CN110563921B - Method for preparing isocyanate microcapsules by thiol-isocyanate click chemistry - Google Patents
Method for preparing isocyanate microcapsules by thiol-isocyanate click chemistry Download PDFInfo
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- CN110563921B CN110563921B CN201910868535.3A CN201910868535A CN110563921B CN 110563921 B CN110563921 B CN 110563921B CN 201910868535 A CN201910868535 A CN 201910868535A CN 110563921 B CN110563921 B CN 110563921B
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- 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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- 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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
本发明涉及一种采用硫醇‑异氰酸酯点击化学反应制备异氰酸酯微胶囊的方法，利用芳香族异氰酸酯和脂肪族异氰酸酯的活性差异与，以及与硫醇反应活性的差异，采用胺催化硫醇‑异氰酸酯点击化学，使用活性较高的芳香族异氰酸酯对活性较低的脂肪族异氰酸酯进行包封，制备自修复微胶囊。解决了现有技术中异氰酸酯是防腐蚀涂层中的单组分修复剂，然后其难以包覆的问题。以点击化学的优势，巧妙利用活性差异进行完成了包覆。该方法提供了一种新的制备异氰酸酯微胶囊的方法，对自修复复合材料意义重大。
The invention relates to a method for preparing isocyanate microcapsules by adopting a thiol-isocyanate click chemical reaction. The difference in activity between aromatic isocyanates and aliphatic isocyanates, and the difference in reactivity with thiols, is used to catalyze thiol-isocyanate clicks with amines. In chemistry, self-healing microcapsules are prepared by encapsulating a less reactive aliphatic isocyanate with a more reactive aromatic isocyanate. The problem in the prior art that the isocyanate is a one-component repair agent in the anti-corrosion coating and then it is difficult to coat is solved. With the advantages of click chemistry, the coating is completed by cleverly using the difference in activity. This method provides a new method for preparing isocyanate microcapsules, which is of great significance for self-healing composite materials.
Description
Technical Field
The invention belongs to a preparation method of microcapsules, relates to a method for preparing isocyanate microcapsules by mercaptan-isocyanate click chemical reaction, and particularly relates to a self-repairing microcapsule prepared by adopting an amine catalysis mercaptan/isocyanate click method and encapsulating aliphatic isocyanate with low activity by using aromatic isocyanate with high 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 and solvent volatilization methods, and microfluid and electrostatic spraying methods which need special equipment, mainly have the following defects: 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 that are difficult to coat.
The existing method for coating isocyanate mainly comprises a method for preparing isocyanate microcapsules by carrying out interfacial polycondensation reaction on isocyanate prepolymer and alcohol or amine, but the reactions need heating and have longer reaction time. The invention introduces the rapid and efficient mercaptan-click reaction into the field of isocyanate coating, and provides a method for coating low-activity isocyanate by using the activity difference of isocyanate through the reaction of mercaptan and high-activity isocyanate, and the method can be finished within 20min without external energy (heating, UV and the like). Provides a new method for simple, efficient and green coating of isocyanate.
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 is characterized in that the difference of the reactivity of aromatic isocyanate and aliphatic isocyanate with mercaptan is utilized, mercaptan-isocyanate click chemistry is catalyzed by amine, and the aliphatic isocyanate with low activity is encapsulated by the aromatic isocyanate with high activity, so that the self-repairing microcapsules are prepared. Solves the problem that isocyanate is difficult to coat as a single-component repairing agent in an anti-corrosion coating in the prior art. The coating is completed by skillfully utilizing the activity difference with the advantage 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 IPDI @ PTMMP-TDI microcapsules of example 1;
FIG. 2 is a TGA plot of IPDI @ PTMMP-TDI microcapsules of example 1;
FIG. 3 is a graph showing the particle size distribution of the IPDI @ PTMP-TDI microcapsules 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 Hexamethylene Diisocyanate (HDI) 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 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 (4)
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: washing the isocyanate B-coated microcapsule obtained in the step (3) with distilled water, filtering, and drying in the air to obtain a dried microcapsule coated with the repairing agent;
and the stirring emulsification in the step 3 adopts a mechanical rotating speed of 500-3000 rpm.
2. 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.
3. Process for the preparation of isocyanate microcapsules using thiol-isocyanate click chemistry according to claim 1 or 2, 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.
4. Process for the preparation of isocyanate microcapsules using thiol-isocyanate click chemistry according to claim 1 or 2, 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.
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| KR20160000995A (en) * | 2014-06-26 | 2016-01-06 | 홍영근 | Self-healing asphalt containing microcapsules |
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