CN110563921A - Method for preparing isocyanate microcapsule by mercaptan-isocyanate click chemical reaction - Google Patents
Method for preparing isocyanate microcapsule by mercaptan-isocyanate click chemical reaction Download PDFInfo
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- CN110563921A CN110563921A CN201910868535.3A CN201910868535A CN110563921A CN 110563921 A CN110563921 A CN 110563921A CN 201910868535 A CN201910868535 A CN 201910868535A CN 110563921 A CN110563921 A CN 110563921A
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- isocyanate
- mercaptan
- microcapsules
- click chemistry
- thiol
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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
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for preparing isocyanate microcapsules by adopting mercaptan-isocyanate click chemistry reaction, which utilizes the activity difference of aromatic isocyanate and aliphatic isocyanate and the difference of the activity of the reaction of the aromatic isocyanate and aliphatic isocyanate with mercaptan, adopts amine to catalyze mercaptan-isocyanate click chemistry, and uses aromatic isocyanate with higher activity to encapsulate aliphatic isocyanate with lower activity to prepare self-repairing microcapsules. Solves the problem that the isocyanate is a single-component repairing agent in the anti-corrosion coating and is difficult to coat in the prior art. The coating is completed by skillfully utilizing the activity difference with the advantages of click chemistry. The method provides a new method for preparing the isocyanate microcapsule, and has great significance for self-repairing composite materials.
Description
Technical Field
the invention belongs to a preparation method of microcapsules, relates to a method for preparing isocyanate microcapsules by adopting mercaptan-isocyanate click chemical reaction, and particularly relates to a method for preparing self-repairing microcapsules by adopting an amine catalysis mercaptan/isocyanate click method and encapsulating aliphatic isocyanate with lower activity by using aromatic isocyanate with higher activity.
background
Researchers imitate the self-repairing function of organisms to design self-repairing materials, and the self-repairing materials have the function of self-healing damage after being damaged. At present, self-repairing materials are gradually applied to exploratory applications (such as protective coatings of ships, submarines and aerospace vehicles) in various industrial fields. Microcapsule type self-repairing material, namely, microcapsules containing active repairing agents are embedded in a polymer material body in advance to realize the repair of matrix cracks. Compared with other methods for preparing externally-applied self-repairing materials, the method is simple to operate and mature in preparation technology; in addition, compared with the intrinsic self-repairing material, the microcapsule self-repairing material does not need to change the material structure, and has small influence on the material performance. The traditional methods for preparing microcapsules, such as in-situ polymerization, interfacial polymerization, solvent volatilization methods, and special equipment such as microfluid and electrostatic spraying methods, mainly have the following disadvantages: 1, the preparation process is complex, the flow is long and the energy consumption is large; 2 special equipment is required to be built, and the cost is high.
In addition, isocyanates are one-component repair agents in corrosion protection coatings, which are then difficult to coat.
Disclosure of Invention
Technical problem to be solved
in order to avoid the defects of the prior art, the invention provides a method for preparing isocyanate microcapsules by adopting a thiol-isocyanate click chemical reaction.
technical scheme
A method for preparing isocyanate microcapsules by adopting thiol-isocyanate click chemistry reaction is characterized by comprising the following steps:
Step 1: taking an aqueous solution prepared from a surfactant and distilled water as a water phase; the mass percent of the surfactant to the distilled water is 0.2-5 wt.%;
step 2: mixing mercaptan, isocyanate A and isocyanate B to obtain an oil phase; wherein: the molar ratio of the functional groups of the mercaptan to the isocyanate A is 1: 1, the mass ratio of the functional groups of the mercaptan to the isocyanate A is 1.27-2.29: 1, and the mass ratio of the isocyanate B to the shell monomer is 0.56-4: 1;
the shell layer monomer is mercaptan and isocyanate A;
The isocyanate A is toluene diisocyanate TDI or 4, 4-diphenylmethane diisocyanate MDI;
the isocyanate B is isophorone diisocyanate (IPDI) or Hexamethylene Diisocyanate (HDI) with the reaction activity lower than that of the isocyanate A;
And step 3: slowly adding the oil phase into the water phase, stirring and emulsifying for 10-30 min to form a stable emulsion, immediately adding 1-3 mL of triethylamine, and reacting for 1-20 min to obtain an isocyanate B-coated microcapsule; the mass ratio of the oil phase to the water phase is 1: 2-8;
and 4, step 4: and (3) washing the microcapsules coated with the isocyanate B obtained in the step (3) by using distilled water, filtering, and drying in the air to obtain the dried microcapsules coated with the repairing agent.
And the stirring emulsification in the step 3 adopts a mechanical rotating speed of 500-3000 rpm.
The distilled water in the step 4 is washed three times.
The surfactant is at least one or two of polyvinyl alcohol PVA, sodium dodecyl sulfate SDS or sodium dodecyl benzene sulfonate SDBS which are mixed according to any proportion.
The mercaptan is at least one of one or a mixture of two or more of trimethylolpropane (3-mercaptopropane acid ester) TMMP, tris (2-hydroxyethyl) isocyanurate-tris (mercaptopropionate) TEMPIC and pentaerythritol tetrakis (3-mercaptopropionate) PETMP mixed in any ratio.
Advantageous effects
The invention provides a method for preparing isocyanate microcapsules by adopting mercaptan-isocyanate click chemistry reaction, which utilizes the activity difference of aromatic isocyanate and aliphatic isocyanate and the difference of the activity of the reaction of the aromatic isocyanate and aliphatic isocyanate with mercaptan, adopts amine to catalyze mercaptan-isocyanate click chemistry, and uses aromatic isocyanate with higher activity to encapsulate aliphatic isocyanate with lower activity to prepare self-repairing microcapsules. Solves the problem that the isocyanate is a single-component repairing agent in the anti-corrosion coating and is difficult to coat in the prior art. The coating is completed by skillfully utilizing the activity difference with the advantages of click chemistry. The method provides a new method for preparing the isocyanate microcapsule, and has great significance for self-repairing composite materials.
drawings
FIG. 1 is an SEM picture of the preparation of IPDI @ PTMMP-TDI microcapsules of example 1;
FIG. 2 is a TGA plot of the IPDI @ PTMMP-TDI microcapsule preparation of example 1;
FIG. 3 is a graph showing the particle size distribution of the IPDI @ PTMP-TDI microcapsule preparation of example 1.
Detailed Description
the invention will now be further described with reference to the following examples and drawings:
Example 1: preparation of IPDI @ PTMP-TDI microcapsule
2g of polyvinyl alcohol (PVA) and 98mL of distilled water are mixed and respectively added into a 250mL three-necked bottle with a condenser tube, the rotating speed is 300rpm/min, the temperature is 80 ℃, and the PVA aqueous solution is obtained after 2h dissolution.
uniformly mixing trimethylolpropane (3-mercaptopropane acid ester) (TMMP), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI) to obtain an oil phase, using the PVA aqueous solution as a water phase, respectively adding the water phase into a three-neck flask, mechanically stirring and emulsifying at a high speed for 5-10 min, and dropwise adding 1-2 mL of triethylamine. After reacting for 20min at room temperature, filtering, washing and drying. Wherein the molar ratio of TMMP to TDI is 1: 1, the mass ratio of IPDI to shell monomer is 3: 2, the mass ratio of oil to water is 1: 4.
Example 2: preparation of HDI @ PTMP-TDI microcapsule
2g of polyvinyl alcohol (PVA) and 98mL of distilled water are mixed and respectively added into a 250mL three-necked bottle with a condenser tube, the rotating speed is 300rpm/min, the temperature is 80 ℃, and the PVA aqueous solution is obtained after 2h dissolution.
uniformly mixing trimethylolpropane (3-mercaptopropane acid ester) (TMMP), Toluene Diisocyanate (TDI) and epoxy resin (E-51) to obtain an oil phase, adding the PVA aqueous solution serving as a water phase into three-neck flasks respectively, mechanically stirring and emulsifying at a high speed for 5-10 min, and dropwise adding 1-2 mL of triethylamine. After reacting for 20min at room temperature, filtering, washing and drying. Wherein the molar ratio of TMMP to TDI is 1: 1, the mass ratio of HDI to shell monomer is 3: 2, the mass ratio of oil to water is 1: 4.
Example 3: preparation of IPDI @ PTMP-TDI microcapsule
2g of polyvinyl alcohol (PVA) and 98mL of distilled water are mixed and respectively added into a 250mL three-necked bottle with a condenser tube, the rotating speed is 300rpm/min, the temperature is 80 ℃, and the PVA aqueous solution is obtained after 2h dissolution.
uniformly mixing trimethylolpropane (3-mercaptopropane acid ester) (TMMP), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI) to obtain an oil phase, adding the PVA aqueous solution serving as a water phase into three-neck flasks respectively, mechanically stirring at 1000rpm/min to emulsify for 5-10 min at a high speed, and dropwise adding 1-2 mL of triethylamine. After reacting for 20min at room temperature, filtering, washing and drying. Wherein the molar ratio of TMMP to TDI is 1: 1, the mass ratio of IPDI to shell monomer is 3: 2, the mass ratio of oil to water is 1: 6.
Claims (5)
1. a method for preparing isocyanate microcapsules by adopting thiol-isocyanate click chemistry reaction is characterized by comprising the following steps:
Step 1: taking an aqueous solution prepared from a surfactant and distilled water as a water phase; the mass percent of the surfactant to the distilled water is 0.2-5 wt.%;
Step 2: mixing mercaptan, isocyanate A and isocyanate B to obtain an oil phase; wherein: the molar ratio of the functional groups of the mercaptan to the isocyanate A is 1: 1, the mass ratio of the functional groups of the mercaptan to the isocyanate A is 1.27-2.29: 1, and the mass ratio of the isocyanate B to the shell monomer is 0.56-4: 1;
The shell layer monomer is mercaptan and isocyanate A;
the isocyanate A is toluene diisocyanate TDI or 4, 4-diphenylmethane diisocyanate MDI;
the isocyanate B is isophorone diisocyanate (IPDI) or Hexamethylene Diisocyanate (HDI) with the reaction activity lower than that of the isocyanate A;
And step 3: slowly adding the oil phase into the water phase, stirring and emulsifying for 10-30 min to form a stable emulsion, immediately adding 1-3 mL of triethylamine, and reacting for 1-20 min to obtain an isocyanate B-coated microcapsule; the mass ratio of the oil phase to the water phase is 1: 2-8;
And 4, step 4: and (3) washing the microcapsules coated with the isocyanate B obtained in the step (3) by using distilled water, filtering, and drying in the air to obtain the dried microcapsules coated with the repairing agent.
2. The process for the preparation of isocyanate microcapsules using thiol-isocyanate click chemistry according to claim 1, wherein: and the stirring emulsification in the step 3 adopts a mechanical rotating speed of 500-3000 rpm.
3. The process for the preparation of isocyanate microcapsules using thiol-isocyanate click chemistry according to claim 1, wherein: the distilled water in the step 4 is washed three times.
4. The process for the preparation of isocyanate microcapsules using thiol-isocyanate click chemistry according to claim 1 or 2 or 3, characterized in that: the surfactant is at least one or two of polyvinyl alcohol PVA, sodium dodecyl sulfate SDS or sodium dodecyl benzene sulfonate SDBS which are mixed according to any proportion.
5. The process for the preparation of isocyanate microcapsules using thiol-isocyanate click chemistry according to claim 1 or 2 or 3, characterized in that: the mercaptan is at least one of one or a mixture of two or more of trimethylolpropane (3-mercaptopropane acid ester) TMMP, tris (2-hydroxyethyl) isocyanurate-tris (mercaptopropionate) TEMPIC and pentaerythritol tetrakis (3-mercaptopropionate) PETMP mixed in any ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910868535.3A CN110563921B (en) | 2019-09-16 | 2019-09-16 | Method for preparing isocyanate microcapsule by mercaptan-isocyanate click chemical reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910868535.3A CN110563921B (en) | 2019-09-16 | 2019-09-16 | Method for preparing isocyanate microcapsule by mercaptan-isocyanate click chemical reaction |
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| CN110563921A true CN110563921A (en) | 2019-12-13 |
| CN110563921B CN110563921B (en) | 2021-07-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651407A (en) * | 2022-10-24 | 2023-01-31 | 西北工业大学 | Microcapsule with multiple self-repairing performance, coating and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100320421A1 (en) * | 2005-09-19 | 2010-12-23 | U.S.A. as Represented by the Administrator of the National Aeronautics and Spac Adr | Hydrophilic-Core Microcapsules and their Formation |
| CN105080441A (en) * | 2015-07-28 | 2015-11-25 | 西北工业大学 | Preparation method of microcapsules coated with liquid alkene |
| KR20160000995A (en) * | 2014-06-26 | 2016-01-06 | 홍영근 | Self-healing asphalt containing microcapsules |
| CN106943969A (en) * | 2017-04-07 | 2017-07-14 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate |
| CN108525618A (en) * | 2018-04-09 | 2018-09-14 | 西北工业大学 | A kind of preparation method of double-walled room microcapsules |
-
2019
- 2019-09-16 CN CN201910868535.3A patent/CN110563921B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100320421A1 (en) * | 2005-09-19 | 2010-12-23 | U.S.A. as Represented by the Administrator of the National Aeronautics and Spac Adr | Hydrophilic-Core Microcapsules and their Formation |
| KR20160000995A (en) * | 2014-06-26 | 2016-01-06 | 홍영근 | Self-healing asphalt containing microcapsules |
| CN105080441A (en) * | 2015-07-28 | 2015-11-25 | 西北工业大学 | Preparation method of microcapsules coated with liquid alkene |
| CN106943969A (en) * | 2017-04-07 | 2017-07-14 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate |
| CN108525618A (en) * | 2018-04-09 | 2018-09-14 | 西北工业大学 | A kind of preparation method of double-walled room microcapsules |
Non-Patent Citations (2)
| Title |
|---|
| ZHENGLONG HE ETC.: "Self-healing isocyanate microcapsules for efficient restoration of fracture damage of polyurethane and epoxy resins", 《J MATER SCI》 * |
| 梁丰收: "异氰酸酯自修复微胶囊的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技 I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651407A (en) * | 2022-10-24 | 2023-01-31 | 西北工业大学 | Microcapsule with multiple self-repairing performance, coating and preparation method |
| CN115651407B (en) * | 2022-10-24 | 2023-10-13 | 西北工业大学 | Microcapsule with multiple self-repairing performance, coating and preparation method |
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