CN114950293A - Hydrophobic double-shell isocyanate type self-repairing microcapsule and preparation method and application thereof - Google Patents
Hydrophobic double-shell isocyanate type self-repairing microcapsule and preparation method and application thereof Download PDFInfo
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- CN114950293A CN114950293A CN202210662546.8A CN202210662546A CN114950293A CN 114950293 A CN114950293 A CN 114950293A CN 202210662546 A CN202210662546 A CN 202210662546A CN 114950293 A CN114950293 A CN 114950293A
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 85
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 239000011162 core material Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 13
- 239000004305 biphenyl Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 5
- 229920002635 polyurethane Polymers 0.000 claims abstract description 5
- 125000005504 styryl group Chemical group 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 235000010489 acacia gum Nutrition 0.000 claims description 7
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000008439 repair process Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000011257 shell material Substances 0.000 description 46
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 9
- 239000011527 polyurethane coating Substances 0.000 description 7
- 238000004945 emulsification Methods 0.000 description 6
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000002775 capsule Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- -1 fluorine modified silicon dioxide Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Images
Classifications
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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
- B01J13/16—Interfacial polymerisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a hydrophobic double-shell isocyanate type self-repairing microcapsule as well as a preparation method and application thereof, belonging to the technical field of polymer chemistry. Firstly, preparing a multifunctional isocyanate prepolymer core material TMP-IPDI by using TMP and IPDI monomers, and then preparing fluorescent isocyanate type self-repairing microcapsule powder by using polyurethane as a wall material and the prepared core material and fluorescent agent 4, 4-bis (2-sodium disulfonate styryl) biphenyl; and finally, carrying out secondary coating on the prepared fluorescent isocyanate type self-repairing microcapsule by using silicon dioxide modified by tridecafluorooctyltrimethoxysilane to obtain the hydrophobic double-shell isocyanate type self-repairing microcapsule. The method is simple to operate, and the prepared microcapsule has high self-repairing efficiency and good compactness, can be used as coating filler to repair coating microcracks, and has the functions of hydrophobicity, corrosion resistance and the like.
Description
Technical Field
The invention belongs to the technical field of polymer chemistry, and particularly relates to a hydrophobic double-shell isocyanate type self-repairing microcapsule as well as a preparation method and application thereof.
Background
In the using process of the coating material, the micro-nano rough structure on the surface of the coating material is extremely easy to be scratched by external force and damaged, so that the performance of the coating material is influenced, and the large-scale popularization and practical application of the coating material are limited to a greater extent.
In order to overcome the above problems, some researchers add self-repairing microcapsules to a coating material to prepare a self-repairing coating material having excellent surface stability and recyclability. When the surface is damaged, the microcapsules are broken and the capsule core flows out to repair the microcracks. The coating properties can be improved spontaneously or under certain conditions. At present, the traditional self-repairing microcapsule contains a repairing agent (capsule core) with high viscosity and poor fluidity, and the repairing agent needs a curing agent and the conditions of external light, electricity and the like to play a repairing role, so that the repairing agent is limited in practical application and has high cost. Aiming at the problems, the isocyanate type microcapsule is prepared in a laboratory, and the principle is that when a shell material is broken, the isocyanate capsule core can realize self-repairing by the participation of water and oxygen in the air, and the isocyanate type microcapsule has the advantages of small viscosity, strong fluidity, low cost, small pollution and the like.
However, the reactivity of a single isocyanate (capsule core) monomer is low, and the problem of low corrosion resistance and self-repairing efficiency exists as a core material of the microcapsule self-repairing coating, while the traditional microcapsule shell prepared by adopting an interfacial polymerization method has poor compactness and low mechanical strength, and the isocyanate capsule core which can participate in the reaction in the air can not be effectively protected for a long time, so that the microcapsule has the problems of short storage time, poor environmental tolerance and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention discloses a hydrophobic double-shell isocyanate type self-repairing microcapsule, a preparation method and application thereof, the operation is simple, and the prepared microcapsule has high self-repairing efficiency and good compactness.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule, which comprises the following steps:
s1: preparing a polyfunctional isocyanate prepolymer core material TMP-IPDI by using TMP and IPDI monomers;
s2: preparing fluorescent isocyanate type self-repairing microcapsule powder by taking polyurethane as a wall material, a core material prepared from S1 and fluorescent agent 4, 4-bis (2-disulfonate styryl) biphenyl;
s3: and (3) coating the fluorescent isocyanate type self-repairing microcapsule prepared by S2 for the second time by using silicon dioxide modified by tridecafluorooctyltrimethoxysilane to obtain the hydrophobic double-shell isocyanate type self-repairing microcapsule.
Preferably, S1 is specifically: mixing 2 parts of TMP, 10 parts of cyclohexanone and 6 parts of benzene in parts by mass, stirring, placing in a heating bath, heating to 75 ℃, and then cooling to 60 ℃ to obtain a dry solution for later use; and (2) putting 13 parts of IPDI in a heating bath at 40 ℃, adding 0.08 part of DBTDL under stirring, dropwise adding the drying solution, raising the reaction temperature to 60 ℃ after the dropwise adding is finished, and continuously reacting for 5 hours to obtain the polyfunctional isocyanate prepolymer core material TMP-IPDI.
Further preferably, the dropping time of the dried solution is not more than 1 hour.
Preferably, S2 is specifically: weighing 5 parts of ethyl acetate, 0.8-4.1 parts of HDI tripolymer, 5 parts of TMP-IPDI prepared from S1 and 0.1-0.5 part of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl in parts by mass, and uniformly stirring at room temperature to obtain an oil phase system; putting Arabic gum into 120 parts of distilled water, and stirring uniformly at room temperature to obtain a water phase system; slowly pouring the oil phase system into the water phase system under the high-speed stirring state of the prepared water phase system, and continuously emulsifying for 15min after mixing to obtain a suspension system; adding 0.2-1.0 part of BDO into a suspension system, continuously reacting for 2-6h at the temperature of 40-80 ℃ and the rotation speed of 300-700rpm, naturally cooling the obtained microcapsule suspension after the reaction is finished, and repeatedly performing suction filtration, washing and drying to obtain the fluorescent isocyanate type self-repairing microcapsule powder.
Further preferably, the rotation speed of the aqueous system during high-speed stirring is 8000 rpm.
Preferably, S3 is specifically: taking 2 parts by mass of fluorescent isocyanate type self-repairing microcapsule powder prepared by S2, dispersing the fluorescent isocyanate type self-repairing microcapsule powder in 10 parts by mass of deionized water, adding 2-10 parts by mass of tetraethoxysilane alcohol solution prepared by TEOS and ethanol, stirring the mixture for 30min at the rotating speed of 500r/min at 50 ℃, and then adjusting the pH value to 9 to initiate the hydrolysis reaction of TEOS; continuously stirring for 30min, adding tridecafluorooctyl trimethoxysilane, and reacting for 5 h; raising the temperature to 85 ℃, continuing stirring, and condensing and refluxing until the ethanol is completely evaporated; reducing the temperature to 40 ℃, aging for 12h, and keeping stirring; and after the reaction is finished, washing and filtering the product, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain the hydrophobic double-shell isocyanate type self-repairing microcapsule.
Further preferably, ammonia or hydrochloric acid is used for pH adjustment dropwise; the washing was with petroleum ether and deionized water.
The invention discloses a hydrophobic double-shell isocyanate type self-repairing microcapsule prepared by the preparation method, which is spherical in appearance, flat and smooth in surface, 10-70um in particle size and 0.67-4.69um in wall thickness.
The invention discloses an application of the hydrophobic double-shell isocyanate type self-repairing microcapsule as a self-repairing filler in a coating.
Preferably, the mass fraction of the hydrophobic double-shell isocyanate type self-repairing microcapsules in the coating is 3% -5%.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule, which adopts an interfacial polymerization method to prepare a fluorescent isocyanate type self-repairing microcapsule taking environment-friendly polyurethane as a wall material and taking TMP-IPDI and 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl with multiple functionality and high molecular weight as core materials. The method is characterized in that a sol-gel method is adopted, silicon dioxide prepared by hydrolyzing tetraethoxysilane is adsorbed on the surface layer of the microcapsule to form a silicon dioxide double shell, tridecafluorooctyltrimethoxysilane is used for modifying the silicon dioxide to prepare the double-shell isocyanate type self-repairing microcapsule with hydrophobic, anticorrosion and fluorescence detection performances, and the fluorescent double-shell microcapsule is applied to a polyurethane coating. When the coating has microcracks under the action of external force, the microcapsules at the microcracks are broken, the polyfunctional isocyanate and the fluorescent agent 4, 4-bis (2-disulfonate styryl) biphenyl wrapped in the microcapsules flow out, and the isocyanate groups react with water in the air to generate polyurea which is filled at the microcracks, so that the microcrack repairing effect is achieved. Meanwhile, green fluorescence generated by the repair part through irradiation of an ultraviolet lamp achieves a self-repairing self-detection function; fluorine on the surface of the modified silicon dioxide double-shell microcapsule can migrate to the surface of the coating, so that the surface of the coating has a hydrophobic function, and the hydrophobic function can be recovered at a repaired position. Through the treatment, the fluorescent double-shell isocyanate type self-repairing microcapsule is successfully prepared and applied to the polyurethane coating, so that the polyurethane coating has excellent self-repairing performance. The TMP-IPDI core material with multiple functionality and high molecular weight has higher reaction activity, and the self-repairing efficiency of the coating is improved. The silicon dioxide is modified by the tridecafluorooctyl trimethoxy silane, so that the coating has a self-repairing and self-detecting function and simultaneously the performances of hydrophobicity, corrosion resistance and the like of the coating are enhanced.
Further, the benzene is selected during the core preparation process in order to remove water from the TMP and prevent the reaction of water and IPDI to form polyurea.
Furthermore, the dropping time of the drying solution is longer in the preparation process of the core material, so that TMP and IPDI are uniformly and fully reacted, and the phenomenon of agglomeration is prevented from causing insufficient reaction.
Furthermore, 4-bis (2-disulfonate styryl) biphenyl in the fluorescent double-shell isocyanate type microcapsule core material is selected, the fluorescent agent is low in cost and strong in fluorescence, and the fluorescent agent can be added by only 2% of the total amount of the microcapsule to enable the microcapsule to have strong fluorescence performance.
Further, the rotation speed is selected during the emulsification process, so that the oil phase is uniformly dispersed in the water phase, and an emulsion with uniform size and small particle size is formed.
Further, the amount of ethyl orthosilicate is selected in the double-shell coating process, so that the double-shell particle size is the smallest and the coating is the most compact, and the double-shell self-repairing microcapsule with small particle size and good compactness is formed.
Further, the pH value is selected in the double-shell coating process, so that the double-shell coating is most compact, the compactness of the isocyanate type self-repairing microcapsule is enhanced, and the self-repairing efficiency of the isocyanate type self-repairing microcapsule is improved.
According to the hydrophobic double-shell isocyanate type self-repairing microcapsule prepared by the method, the core material of the microcapsule is polyfunctional isocyanate, and the reaction activity is high. The surface of the microcapsule is provided with a compact silicon dioxide lamellar, and the structure can improve the sealing property of the isocyanate type microcapsule and lead the storage time of the microcapsule to be longer. The fluorine modified silicon dioxide endows the microcapsule surface with functions of hydrophobicity and the like.
The application of the hydrophobic double-shell isocyanate type self-repairing microcapsule disclosed by the invention as a self-repairing filler in a coating can repair microcracks of the coating, and the modified double-shell microcapsule enables the coating to achieve the self-repairing function and simultaneously has the functions of hydrophobicity, corrosion resistance and the like.
Drawings
FIG. 1 is an infrared image of a double-shell microcapsule core material prepared by the present invention;
FIG. 2 is an infrared image of single and double shell microcapsules prepared in accordance with the present invention;
FIG. 3 is a particle size and scanning diagram of the double-shell microcapsule prepared by the present invention;
FIG. 4 is a scanned image of double-shell microcapsules made according to the present invention;
FIG. 5 is a scanned image of the double-shell microcapsule wall material prepared by the present invention;
FIG. 6 is a graph of contact angles of coatings produced by different double-shell microcapsule loadings according to the present invention;
FIG. 7 is a scanned graph of a polyurethane coating containing 3% microcapsule addition before self-healing;
FIG. 8 is a scan of a polyurethane coating after self-healing with 3% microcapsule loading.
Detailed Description
In this context, TMP is trimethylolpropane, IPDI is isophorone diisocyanate, DBTDL is di-n-butyltin dilaurate, HDI is hexamethylene diisocyanate, BDO is 1, 4-butanediol, and TEOS is tetraethoxysilane.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The method comprises the following steps: preparation of multifunctional isocyanate prepolymer core material
2g TMP, 10g cyclohexanone and 6g benzene were added together and stirred in a 100 ml three-necked round-bottomed flask equipped with a condenser and a magnetic stirrer and placed in a heating bath to heat to 75 ℃; benzene removed the water from the solution, and then the solution was cooled to 60 ℃ to obtain a dry solution. The solution was added to the dropping funnel. 13g of IPDI was charged to a three-necked round bottom flask equipped with a condenser and a magnetic stirrer and placed in a heating bath. The temperature was controlled at 40 ℃ and 0.08g of DBTDL was added with magnetic stirring. The solution in the dropping funnel was transferred to the flask over 1 h. Then, the reaction temperature was raised to about 60 ℃ and the reaction was continued for 5 hours.
Step two: preparation of fluorescent isocyanate type self-repairing microcapsule
Preparing an oil phase: 5g of TMP-IPDI, 1% of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl, 4.1g of HDI trimer and 5g of ethyl acetate are weighed and stirred uniformly at room temperature to form an oil phase system.
Preparing a water phase: a certain amount of Arabic gum is weighed respectively, put into 120mL of distilled water and stirred uniformly at room temperature to serve as a water phase system.
Emulsifying the suspension: and (3) placing the water phase system under the condition that the rotating speed of a digital display dispersion machine is 8000rpm, slowly pouring the oil phase system into the water phase system, mixing the two, and continuously emulsifying for 15min to obtain a suspension system.
Preparing microcapsules: pouring the suspension system obtained by emulsification into a three-neck flask, placing the three-neck flask into a constant-temperature water bath kettle, then adding 1g of BDO (dissolved in 5mL of water), after the addition is finished, allowing the system to continuously react for 2h under the conditions of 40 ℃ and 300rpm, after the reaction is finished, naturally cooling the obtained microcapsule suspension, repeatedly performing suction filtration, washing and drying to obtain microcapsule white powder.
Step three: preparation of modified silicon dioxide double-shell isocyanate type microcapsule
2g of the prepared fluorescent isocyanate type microcapsule is dispersed in 10g of deionized water, and transferred to a three-neck flask, 2g of TEOS and (1:1) ethanol are prepared into ethyl orthosilicate alcohol solution, and the mixture is uniformly stirred. Pouring the mixture into a three-neck flask containing the fluorescent isocyanate type microcapsules, and stirring the mixture for 30min at the rotating speed of 500r/min at 50 ℃ to wrap the microcapsules in the TEOS solution to be fully and uniformly dispersed. To the flask was added dropwise ammonia (hydrochloric acid) to adjust the pH of the solution to 9. The hydrolysis reaction of TEOS was initiated. Stirring is continued, after 30min, a certain amount of tridecafluorooctyltrimethoxysilane is added, and the reaction is carried out for 5 h. The temperature is raised to 85 ℃, stirring is continued, and condensation reflux is carried out until all the ethanol is evaporated. The temperature is reduced to 40 ℃, and the mixture is aged for 12 hours without stopping stirring. After the reaction is finished, washing and filtering the product with petroleum ether and deionized water, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain modified SiO 2 a/PU microcapsule.
Example 2
A preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule comprises the following steps:
example 2
The method comprises the following steps: preparation of multifunctional isocyanate prepolymer core material
2g TMP, 10g cyclohexanone and 6g benzene were added together and stirred in a 100 ml three-necked round-bottomed flask equipped with a condenser and a magnetic stirrer and placed in a heating bath to heat to 75 ℃; benzene removed the water from the solution, and then the solution was cooled to 60 ℃ to obtain a dry solution. The solution was added to the dropping funnel. 13g of IPDI was charged to a three-necked round bottom flask equipped with a condenser and a magnetic stirrer and placed in a heating bath. The temperature was controlled at 40 ℃ and 0.08g of DBTDL was added with magnetic stirring. The solution in the dropping funnel was transferred to the flask over 1 h. Then, the reaction temperature was raised to about 60 ℃ and the reaction was continued for 5 hours.
Step two: preparation of fluorescent isocyanate type self-repairing microcapsule
Preparing an oil phase: 5g of TMP-IPDI, 0.2g of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl, 2.1g of HDI trimer and 5g of ethyl acetate were weighed and stirred uniformly at room temperature to prepare an oil phase system.
Preparing a water phase: a certain amount of Arabic gum is weighed respectively, put into 120mL of distilled water and stirred uniformly at room temperature to serve as a water phase system.
Emulsifying the suspension: and (3) placing the water phase system under the condition that the rotating speed of a digital display dispersion machine is 8000rpm, slowly pouring the oil phase system into the water phase system, mixing the two, and continuously emulsifying for 15min to obtain a suspension system.
Preparing microcapsules: pouring the suspension system obtained by emulsification into a three-neck flask, placing the three-neck flask into a constant-temperature water bath kettle, then adding 0.4g of BDO (dissolved in 5mL of water), after the addition is finished, continuously reacting the system for 3h under the conditions of 50 ℃ and 400rpm, after the reaction is finished, naturally cooling the obtained microcapsule suspension, repeatedly carrying out suction filtration, washing and drying to obtain microcapsule white powder.
Step three: preparation of modified silicon dioxide double-shell isocyanate type microcapsule
2g of the prepared fluorescent isocyanate type microcapsule is dispersed in 10g of deionized water, and transferred to a three-neck flask, 4g of TEOS and (1:1) ethanol are prepared into ethyl orthosilicate alcohol solution, and the mixture is uniformly stirred. Pouring into a three-neck flask containing fluorescent isocyanate type microcapsules, and stirring at 50 ℃ at a rotating speed of 500r/min for 30min to ensure that the microcapsules are wrapped in the TEOS solution and are fully and uniformly dispersed. To the flask was added dropwise ammonia (hydrochloric acid) to adjust the pH of the solution to 9. The hydrolysis reaction of TEOS was initiated. Stirring is continued, after 30min, a certain amount of tridecafluorooctyltrimethoxysilane is added, and the reaction is carried out for 5 h. The temperature is raised to 85 ℃, stirring is continued, and condensation reflux is carried out until all ethanol is evaporated. The temperature is reduced to 40 ℃, and the mixture is aged for 12 hours without stopping stirring. After the reaction is finished, washing and filtering the product with petroleum ether and deionized water, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain modified SiO 2 a/PU microcapsule.
Example 3
A preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule comprises the following steps:
example 3
The method comprises the following steps: preparation of multifunctional isocyanate prepolymer core material
2g TMP, 10g cyclohexanone and 6g benzene were added together and stirred in a 100 ml three-necked round-bottomed flask equipped with a condenser and a magnetic stirrer and placed in a heating bath to heat to 75 ℃; benzene removed the water from the solution, and then the solution was cooled to 60 ℃ to obtain a dry solution. The solution was added to the dropping funnel. 13g of IPDI was charged to a three-necked round bottom flask equipped with a condenser and a magnetic stirrer and placed in a heating bath. The temperature was controlled at 40 ℃ and 0.08g of DBTDL was added with magnetic stirring. The solution in the dropping funnel was transferred to the flask over 1 h. Then, the reaction temperature was raised to about 60 ℃ and the reaction was continued for 5 hours.
Step two: preparation of fluorescent isocyanate type self-repairing microcapsule
Preparing an oil phase: 5g of TMP-IPDI, 0.3g of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl, 1.4g of HDI trimer and 5g of ethyl acetate were weighed and stirred uniformly at room temperature to prepare an oil phase system.
Preparing a water phase: a certain amount of Arabic gum is weighed respectively, put into 120mL of distilled water and stirred uniformly at room temperature to serve as a water phase system.
Emulsifying the suspension: and (3) placing the water phase system under the condition that the rotating speed of a digital display dispersion machine is 8000rpm, slowly pouring the oil phase system into the water phase system, mixing the two, and continuously emulsifying for 15min to obtain a suspension system.
Preparing microcapsules: pouring the suspension system obtained by emulsification into a three-neck flask, placing the three-neck flask into a constant-temperature water bath kettle, then adding 0.3g of BDO (dissolved in 5mL of water), after the addition is finished, allowing the system to continuously react for 4 hours at the temperature of 60 ℃ and the speed of 500rpm, after the reaction is finished, naturally cooling the obtained microcapsule suspension, repeatedly carrying out suction filtration, washing and drying to obtain microcapsule white powder.
Step three: preparation of modified silicon dioxide double-shell isocyanate type microcapsule
2g of the prepared fluorescent isocyanate-type microcapsules were dispersed in 10g of deionized water and transferred to a three-necked flask. 6g of TEOS and (1:1) ethanol are mixed to prepare ethyl orthosilicate alcoholic solution, and the mixture is stirred uniformly. Pouring into a three-neck flask containing fluorescent isocyanate type microcapsules, and stirring at 50 ℃ at a rotating speed of 500r/min for 30min to ensure that the microcapsules are wrapped in the TEOS solution and are fully and uniformly dispersed. To the flask was added dropwise ammonia (hydrochloric acid) to adjust the pH of the solution to 9. The hydrolysis reaction of TEOS was initiated. Stirring is continued, after 30min, a certain amount of tridecafluorooctyltrimethoxysilane is added, and the reaction is carried out for 5 h. The temperature is raised to 85 ℃, stirring is continued, and condensation reflux is carried out until all ethanol is evaporated. The temperature is reduced to 40 ℃, and the mixture is aged for 12 hours without stopping stirring. After the reaction is finished, washing and filtering the product with petroleum ether and deionized water, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain modified SiO 2 a/PU microcapsule.
Example 4
A preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule comprises the following steps:
example 4
The method comprises the following steps: preparation of multifunctional isocyanate prepolymer core material
2g TMP, 10g cyclohexanone and 6g benzene were added together and stirred in a 100 ml three-necked round-bottomed flask equipped with a condenser and a magnetic stirrer and placed in a heating bath to heat to 75 ℃; benzene removed the water from the solution, and then the solution was cooled to 60 ℃ to obtain a dry solution. The solution was added to the dropping funnel. 13g of IPDI was charged to a three-necked round bottom flask equipped with a condenser and a magnetic stirrer and placed in a heating bath. The temperature was controlled at 40 ℃ and 0.08g of DBTDL was added with magnetic stirring. The solution in the dropping funnel was transferred to the flask over 1 h. Then, the reaction temperature was raised to about 60 ℃ and the reaction was continued for 5 hours.
Step two: preparation of fluorescent isocyanate type self-repairing microcapsule
Preparing an oil phase: 5g of TMP-IPDI, 0.4g of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl, 1.0g of HDI trimer and 5g of ethyl acetate were weighed and stirred uniformly at room temperature to prepare an oil phase system.
Preparing a water phase: a certain amount of Arabic gum is weighed respectively, put into 120mL of distilled water and stirred uniformly at room temperature to serve as a water phase system.
Emulsifying the suspension: and (3) placing the water phase system under the condition that the rotating speed of a digital display dispersion machine is 8000rpm, slowly pouring the oil phase system into the water phase system, mixing the two, and continuously emulsifying for 15min to obtain a suspension system.
Preparing microcapsules: pouring the suspension system obtained by emulsification into a three-neck flask, placing the three-neck flask into a constant-temperature water bath kettle, then adding 0.2g of BDO (dissolved in 5mL of water), after the addition is finished, allowing the system to continuously react for 5 hours at 70 ℃ and 600rpm, after the reaction is finished, naturally cooling the obtained microcapsule suspension, and repeatedly performing suction filtration, washing and drying to obtain microcapsule white powder.
Step three: preparation of modified silicon dioxide double-shell isocyanate type microcapsule
2g of the prepared fluorescent isocyanate type microcapsule is dispersed in 10g of deionized water, and transferred to a three-neck flask, 8g of TEOS and (1:1) ethanol are prepared into ethyl orthosilicate alcohol solution, and the mixture is uniformly stirred. Pouring into a three-neck flask containing fluorescent isocyanate type microcapsules, and stirring at 50 ℃ at a rotating speed of 500r/min for 30min to ensure that the microcapsules are wrapped in the TEOS solution and are fully and uniformly dispersed. To the flask was added dropwise ammonia (hydrochloric acid) to adjust the pH of the solution to 9. The hydrolysis reaction of TEOS was initiated. Stirring is continued, after 30min, a certain amount of tridecafluorooctyltrimethoxysilane is added, and the reaction is carried out for 5 h. The temperature is raised to 85 ℃, stirring is continued, and condensation reflux is carried out until all ethanol is evaporated. The temperature is reduced to 40 ℃, and the mixture is aged for 12 hours without stopping stirring. After the reaction is finished, washing and filtering the product with petroleum ether and deionized water, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain modified SiO 2 a/PU microcapsule.
Example 5
A preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule comprises the following steps:
example 5
The method comprises the following steps: preparation of multifunctional isocyanate prepolymer core material
2g TMP, 10g cyclohexanone and 6g benzene were added together and stirred in a 100 ml three-necked round-bottomed flask equipped with a condenser and a magnetic stirrer and placed in a heating bath to heat to 75 ℃; benzene removed the water from the solution, and then the solution was cooled to 60 ℃ to obtain a dry solution. The solution was added to the dropping funnel. 13g of IPDI was charged to a three-necked round bottom flask equipped with a condenser and a magnetic stirrer and placed in a heating bath. The temperature was controlled at 40 ℃ and 0.08g of DBTDL was added with magnetic stirring. The solution in the dropping funnel was transferred to the flask over 1 h. Then, the reaction temperature was raised to about 60 ℃ and the reaction was continued for 5 hours.
Step two: preparation of fluorescent isocyanate type self-repairing microcapsule
Preparing an oil phase: 5g of TMP-IPDI, 0.5g of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl, 0.8g of HDI trimer and 5g of ethyl acetate were weighed and stirred uniformly at room temperature to prepare an oil phase system.
Preparing a water phase: a certain amount of Arabic gum is weighed respectively, put into 120mL of distilled water and stirred uniformly at room temperature to serve as a water phase system.
Emulsifying the suspension: and (3) placing the water phase system under the condition that the rotating speed of a digital display dispersion machine is 8000rpm, slowly pouring the oil phase system into the water phase system, mixing the two, and continuously emulsifying for 15min to obtain a suspension system.
Preparing microcapsules: pouring the suspension system obtained by emulsification into a three-neck flask, placing the three-neck flask into a constant-temperature water bath kettle, then adding 0.2g of BDO (dissolved in 5mL of water), after the addition is finished, allowing the system to continuously react for 6h under the conditions of 80 ℃ and 700rpm, after the reaction is finished, naturally cooling the obtained microcapsule suspension, repeatedly performing suction filtration, washing and drying to obtain microcapsule white powder.
Step three: preparation of modified silicon dioxide double-shell isocyanate type microcapsule
Taking 2g of prepared fluorescent isocyanate type microcapsule, dispersing in 10g of deionized water, transferring to a three-neck flask, preparing ethyl orthosilicate alcohol solution by 10g of TEOS and (1:1) ethanolAnd stirring uniformly. Pouring into a three-neck flask containing fluorescent isocyanate type microcapsules, and stirring at 50 ℃ at a rotating speed of 500r/min for 30min to ensure that the microcapsules are wrapped in the TEOS solution and are fully and uniformly dispersed. To the flask was added dropwise ammonia (hydrochloric acid) to adjust the pH of the solution to 9. The hydrolysis reaction of TEOS was initiated. Stirring is continued, after 30min, a certain amount of tridecafluorooctyltrimethoxysilane is added, and the reaction is carried out for 5 h. The temperature is raised to 85 ℃, stirring is continued, and condensation reflux is carried out until all ethanol is evaporated. The temperature is reduced to 40 ℃, and the mixture is aged for 12 hours without stopping stirring. After the reaction is finished, washing and filtering the product with petroleum ether and deionized water, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain modified SiO 2 a/PU microcapsule.
FIG. 1 is an infrared image of microcapsule core material, compared with IPDI, core material TMP-IPDI is 2273cm -1 Has a stretching vibration peak of-NCO at 1472cm -1 Has a stretching vibration peak of-CH 3 at 1365cm -1 The stretching vibration peak of-CH 2 is shown, which indicates that the core material TMP-IPDI is successfully synthesized.
FIG. 2 is an infrared image of polyurethane single shell and silica double shell microcapsules at 1099cm compared to single shell microcapsules -1 The stretching vibration peak of Si-O-Si appears, which indicates that the silicon dioxide double shell is successfully coated.
FIG. 3 is a scanning graph of the particle size of the microcapsule, from which it can be seen that the particle size of the double-shell microcapsule is 29.201um, and the particle size distribution is relatively uniform; the scanning image shows that the microcapsule is spherical and has a flat and smooth surface.
Fig. 4 is a scanned view of microcapsules, from which it can be seen that the surface of the microcapsules is coated with a silica sheet layer, illustrating the successful preparation of double-shell microcapsules.
Fig. 5 shows the grinding of the broken microcapsules, from which it can be seen that the wall thickness of the microcapsules is 2 um.
Fig. 6 shows polyurethane coatings prepared by different microcapsule adding amounts, and it can be seen from the figure that when the microcapsule adding amount is 3% -5%, the coating has good hydrophobicity, wherein the hydrophobicity is optimal when the microcapsule adding amount is 3%, and the contact angle can reach 104.4 °.
Fig. 7 and fig. 8 are scanned before and after self-repairing of the polyurethane coating containing 3% of the added amount of the microcapsules, respectively, and illustrate that the self-repairing effect of the coating is excellent when the added amount of the microcapsules is 3%.
The above detailed description of the embodiments of the present invention and the description of the product phenomena of the different embodiments are only examples, and the present invention is not limited to the above described embodiments. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a hydrophobic double-shell isocyanate type self-repairing microcapsule is characterized by comprising the following steps:
s1: preparing a polyfunctional isocyanate prepolymer core material TMP-IPDI by using TMP and IPDI monomers;
s2: preparing fluorescent isocyanate type self-repairing microcapsule powder by taking polyurethane as a wall material, a core material prepared from S1 and fluorescent agent 4, 4-bis (2-disulfonate styryl) biphenyl;
s3: and (3) coating the fluorescent isocyanate type self-repairing microcapsule prepared by S2 for the second time by using silicon dioxide modified by tridecafluorooctyltrimethoxysilane to obtain the hydrophobic double-shell isocyanate type self-repairing microcapsule.
2. The preparation method of the hydrophobic double-shell isocyanate type self-repairing microcapsule according to claim 1, wherein S1 specifically comprises: mixing 2 parts of TMP, 10 parts of cyclohexanone and 6 parts of benzene in parts by mass, stirring, placing in a heating bath, heating to 75 ℃, and then cooling to 60 ℃ to obtain a dry solution for later use; and (2) putting 13 parts of IPDI in a heating bath at 40 ℃, adding 0.08 part of DBTDL under stirring, dropwise adding the drying solution, raising the reaction temperature to 60 ℃ after the dropwise adding is finished, and continuously reacting for 5 hours to obtain the polyfunctional isocyanate prepolymer core material TMP-IPDI.
3. The preparation method of the hydrophobic double-shell isocyanate-type self-repairing microcapsule as claimed in claim 2, wherein the dropping time of the drying solution is not more than 1 h.
4. The preparation method of the hydrophobic double-shell isocyanate type self-repairing microcapsule according to claim 1, wherein S2 specifically comprises: weighing 5 parts of ethyl acetate, 0.8-4.1 parts of HDI tripolymer, 5 parts of TMP-IPDI prepared from S1 and 0.1-0.5 part of 4, 4-bis (2-disulfonic acid sodium styryl) biphenyl in parts by mass, and uniformly stirring at room temperature to obtain an oil phase system; putting Arabic gum into 120 parts of distilled water, and stirring uniformly at room temperature to obtain a water phase system; slowly pouring the oil phase system into the water phase system under the high-speed stirring state of the prepared water phase system, and continuously emulsifying for 15min after mixing to obtain a suspension system; adding 0.2-1.0 part of BDO into a suspension system, continuously reacting for 2-6h at the temperature of 40-80 ℃ and the rotation speed of 300-700rpm, naturally cooling the obtained microcapsule suspension after the reaction is finished, and repeatedly performing suction filtration, washing and drying to obtain the fluorescent isocyanate type self-repairing microcapsule powder.
5. The preparation method of the hydrophobic double-shell isocyanate type self-repairing microcapsule according to claim 4, wherein the rotation speed of the aqueous phase system during high-speed stirring is 8000 rpm.
6. The preparation method of the hydrophobic double-shell isocyanate type self-repairing microcapsule according to claim 1, wherein S3 specifically comprises: taking 2 parts by mass of fluorescent isocyanate type self-repairing microcapsule powder prepared by S2, dispersing the fluorescent isocyanate type self-repairing microcapsule powder into 10 parts by mass of deionized water, adding 2-10 parts by mass of tetraethoxysilane alcohol solution prepared by TEOS and ethanol, stirring the mixture for 30min at the temperature of 50 ℃ at the rotating speed of 500r/min, and then adjusting the pH to 9 to initiate the hydrolysis reaction of TEOS; continuously stirring for 30min, adding tridecafluorooctyl trimethoxy silane, and reacting for 5 h; raising the temperature to 85 ℃, continuing stirring, and condensing and refluxing until the ethanol is completely evaporated; reducing the temperature to 40 ℃, aging for 12h, and keeping stirring; and after the reaction is finished, washing and filtering the product, and drying the product in a drying oven at 40 ℃ for 2 hours to obtain the hydrophobic double-shell isocyanate type self-repairing microcapsule.
7. The preparation method of the hydrophobic double-shell isocyanate type self-repairing microcapsule according to claim 6, wherein ammonia water or hydrochloric acid is used for dropwise adding in pH adjustment; the washing was with petroleum ether and deionized water.
8. The hydrophobic double-shell isocyanate type self-repairing microcapsule prepared by the preparation method of any one of claims 1 to 7 is characterized by being spherical in appearance, flat and smooth in surface, 10-70um in particle size and 0.67-4.69um in wall thickness.
9. Use of the hydrophobic double-shelled isocyanate-type self-healing microcapsules of claim 8 as self-healing fillers in coatings.
10. The application of the hydrophobic double-shell isocyanate type self-repairing microcapsule as self-repairing filler, which is claimed in claim 9, is characterized in that the mass fraction of the hydrophobic double-shell isocyanate type self-repairing microcapsule in a coating is 3% -5%.
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