CN106397737B - A kind of room curing epoxy hardener microcapsules and preparation method thereof based on the insoluble type amine of water - Google Patents
A kind of room curing epoxy hardener microcapsules and preparation method thereof based on the insoluble type amine of water Download PDFInfo
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- CN106397737B CN106397737B CN201610765355.9A CN201610765355A CN106397737B CN 106397737 B CN106397737 B CN 106397737B CN 201610765355 A CN201610765355 A CN 201610765355A CN 106397737 B CN106397737 B CN 106397737B
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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
- C08G59/5026—Amines cycloaliphatic
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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
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/043—Drying and spraying
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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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/08—Simple coacervation, i.e. addition of highly hydrophilic material
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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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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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
- C08G59/5033—Amines aromatic
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- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of room curing epoxy hardener microcapsules and preparation method thereof based on the insoluble type amine of water.The epoxy hardener microcapsules use the insoluble type amine of water or the insoluble type amine of water type diluent insoluble with water and (or) the insoluble type accelerator mixture of water for capsule-core, using Lauxite as cyst wall, carry out microencapsulation in water and prepare epoxy hardener microcapsules.Preparation method simple process provided by the invention, at low cost, the epoxy hardener microcapsule coated rate of preparation is high, stable storing.Selfreparing by controlling the adjustable rate of release of dosage and reaction speed of diluent and promotor, with epoxy resin micro-capsule composite usage high molecular material at room temperature.
Description
Technical field
The invention belongs to room temperature fast-curing epoxy hardener technical fields, and in particular to a kind of based on the insoluble type amine of water
Room curing epoxy hardener microcapsules and preparation method thereof.
Background technique
High molecular material by external force, is inevitably generated the local damages such as crackle, causes in use
The deterioration of material property.Self-repair material can perceive this damage in time, repair to crackle etc., remove a hidden danger and extend
The service life of material.
Recent years, microcapsules become new focus in the application of high molecular material selfreparing, by by encapsulated epoxy
Resin dispersion is in resin base, and when material damage, microcapsules rupture under the action of crack stress releases epoxy resin, with tree
Polymerization reaction occurs for catalyst or curing agent contact in aliphatic radical body, to realize the reparation of damage surface.But use this side
Formula has an adverse effect to material performance itself if curing agent or catalyst usage amount are larger, if usage amount is smaller,
Then catalyst present on crack planes or curing agent are less, cannot sufficiently carry out selfreparing.
Polythiol is prepared into capsule-type curing agent by Chinese publication CN101116806A, solves problem above, but
Core materials are easy to crosslink with wall material in microencapsulation processes to react and be consumed and exist simultaneously curing agent in capsule and deposit
Store up unstable problem.Chinese patent CN104193965A discloses a kind of imidazoles epoxy hardener microcapsules and its preparation side
Method, but need to be heating and curing in repair process.
Traditional epoxy resin amine room temperature curing agent has hydrophily, therefore it is very tired to carry out microencapsulation in water
Difficulty makes for this purpose, Chinese patent CN103285795A discloses a kind of modified amine curing agent microcapsules and its preparation method and application
With water-soluble modified amine curing agent, but because it is modified not exclusively, a large amount of water-soluble amine monomers are still had in curing agent, in capsule
The waste of curing agent is caused during changing.
United States Patent (USP) US3396117 uses extrusion technique, produces curing agent microcapsules by physical method, utilizes alginic acid
Salt or the mixtures such as alginate and polyvinyl alcohol, gelatin carry out the mixture of packing diethylenetriamine and nonyl phenol as wall material；
Technology is added dropwise using orifice in United States Patent (USP) US3791980, utilizes thermoplastic materials packing ethylenediamine.But the former is prone to wall material
Bacterial degradation, the latter's capsule wall thickness are more than 100 μm, and need special processing unit (plant), are not able to satisfy for selfreparing composite wood
The basic demand in the fields such as material.
Therefore, it is necessary to develop a kind of Novel curing agent microcapsules, to meet the need for fields such as Self-repair Composites
It asks.
Summary of the invention
The object of the present invention is to provide a kind of room curing epoxy hardener microcapsules based on the insoluble type amine of water, the capsules
Use the insoluble type amine of water as raw material, can overcome the shortcomings of that mercaptan is easy polymerization and imidazoles requirement hot setting, so that capsule-core
Curing agent stable storing, and can be damaged in room temperature material for quickly repairing.
It is a further object to provide the above-mentioned room curing epoxy hardener microcapsules based on the insoluble type amine of water
Preparation method, this method is used as core materials using the insoluble type amine of water, facilitates and carry out microencapsulation in water.With Lauxite
For microcapsule wall material.
In order to realize the above goal of the invention, the technical scheme is that
A kind of room curing epoxy hardener microcapsules based on the insoluble type amine of water, the component system comprising following parts by weight
It is standby to form:
In the present invention, the insoluble type amine of the water can be insoluble for the insoluble type fatty amine of water, the insoluble type aliphatic cyclic amine of water and water
One of type aromatic amine is a variety of.
In the present invention, it is 7-12 that the insoluble type fatty amine of the water, which is carbon atom number, preferably 7-10, at least containing there are three living
Hydrogen is sprinkled, the insoluble type fatty amine of water of 4 active hydrogens is preferably comprised；More preferably it is greater than 6 polymethylene diamines containing carbon number, it can be with
Such as heptamethylene diamines included and/or eight methylene diamines.
In the present invention, it is 6-30 that the insoluble type aliphatic cyclic amine of the water, which is carbon atom number, preferably 10-20, at least contain there are three
Active hydrogen preferably comprises the insoluble type aliphatic cyclic amine of water of 4 active hydrogens；More preferably 4,4'- diamino double-hexyl methane, 4,4'-
Di-2-ethylhexylphosphine oxide (2- methyl cyclohexylamine) and 1,8- diamino are to one of terpane or a variety of.
In the present invention, it is 6-30 that the insoluble type aromatic amine of the water, which is carbon atom number, preferably 10-20, at least contain there are three
Active hydrogen preferably comprises the insoluble type aromatic amine of water of 4 active hydrogens；More preferably 4,4'- diaminodiphenyl-methane, diethyl
One of toluenediamine, 4,4'- diamino -3,3'- dimethyl diphenyl methane and 4,4' diaminodiphenyl sulfone are a variety of.
In the present invention, scheme more preferably, the insoluble type amine of the water is selected from 4,4'- diamino double-hexyl methane, 4,
4'- di-2-ethylhexylphosphine oxide (2- methyl cyclohexylamine), 1,8- diamino are to one of terpane and diethyl toluene diamine etc. or a variety of.
In the present invention, the formaldehyde used is usually the formalin of 37wt%.
In the present invention, the diluent is in the hydro carbons for being insoluble or slightly soluble in water, alcohols, esters and ethers etc.
It is one or more, one of can include such as toluene, n-hexyl alcohol, benzyl alcohol, ethyl acetate and butyl ether or a variety of.
In the present invention, the promotor is the acids for being insoluble or slightly soluble in water, phenols, alcohols, tertiary amines, sulphur
One of alcohols and organophosphorus compound etc. are a variety of, can include such as benzoic acid, nonyl phenol, n-hexyl alcohol, benzene first
One of alcohol, triethylamine and triphenylphosphine etc. are a variety of.
In the present invention, the emulsifier is neopelex (DBS), lauryl sodium sulfate (K12), benzene second
Alkene-copolymer-maleic anhydride (SMA), ethylene maleic acid anhydride copolymer, gum arabic, polyoxyethylene sorbitan fat
One of acid esters, gelatin, polyvinyl alcohol (PVA) and polyethylene glycol are a variety of；Preferably neopelex (DBS),
One of lauryl sodium sulfate, gelatin and polyvinyl alcohol are a variety of.
A method of preparing above-mentioned microcapsules, comprising the following steps:
A, formalin and urea proportionally, are added in the reactor, after urea is completely dissolved, adjusts pH value of solution
Value is 8~9, and temperature reaction obtains ureaformaldehyde performed polymer；
B, after the ureaformaldehyde performed polymer that step a is obtained is cooling, it is optionally added into the aqueous solution containing emulsifier, is then added
The insoluble type amine of uniformly mixed water and optional promotor, diluent after being uniformly mixed, heat up after adjusting pH value to 2~4
Reaction；
C, the reaction mixture that step b is obtained is washed through water and/or acetone soln, is filtered, can be obtained after dry
Microcapsule product.
In the present invention, the dissolution of urea, 10~30min of dissolution time can be accelerated in the step a by stirring.
In the present invention, pH value, including but not limited to sodium hydroxide solution, hydroxide are adjusted using lye in the step a
One of potassium solution, sodium carbonate liquor and triethanolamine are a variety of.
In the present invention, the reaction temperature of the step a is 40-70 DEG C, preferably 50~65 DEG C, reaction time 10min
~1.5h, preferably 0.5~1h.
Make after the insoluble type amine of water is added in the present invention, in the step b and stirs 20~30min after optional promotor
Reaction mass is uniformly mixed.
In the present invention, pH value is adjusted using acid solution in the step b, the acid solution includes but is not limited to hydrochloric acid solution, sulphur
One of acid solution, ammonium hydroxide solution and citric acid solution are a variety of.
In the present invention, the step b is warming up to 50~90 DEG C, reacts 2~6h.
In the present invention, the microcapsule product being prepared is usually white, and microcapsule coated rate is high, reachable 65-85%,
Microencapsulated forms are regular, and size is in tens nanometer to hundreds of microns, preferably 50-200 μm, and more preferable 70-185 μm.
The present invention is controlled by change mixing speed, emulsifier and dosage, the pH value of reaction system and reaction temperature
Clad ratio, dispersibility and the particle size of microcapsules processed.By adjusting the insoluble type amine microcapsules packet of water prepared by the above parameter
Rate height is covered, up to 65-85%, microencapsulated forms are regular, of uniform size.
The present invention controls the viscosity and reaction speed of capsule-core curing agent by adjusting diluent, the type of promotor and dosage
Degree, to control the rate of release and selfreparing reaction speed of capsule-core curing agent.
The invention has the following advantages:
(1) insoluble using the insoluble type amine of water or water for the defect of physical method production curing agent microcapsules in the present invention
Type amine type diluent insoluble with optional water and/or the insoluble type accelerator mixture of optional water are capsule-core, and Lauxite is capsule
Wall carries out microencapsulation in water, and the curing agent microcapsule coated rate of this method preparation is high, and stability is good, easily disperses；
(2) preparation method is simple by the present invention, and the reaction time is short, and the insoluble type amine of the water after cladding is in certain external force
Under break cyst wall and slow release；By changing mixing speed, emulsifier and dosage, the pH value of reaction system and reaction temperature
Degree can control the clad ratio, average wall thickness and particle size of curing agent microcapsules.
(3) microcapsules prepared by the present invention can directly cooperate with epoxy resin micro-capsule, for high molecular material from
Repair, by change diluent type and dosage, the type of promotor and dosage can control curing agent rate of release and
With the reaction speed of epoxy resin, remediation efficiency is finally controlled.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further explained, and the invention is not limited to following realities
Apply example.
Embodiment 1
Configured with tri- mouthfuls of churned mechanically 250ml be added in reaction flask 16g urea and 32.43g37wt% formaldehyde it is molten
It sprinkles, after urea is completely dissolved, the pH value of solution is slowly adjusted using sodium hydroxide solution to 8, is then rapidly heated to 50 DEG C,
It is stirred at reflux the performed polymer that lower reaction 0.5h. obtains the urea-formaldehyde of clear viscous, cooled to room temperature.By 240g 4,4'-
Diamino double-hexyl methane and 2g toluene and 0.6g n-hexyl alcohol after mixing, are slowly added in above-mentioned solution, with 300r/min
After 20~30min of stirring and emulsifying, be slowly dropped into hydrochloric acid solution adjust reaction system pH value to 2, after microcapsules are formed completely,
It increases temperature and solidifies 2h to 50 DEG C of, reaction terminates.It is filtered, washed, is dried to obtain the curing agent microcapsules of white.Synthesis
Curing agent microcapsules are 185 μm through analysis average grain diameter, and the average wall thickness of microcapsules is 12 μm.
Embodiment 2- embodiment 7
Microcapsule preparation method is substantially the same manner as Example 1, and see Table 1 for details for formula table and reaction condition, and what is be prepared is micro-
See Table 3 for details for the parameters such as capsule clad ratio.
Embodiment 8
100 parts of epoxy resin E51 and 22 parts of IPDA are taken, the epoxy resin micro-capsule and embodiment 1 that stoichiometric is added are made
Standby curing agent microcapsules are uniformly mixed, bubble are removed under reduced pressure, pours into silica gel mould after room temperature curing for 24 hours, is put into baking oven
80 DEG C of solidification 1.5h of constant temperature.After natural cooling, removes silica gel mould and obtain fracture toughness test part, using INSTRON 33,440,000
Energy cupping machine carries out fracture toughness experiment, and under room temperature, tensile speed is set as 1mm/min, and initial samples are stretched to
Failure, fracture toughness at this time are K0, load is removed, is slowly closed crack surface, after placing 3h at room temperature, is repeated
Test, the fracture toughness K after being repaired1, η=K0/K1=70% i.e. in the epoxy resin agent microcapsules and curing agent microcapsules
Under the conditions of remediation efficiency.
Embodiment 9- embodiment 14
Remediation efficiency test, method and implementation successively are carried out to solidification agent capsules prepared by embodiment 2- embodiment 7 respectively
Example 8 is essentially identical, and remediation efficiency is shown in Table 4.
Comparative example 1- comparative example 2
Comparative example 1 is prepared according to the formula and reaction condition in table 2 respectively referring to the microcapsule preparation method of embodiment 1
With the curing agent microcapsules of comparative example 2, see Table 3 for details for the parameters such as clad ratio.
Comparative example 3- comparative example 4
The curing agent microcapsules successively prepared respectively to comparative example 1 and comparative example 2 carry out remediation efficiency test, method and reality
It is essentially identical to apply example 8, see Table 4 for details for remediation efficiency.
The formula table of 1 embodiment 1-8 curing agent microcapsules raw material components of table
The formula and reaction condition table of 2 comparative example 1-2 microcapsules raw material components of table
3 curing agent microencapsulated forms of table
4 curing agent microcapsules type of table and remediation efficiency
| Curing agent microcapsules | Remediation efficiency η (%) | |
| Embodiment 8 | Embodiment 1 | 75 |
| Embodiment 9 | Embodiment 2 | 81 |
| Embodiment 10 | Embodiment 3 | 85 |
| Embodiment 11 | Embodiment 4 | 70 |
| Embodiment 12 | Embodiment 5 | 77 |
| Embodiment 13 | Embodiment 6 | 73 |
| Embodiment 14 | Embodiment 7 | 78 |
| Comparative example 3 | Comparative example 1 | 45 |
| Comparative example 4 | Comparative example 2 | 52 |
Claims (19)
1. a kind of room curing epoxy hardener microcapsules based on the insoluble type amine of water, the component preparation comprising following parts by weight
It forms:
The insoluble type amine of the water is the insoluble type aliphatic cyclic amine of water.
2. epoxy hardener microcapsules according to claim 1, which is characterized in that the component system comprising following parts by weight
It is standby to form:
3. epoxy hardener microcapsules according to claim 2, which is characterized in that the component system comprising following parts by weight
It is standby to form:
4. epoxy hardener microcapsules according to claim 1, which is characterized in that the insoluble type aliphatic cyclic amine of the water, carbon
Atomicity is 6-30, at least containing there are three active hydrogens.
5. epoxy hardener microcapsules according to claim 4, which is characterized in that the insoluble type aliphatic cyclic amine carbon of the water is former
Subnumber is 10-20.
6. epoxy hardener microcapsules according to claim 4, which is characterized in that the insoluble type aliphatic cyclic amine of the water is at least
Contain 4 active hydrogens.
7. epoxy hardener microcapsules according to claim 4, which is characterized in that the insoluble type aliphatic cyclic amine of the water is 4,
4'- diamino bicyclic hexyl methane, 4,4' methylene bis (2- methyl cyclohexylamine) and 1,8- diamino are to one of terpane
Or it is a variety of.
8. epoxy hardener microcapsules according to claim 1, which is characterized in that the diluent be it is not soluble in water or
Person is slightly soluble in one of hydro carbons, alcohols, esters and ethers of water or a variety of.
9. epoxy hardener microcapsules according to claim 8, which is characterized in that the diluent be toluene, just oneself
One of alcohol, benzyl alcohol, ethyl acetate and butyl ether are a variety of.
10. epoxy hardener microcapsules according to claim 1, which is characterized in that the promotor is not soluble in water
Or one of acids, phenols, alcohols, tertiary amines, thio-alcohol and organophosphorus compound for being slightly soluble in water or a variety of；It is described
Emulsifier be neopelex, lauryl sodium sulfate, one copolymer-maleic anhydride of styrene, ethylene maleic acid
One in anhydride copolymer, gum arabic, polyoxyethylene sorbitan fatty acid ester, gelatin, polyvinyl alcohol and polyethylene glycol
Kind is a variety of.
11. epoxy hardener microcapsules according to claim 10, which is characterized in that the promotor be benzoic acid,
One of nonyl phenol, n-hexyl alcohol, benzyl alcohol, triethylamine and triphenylphosphine are a variety of.
12. epoxy hardener microcapsules according to claim 10, which is characterized in that the emulsifier is dodecyl
One of benzene sulfonic acid sodium salt, lauryl sodium sulfate, gelatin and polyvinyl alcohol are a variety of.
13. a kind of method for preparing epoxy hardener microcapsules of any of claims 1-12, comprising the following steps:
A, formalin and urea are proportionally added in the reactor, after urea is completely dissolved, adjusting solution ph is 8
~9, temperature reaction obtains ureaformaldehyde performed polymer；
B, after the ureaformaldehyde performed polymer that step a is obtained is cooling, it is optionally added into the aqueous solution containing emulsifier, mixing is then added
After being uniformly mixed, it is anti-to heating after 2~4 to adjust pH value for the uniform insoluble type amine of water and optional promotor and diluent
It answers；
C, the obtained reaction mixture of step b is washed, epoxy hardener microcapsule product can be obtained after dry.
14. according to the method for claim 13, which is characterized in that adjust pH value using lye in the step a；Step a
Reaction temperature be 40~70 DEG C, the reaction time be 10min~1.5h.
15. according to the method for claim 14, which is characterized in that the lye is sodium hydroxide solution, potassium hydroxide is molten
One of liquid, sodium carbonate liquor and triethanolamine are a variety of.
16. according to the method for claim 14, which is characterized in that reaction temperature is 50~65 DEG C.
17. according to the method for claim 14, which is characterized in that the reaction time is 0.5~1h.
18. according to the method for claim 13, which is characterized in that adjust pH value using acid solution in the step b；The step
Rapid b is warming up to 50~90 DEG C, reacts 2~6h.
19. according to the method for claim 18, which is characterized in that the acid solution is hydrochloric acid solution, sulfuric acid solution and lemon
One of acid solution is a variety of.
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| CN107088389A (en) * | 2017-05-26 | 2017-08-25 | 天津工业大学 | A kind of two-component capsule and preparation method thereof |
| CN108219036B (en) * | 2018-01-10 | 2019-05-03 | 肥城林原高分子材料有限公司 | A kind of polyvinyl alcohol ester and the preparation method and application thereof |
| CN109837132A (en) * | 2019-03-06 | 2019-06-04 | 天津职业技术师范大学(中国职业培训指导教师进修中心) | A kind of composite lubricated material of porous oil-containing and preparation method thereof |
| CN112481764B (en) * | 2020-11-23 | 2021-11-16 | 江阴远闻纺织有限公司 | Spandex core-spun yarn defect-free production process |
| CN112811845B (en) * | 2020-12-31 | 2022-07-05 | 北京工业大学 | Preparation method of cement-based self-repairing material based on oil-soluble amine microcapsules |
| CN112831256B (en) * | 2021-03-08 | 2022-01-11 | 盛达建材集团有限公司 | Stone surface anti-slip and anti-wear treatment process |
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| CN101665674A (en) * | 2009-09-30 | 2010-03-10 | 烟台德邦科技有限公司 | Single-component thread locking epoxy precoated adhesive and preparation method thereof |
| CN103285795A (en) * | 2013-05-08 | 2013-09-11 | 广东药学院 | Modified amine curing agent microcapsule as well as preparation method and applications thereof |
| CN104177983A (en) * | 2014-08-28 | 2014-12-03 | 漳州鑫展旺化工有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665674A (en) * | 2009-09-30 | 2010-03-10 | 烟台德邦科技有限公司 | Single-component thread locking epoxy precoated adhesive and preparation method thereof |
| CN103285795A (en) * | 2013-05-08 | 2013-09-11 | 广东药学院 | Modified amine curing agent microcapsule as well as preparation method and applications thereof |
| CN104177983A (en) * | 2014-08-28 | 2014-12-03 | 漳州鑫展旺化工有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
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Denomination of invention: The invention relates to a room temperature curing epoxy curing agent microcapsule based on water-insoluble amine and a preparation method thereof Effective date of registration: 20211123 Granted publication date: 20181207 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
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