule, wherein, the deionized water and quilt of each washing
The female slurry volume ratio of washing is 1-4：1.
2. a kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate as claimed in claim 1,
It is characterized in that described shell material is polyphenyl polymethylene polyisocyanates, toluene diisocyanate trimer, diphenyl-methane
One or more in diisocyanate trimer, hexamethylene diisocyanate trimer.
3. a kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate as claimed in claim 1,
It is characterized in that described amine cross-linking agent be one kind in ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or
It is a variety of.
4. a kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate as claimed in claim 1,
It is characterized in that the low activity liquid isocyanate is IPDI, hexamethylene diisocyanate, two rings
One or more in hexyl methane diisocyanate.
5. a kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate as claimed in claim 1,
It is characterized in that described polyvinyl alcohol is 85-98% alcoholysis degrees, molecular weight 20000-180000g/mol polyvinyl alcohol.
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| CN108219641A (en) * | 2018-01-03 | 2018-06-29 | 华南理工大学 | A kind of lignosulfonates dispersion self-healing carbamide paint and preparation method thereof and coating and application |
| CN110563921A (en) * | 2019-09-16 | 2019-12-13 | 西北工业大学 | Method for preparing isocyanate microcapsule by mercaptan-isocyanate click chemical reaction |
| CN111790325A (en) * | 2020-07-17 | 2020-10-20 | 中山纳微新材料科技有限公司 | Double-shell self-repairing microcapsule and preparation method and application thereof |
| CN112250830A (en) * | 2020-09-24 | 2021-01-22 | 长安大学 | Environment-friendly road microcapsule, preparation method thereof and application of illegal cooking oil |
| CN113337193A (en) * | 2021-05-05 | 2021-09-03 | 桂林理工大学 | Microcapsule type double-component waterborne polyurethane self-repairing coating and preparation method thereof |
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| CN114716177A (en) * | 2022-04-08 | 2022-07-08 | 北京工业大学 | Preparation method of cement particle microcapsule suitable for self-repairing cement-based material |
| CN114851338A (en) * | 2022-03-25 | 2022-08-05 | 广西丰林木业集团股份有限公司 | Aldehyde-free waterproof floor base material and preparation method thereof |
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| CN108219641A (en) * | 2018-01-03 | 2018-06-29 | 华南理工大学 | A kind of lignosulfonates dispersion self-healing carbamide paint and preparation method thereof and coating and application |
| US11905430B2 (en) | 2018-01-03 | 2024-02-20 | South China University Of Technology | Lignosulfonate dispersion self-healing polyurea coating, preparation method therefor, coating layer thereof and application thereof |
| CN110563921A (en) * | 2019-09-16 | 2019-12-13 | 西北工业大学 | Method for preparing isocyanate microcapsule by mercaptan-isocyanate click chemical reaction |
| CN111790325B (en) * | 2020-07-17 | 2022-09-09 | 香港科技大学 | Double-shell self-repairing microcapsule and preparation method and application thereof |
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| CN113813891B (en) * | 2021-09-28 | 2023-08-11 | 佛山科学技术学院 | Polyurethane microcapsule and preparation method thereof |
| CN113813891A (en) * | 2021-09-28 | 2021-12-21 | 佛山科学技术学院 | Polyurethane microcapsule and preparation method thereof |
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Application publication date: 20170714 |