CN108525618B - Preparation method of double-wall-chamber microcapsule - Google Patents
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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Abstract
The invention relates to a preparation method of a double-wall chamber microcapsule, which takes macromolecules which have amphipathy and can initiate polymerization again as a stabilizing agent to prepare small capsules coated with a repairing agent, takes the small capsules as the stabilizing agent of Pickering emulsion, adopts a mercaptan/isocyanate point beating method, and prepares the double-wall chamber microcapsule by a method of stabilizing the self-assembly of the capsules and adsorbing the self-assembly of the capsules on the surface of the large capsules. The prepared double-wall chamber microcapsule has the advantages that the inner wall and the outer wall of the microcapsule contain the repairing agent at the same time, the performance of responding cracks and releasing the repairing agent for many times can be realized, and the preparation of the intelligent self-repairing material is deeply influenced.
Description
Technical Field
The invention relates to a preparation method of a double-wall chamber microcapsule, in particular to a preparation method of a double-wall chamber microcapsule, which uses macromolecules which have amphipathy and can initiate polymerization again as a stabilizing agent to prepare small capsules for coating a repairing agent, uses the small capsules as a stabilizing agent of Pickering emulsion, and adopts a mercaptan/isocyanate click method to prepare the double-wall chamber microcapsule.
Background
Microcapsules refer to micro reservoirs that encapsulate a dispersed functional liquid, solid or gas to form a core-shell structure, with the outer shell of the capsule acting as a barrier to protect the core material from performance failure in the external environment. In recent years, microcapsules as a storage liquid are widely applied to intelligent self-repairing materials, remarkable results are achieved, and meanwhile, the development of a polymer self-repairing system is promoted. The microcapsules act as a storage medium for the healing agent in the polymer matrix, releasing the core material upon material damage. Compared with other methods, the microcapsule-based self-repairing material has a larger development prospect, but still has the problem that the multiple self-repairing is difficult to realize. Aiming at the aim of realizing multiple repair, the invention designs and provides a microcapsule with a double-wall chamber structure, wherein small capsules are adsorbed on the surface of the outer wall of a large capsule, the small-sized capsules and the large capsule can simultaneously encapsulate a repair agent, and the repair agent can be released for multiple times when cracks propagate to repair a matrix.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of a double-walled chamber microcapsule, which adopts an amphiphilic self-stabilizing microcapsule as a Pickering emulsion and adopts a mercaptan/isocyanate click method to prepare the multi-walled chamber microcapsule. The inner wall and the outer wall of the double-wall chamber microcapsule prepared by the method contain the repairing agent at the same time, so that the matrix can be repaired for many times.
Technical scheme
A method for preparing microcapsules with double wall chambers is characterized by comprising the following steps:
step 1: mixing 1, 1-diphenylethylene DPE and glycidyl acrylate GMA with deionized water, and heating to 65-80 ℃ in a water bath; wherein the mass fraction of glycidyl acrylate GMA in deionized water is 5-14%, and the mass fraction of 1, 1-diphenylethylene DPE in GMA is 0.6-3%;
step 2: adding 45-180 mL of initiator aqueous solution, heating in a water bath under stirring for reacting for 16-24 h, and performing rotary evaporation to remove water to obtain a DPE-PGMA prepolymer; the concentration of the initiator aqueous solution is 0.5-2.0 g/L;
and step 3: adding the DPE-PGMA prepolymer into the activated dialysis bag, and sealing; putting the mixture into deionized water for dialysis for one week, respectively measuring the conductivities of the deionized water soaked in the dialysis bag and the freshly prepared deionized water, calculating the difference, and pouring out the prepolymer with the absolute value less than 0.001;
and 4, step 4: mixing the DPE-PGMA prepolymer, the monomer, the core material A and deionized water, and stirring and emulsifying at a high speed for 10-40 min; heating to 80 ℃ in a water bath, mechanically stirring for 150-500 rmp, heating in the water bath for reaction for 10-16 h, centrifuging, washing with alcohol for 1 time, and washing with water for 3 times to obtain microcapsules; wherein the DPE-PGMA prepolymer accounts for 7-14% of the total reaction liquid by mass, and the monomer and the core material A respectively account for 4-15% of the total reaction liquid by mass;
and 5: preparing the microcapsule of the step 4 into a capsule emulsion with the mass concentration of 0.5-6%, mixing the capsule emulsion with shell layer monomer mercaptan, isocyanate and the core material B, mechanically stirring and emulsifying at a high speed for 5-10 min, then dropwise adding 1-2 mL of triethylamine, reacting at room temperature for 20min, and then performing suction filtration, washing and drying to obtain the double-wall-chamber microcapsule; wherein the molar ratio of the shell layer monomer mercaptan to the functional groups of the isocyanate is 1: 1, and the mass ratio of the core material B to the shell layer monomer mercaptan is 0.5-2: 1.
The initiator is potassium persulfate KPS, ammonium persulfate APS, azobisisobutyronitrile AIBN or dibenzoyl peroxide BPO.
The monomer is methyl methacrylate MMA, diethylbenzene DVB or a mixture of the two monomers in any proportion.
The core material A is one or a mixture of two or more than two of dicyclopentadiene DCPD, epoxy E-51 and epoxy 184 which are mixed in any proportion.
The mercaptan is 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.
The isocyanate is one or a mixture of two or more of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI) which are mixed in any ratio.
The core material B is at least one of dicyclopentadiene DCPD and a mixture of dicyclopentadiene and toluene in any proportion.
Advantageous effects
The invention provides a preparation method of a double-wall chamber microcapsule, which takes macromolecules which have amphipathy and can initiate polymerization again as a stabilizing agent to prepare a small capsule for coating a repairing agent, takes the small capsule as the stabilizing agent of Pickering emulsion, adopts a mercaptan/isocyanate point beating method, and prepares the double-wall chamber microcapsule by a method of stabilizing the self-assembly of the capsule and adsorbing the self-assembly of the capsule on the surface of the large capsule. The prepared double-wall chamber microcapsule has the advantages that the inner wall and the outer wall of the microcapsule contain the repairing agent at the same time, the performance of responding cracks and releasing the repairing agent for many times can be realized, and the preparation of the intelligent self-repairing material is deeply influenced.
Drawings
FIG. 1 is an SEM picture of P (GMA-co-MMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD double-walled chamber microcapsules of example 1;
FIG. 2 is a TGA diagram of a double-walled-chamber microcapsule of P (GMA-co-MMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD in example 1;
FIG. 3 is the particle size distribution diagram of P (GMA-co-MMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD double-walled-chamber microcapsules in example 1.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1: preparation of P (GMA-co-MMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD double-wall-chamber microcapsule
DPE, glycidyl acrylate (GMA) and deionized water are mixed, added into a three-neck flask, mechanically stirred and heated to 80 ℃ in a water bath. Wherein GMA accounts for 8.75 percent of the mass fraction of the deionized water, and DPE accounts for 1.29 percent of the mass fraction of the GMA; preparing 0.75g/L water-soluble initiator, and adding 120mL into a three-necked bottle after the temperature of the water bath kettle rises to 80 ℃. Under mechanical stirring, heating in a water bath for reacting for 16-24 h, and then removing water by rotary evaporation; adding the DPE-PGMA prepolymer into the activated dialysis bag, and sealing. And putting the mixture into deionized water for dialysis for one week, respectively measuring the conductivities of the deionized water soaked in the dialysis bag and the freshly prepared deionized water, calculating the difference, obtaining a prepolymer when the absolute value is less than 0.001, and measuring the solid content after rotary evaporation.
Mixing DPE-PGMA prepolymer, DVB, MMA and dicyclopentadiene (DPCD) with deionized water, adding into a three-neck bottle, mechanically stirring, and emulsifying at high speed for 30 min. And (3) emulsifying the reaction solution to obtain a milky white uniform in color, heating the milky white uniform in color in a water bath to 80 ℃, mechanically stirring the milky white uniform in color at a speed of 200rmp/min, heating the milky white uniform in color in the water bath to react for 10-16 h, centrifuging the milky white uniform in color, washing the milky white uniform in color with alcohol for 1 time, and washing the milky white uniform in color with water for 3 times to obtain the small-size P (GMA-co-MMA-co-. Wherein the mass fraction of the DPE-PGMA prepolymer in the total reaction liquid is 11.57%, the mass fractions of the monomer and the DCPD in the total reaction liquid are 8.18% and 6.945%, respectively, and the mass ratio of the DVB to the MMA is 1.25: 1;
preparing small-size capsule emulsion with the mass concentration of 1.5%, and adding the small-size capsule emulsion into a three-neck flask. Mixing and stirring trimethylolpropane (3-mercaptopropane acid ester) (TMMP), isophorone diisocyanate (IPDI) and DCPD uniformly, adding into a three-neck flask, mechanically stirring, emulsifying at a high speed for 5-10 min, pouring into a beaker, and dropwise adding 1-2 mL of triethylamine. After the reaction is carried out for 20min at room temperature, the double-walled-chamber microcapsule is prepared by carrying out suction filtration, water washing and drying on the mixture to obtain the P (GMA-co-MMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD double-walled-chamber microcapsule. Wherein the molar ratio of the functional groups of mercaptan and isocyanate is 1: 1, the mass ratio of DCPD to the shell layer material monomer is 1: 1.
example 2P (GMA-co-MMA-co-DVB) @ E-51/(TMMP-co-IPDI) @ DCPD double-walled-chamber microcapsule preparation
DPE, glycidyl acrylate (GMA) and deionized water are mixed, added into a three-neck flask, mechanically stirred and heated to 80 ℃ in a water bath. Wherein GMA accounts for 8.75 percent of the mass fraction of the deionized water, and DPE accounts for 1.29 percent of the mass fraction of the GMA; preparing 0.75g/L water-soluble initiator, and adding 120mL into a three-necked bottle after the temperature of the water bath kettle rises to 80 ℃. Under mechanical stirring, heating in a water bath for reacting for 16-24 h, and then removing water by rotary evaporation; adding the DPE-PGMA prepolymer into the activated dialysis bag, and sealing. Putting the mixture into deionized water for dialysis for one week, respectively measuring the conductivities of the deionized water soaked in the dialysis bag and the freshly prepared deionized water, calculating the absolute value of the difference to be less than 0.001, discharging a prepolymer, and measuring the solid content after rotary evaporation;
mixing DPE-PGMA prepolymer, DVB, MMA, epoxy (E-51) and deionized water, adding into a three-neck bottle, and mechanically stirring and emulsifying at high speed for 30 min. And (3) emulsifying the reaction solution to obtain a milky white uniform in color, heating the emulsified reaction solution to 80 ℃ in a water bath, mechanically stirring the mixture at a speed of 200rmp/min, heating the mixture in the water bath for reaction for 10 to 16 hours, centrifuging the mixture, washing the mixture with alcohol for 1 time, and washing the mixture with water for 3 times to obtain the small-size P (GMA-co-MMA-co-DVB) @ E-51 microcapsule. Wherein the DPE-PGMA prepolymer accounts for 10.84 percent of the total reaction liquid by mass, the monomer and the E-51 respectively account for 6.19 percent and 7.05 percent of the total reaction liquid by mass, and the mass ratio of DVB to MMA is 1: 1;
preparing small-size capsule emulsion with the mass concentration of 1.5%, and adding the small-size capsule emulsion into a three-neck flask. Mixing and stirring trimethylolpropane (3-mercaptopropane acid ester) (TMMP), isophorone diisocyanate (IPDI) and DCPD uniformly, adding into a three-neck flask, mechanically stirring, emulsifying at a high speed for 5-10 min, pouring into a beaker, and dropwise adding 1-2 mL of triethylamine. After the reaction is carried out for 20min at room temperature, the double-walled-chamber microcapsule is prepared by P (GMA-co-MMA-DVB) @ E-51/(TMMP-co-IPDI) @ DCPD double-walled-chamber microcapsule after suction filtration, water washing and drying. Wherein the molar ratio of the functional groups of mercaptan and isocyanate is 1: 1, the mass ratio of DCPD to the shell layer material monomer is 1: 1.
example 3: preparation of P (GMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD double-wall chamber microcapsule
DPE, glycidyl acrylate (GMA) and deionized water are mixed, added into a three-neck flask, mechanically stirred and heated to 80 ℃ in a water bath. Wherein GMA accounts for 8.75 percent of the mass fraction of the deionized water, and DPE accounts for 1.29 percent of the mass fraction of the GMA; preparing 0.75g/L water-soluble initiator, and adding 120mL into a three-necked bottle after the temperature of the water bath kettle rises to 80 ℃. Under mechanical stirring, heating in a water bath for reacting for 16-24 h, and then removing water by rotary evaporation; adding the DPE-PGMA prepolymer into the activated dialysis bag, and sealing. And putting the mixture into deionized water for dialysis for one week, respectively measuring the conductivities of the deionized water soaked in the dialysis bag and the freshly prepared deionized water, calculating the difference, obtaining a prepolymer when the absolute value is less than 0.001, and measuring the solid content after rotary evaporation.
Mixing DPE-PGMA prepolymer, DVB and dicyclopentadiene (DPCD) with deionized water, adding into a three-neck bottle, mechanically stirring, and emulsifying at high speed for 30 min. And (3) emulsifying the reaction solution to obtain a milky white uniform in color, heating the milky white uniform in color in a water bath to 80 ℃, mechanically stirring the milky white uniform in color at a speed of 200rmp/min, heating the milky white uniform in color in the water bath to react for 10-16 h, centrifuging the milky white uniform in color, washing the milky white uniform in color with alcohol for 1 time, and washing the milky white uniform in color with water for 3 times to obtain the small-size P (GMA-co-MMA-co-. Wherein the DPE-PGMA prepolymer accounts for 7 percent of the total reaction liquid by mass, and the monomer and the DCPD respectively account for 7 percent of the total reaction liquid by mass;
preparing small-size capsule emulsion with the mass concentration of 3%, and adding the small-size capsule emulsion into a three-neck flask. Mixing and stirring trimethylolpropane (3-mercaptopropane acid ester) (TMMP), isophorone diisocyanate (IPDI) and DCPD uniformly, adding into a three-neck flask, mechanically stirring, emulsifying at a high speed for 5-10 min, pouring into a beaker, and dropwise adding 1-2 mL of triethylamine. After the reaction is carried out for 20min at room temperature, the double-walled-chamber microcapsule is prepared by P (GMA-co-DVB) @ DCPD/(TMMP-co-IPDI) @ DCPD through suction filtration, water washing and drying. Wherein the molar ratio of the functional groups of mercaptan and isocyanate is 1: 1, the mass ratio of DCPD to the shell layer material monomer is 1: 1.
Claims (4)
1. a preparation method of a microcapsule with a double-wall chamber structure for adsorbing small capsules on the surface of the outer wall of a large capsule is characterized by comprising the following steps:
step 1: mixing 1, 1-diphenylethylene and glycidyl acrylate with deionized water, and heating to 65-80 ℃ in a water bath; wherein the mass fraction of the glycidyl acrylate in the deionized water is 5-14%, and the mass fraction of the 1, 1-diphenylethylene in the glycidyl acrylate is 0.6-3%;
step 2: adding 45-180 mL of initiator aqueous solution, heating in a water bath under stirring for reacting for 16-24 h, and performing rotary evaporation to remove water to obtain a DPE-PGMA prepolymer; the concentration of the initiator aqueous solution is 0.5-2.0 g/L;
and step 3: adding the DPE-PGMA prepolymer into the activated dialysis bag, and sealing; putting the mixture into deionized water for dialysis for one week, respectively measuring the conductivities of the deionized water soaked in the dialysis bag and the freshly prepared deionized water, calculating the difference, and pouring out the prepolymer with the absolute value less than 0.001;
and 4, step 4: mixing the DPE-PGMA prepolymer, the monomer, the core material A and deionized water, and stirring and emulsifying at a high speed for 10-40 min; heating to 80 ℃ in a water bath, mechanically stirring for 150-500 rmp, heating in the water bath for reaction for 10-16 h, centrifuging, washing with alcohol for 1 time, and washing with water for 3 times to obtain microcapsules; wherein the DPE-PGMA prepolymer accounts for 7-14% of the total reaction liquid by mass, and the monomer and the core material A respectively account for 4-15% of the total reaction liquid by mass;
and 5: preparing the microcapsule of the step 4 into a capsule emulsion with the mass concentration of 0.5-6%, mixing the capsule emulsion with shell layer monomer mercaptan, isocyanate and the core material B, mechanically stirring and emulsifying at a high speed for 5-10 min, then dropwise adding 1-2 mL of triethylamine, reacting at room temperature for 20min, and then performing suction filtration, washing and drying to obtain the double-wall-chamber microcapsule; wherein the molar ratio of the shell layer monomer mercaptan to the functional groups of the isocyanate is 1: 1, and the mass ratio of the core material B to the shell layer monomer mercaptan is 0.5-2: 1;
the monomer is methyl methacrylate, diethylbenzene or a mixture of two monomers mixed in any proportion;
the core material A is a mixture of one, two or more than two of dicyclopentadiene, epoxy E-51 and epoxy 184 mixed in any proportion;
the core material B is at least one of dicyclopentadiene and a mixture of dicyclopentadiene and toluene mixed in any proportion.
2. The method for preparing the microcapsule with double-wall chamber structure, which adsorbs the small capsule on the outer wall surface of the large capsule according to claim 1, wherein: the initiator is potassium persulfate, ammonium persulfate, azobisisobutyronitrile or dibenzoyl peroxide.
3. The method for preparing the microcapsule with double-wall chamber structure, which adsorbs the small capsule on the outer wall surface of the large capsule according to claim 1, wherein: the mercaptan is one or a mixture of two or more of trimethylolpropane (3-mercaptopropane acid ester), tris (2-hydroxyethyl) isocyanurate-tris (mercaptopropionate) and pentaerythritol tetrakis (3-mercaptopropionate) which are mixed in any ratio.
4. The method for preparing the microcapsule with double-wall chamber structure, which adsorbs the small capsule on the outer wall surface of the large capsule according to claim 1, wherein: the isocyanate is one or a mixture of two or more of isophorone diisocyanate, toluene diisocyanate and hexamethylene diisocyanate which are mixed according to any ratio.
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| CN111334176A (en) * | 2020-03-09 | 2020-06-26 | 沪宝新材料科技（上海）股份有限公司 | Solvent-free double-component finish paint for plastic track |
| CN112934135B (en) * | 2021-01-21 | 2023-01-24 | 西北工业大学 | Preparation method of capsule type stable particles for oil-in-water Pickering emulsion |
| CN114790379A (en) * | 2022-04-24 | 2022-07-26 | 西南石油大学 | Double-chamber microcapsule for drilling fluid and preparation method and application thereof |
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| CN102205225B (en) * | 2011-06-02 | 2013-02-27 | 北京科技大学 | Method for preparing enhanced epoxy resin/curing agent double-wall microcapsule |
| CN103254372B (en) * | 2013-04-08 | 2015-07-08 | 中山大学 | Multilayer microcapsule for self-repair polymer materials and its preparation method |
| WO2015171429A1 (en) * | 2014-05-07 | 2015-11-12 | Wichita State University | Nanocomposite microcapsules for self-healing of composite articles |
| CN105080441B (en) * | 2015-07-28 | 2017-10-13 | 西北工业大学 | A kind of preparation method for coating liquid olefinic microcapsules |
| US10316199B2 (en) * | 2016-07-11 | 2019-06-11 | Microtek Laboratories Inc. | Capsules having surfactant tethered outer shells and methods for making same |
| CN107088389A (en) * | 2017-05-26 | 2017-08-25 | 天津工业大学 | A kind of two-component capsule and preparation method thereof |
| CN107312140B (en) * | 2017-06-27 | 2020-03-31 | 沈阳化工研究院有限公司 | Self-repairing microcapsule for metal anticorrosive coating and preparation method thereof |
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