CN114307888A - Isocyanate microcapsule and preparation method thereof - Google Patents
Isocyanate microcapsule and preparation method thereof Download PDFInfo
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- CN114307888A CN114307888A CN202111653141.XA CN202111653141A CN114307888A CN 114307888 A CN114307888 A CN 114307888A CN 202111653141 A CN202111653141 A CN 202111653141A CN 114307888 A CN114307888 A CN 114307888A
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 142
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 140
- 239000003094 microcapsule Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000005416 organic matter Substances 0.000 claims abstract description 43
- 239000002612 dispersion medium Substances 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 16
- 239000002775 capsule Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 14
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 10
- -1 amino, hydroxyl Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001993 wax Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229940057995 liquid paraffin Drugs 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229940083037 simethicone Drugs 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
- BHQIQHCOQQQTKH-UHFFFAOYSA-N CCCCCCCCCCCCCCCCC(CCCCCC)F Chemical compound CCCCCCCCCCCCCCCCC(CCCCCC)F BHQIQHCOQQQTKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 241001391944 Commicarpus scandens Species 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
An isocyanate microcapsule and a preparation method thereof, which relate to the technical field of microcapsule composite materials; isocyanate is taken as a micro-core, a low-melting-point organic matter is taken as a capsule wall to coat the micro-core, and the isocyanate micro-capsule comprises the following raw material components in percentage by mass: 30-87% of a dispersion medium, 5-40% of isocyanate and 1-30% of a low-melting-point organic matter. The isocyanate microcapsule takes low-melting organic matter as a capsule wall and isocyanate as a micro-core; the isocyanate microcapsule can improve the stability of isocyanate, prolong the working life of the isocyanate, prevent the reaction with active ingredients, solidify liquid isocyanate, control and release the isocyanate and improve the added value of the isocyanate; meanwhile, the microcapsule has higher activity, is easy to break, can be controlled to release, and can be used as a repairing agent to endow the substrate with self-repairing capability.
Description
Technical Field
The invention relates to the technical field of microcapsule composite materials, in particular to an isocyanate microcapsule and a preparation method thereof.
Background
The isocyanate has high activity, the molecular structure of the isocyanate is easy to design, and the isocyanate is widely applied to various industries including the fields of adhesives, coatings, medicines, agriculture, composite materials and the like. However, the isocyanate is too high, and part of the isocyanate volatilizes and has certain toxicity, so that the isocyanate is not easy to store and transport; meanwhile, the liquid isocyanate is easy to volatilize, releases bad smell and is harmful to human bodies and the environment in the using process. Therefore, it is necessary to research an isocyanate microcapsule, which is coated with isocyanate through a wall material to improve stability.
Chinese patent No. CN201610423318.X, named functional cross-linking agent-isocyanate microcapsule and its preparation method, has prolonged shelf life and good stability by adding chain extender and compound emulsifier to coat isocyanate to form the functional cross-linking agent-isocyanate microcapsule. The patent No. CN201710826606.4, entitled isocyanate microcapsule and its preparation method, discloses an isocyanate microcapsule with gelatin-gum arabic as wall material, which has excellent stability on the premise of retaining a large amount of original active groups of isocyanate. The patent No. CN201910057948.3 is a Chinese patent named isocyanate microcapsule and a preparation method thereof, and the isocyanate microcapsule is prepared by taking a high molecular polymer as a capsule wall and taking isocyanate as a micro-core, and the problems of short aging period and poor stability of the isocyanate are solved. Although the three schemes enable isocyanate to keep high activity, the capsule wall structure of the isocyanate is too firm, the capsule is not easy to break, the application scenes are limited, and particularly the development of the isocyanate in the field of self-repairing materials is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an isocyanate microcapsule, which can improve the stability of isocyanate, solidify liquid isocyanate, control the release of the microcapsule and be used as a repairing agent to endow self-repairing capability to a substrate.
The second object of the present invention is to provide a method for preparing isocyanate microcapsules, which can prepare isocyanate microcapsules having high stability, reduce the occurrence of side reactions, and easily control the particle size of the isocyanate microcapsules.
One of the purposes of the invention is realized by adopting the following technical scheme:
an isocyanate microcapsule takes isocyanate as a microcapsule core and takes a low-melting-point organic matter as a capsule wall to coat the microcapsule core, and comprises the following raw material components in percentage by mass:
30-87% of a dispersion medium, 5-40% of isocyanate and 1-30% of a low-melting-point organic matter.
Further, the dispersion medium is at least one of water, dimethyl silicone oil, liquid paraffin, C5-18-perfluoroalkyl, hexadecyl fluoro heptane and perfluorotributylamine.
Further, when the dispersion medium is water or a mixture of water and at least one of simethicone, liquid paraffin, C5-18-perfluoroalkyl, hexadecafluoroheptane and perfluorotributylamine, the isocyanate microcapsule further comprises an emulsifier and an acidic stabilizer, and the isocyanate microcapsule consists of the following raw material components in percentage by mass:
30-87% of a dispersion medium, 0.1-7% of an emulsifier, 5-40% of isocyanate, 1-30% of a low-melting-point organic matter and 0.1-3% of an acidic stabilizer.
Further, when the dispersion medium is at least one of simethicone, liquid paraffin, C5-18-perfluoroalkyl, hexadecafluoroheptane and perfluorotributylamine, the isocyanate microcapsule comprises the following raw material components in percentage by mass:
30-87% of a dispersion medium, 0-7% of an emulsifier, 5-40% of isocyanate, 1-30% of a low-melting-point organic matter and 0-3% of an acidic stabilizer.
Further, the isocyanate microcapsule consists of the following raw material components in percentage by mass:
30-87% of a dispersion medium, 5-40% of isocyanate and 1-30% of a low-melting-point organic matter.
Further, the emulsifier is at least one of castor oil polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, sodium carboxymethyl cellulose, polyvinyl alcohol, tween and span;
the acidic stabilizer is at least one of formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, ammonium chloride and ammonium sulfate.
Further, the low-melting-point organic matter is an organic matter with a melting point of 40-90 ℃, and the number of active functional groups contained in molecules of the low-melting-point organic matter is not more than 1; wherein the active functional group is one or more than two of amino, hydroxyl, carboxyl and carboxyl.
Further, the low-melting-point organic matter is at least one of solid wax, stearic acid, stearyl alcohol, glyceryl monostearate, glyceryl tristearate and solid alkane.
The second purpose of the invention is realized by adopting the following technical scheme:
a preparation method of isocyanate microcapsules comprises the following steps:
(1) heating and melting the low-melting-point organic matter, and then adding isocyanate and uniformly mixing to obtain a dispersed phase;
(2) uniformly mixing an emulsifier, a dispersion medium and an acid stabilizer, and heating to the melting temperature of the low-melting-point organic matter to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, stirring and dispersing to obtain a mixed solution;
(4) and cooling the low-melting-point organic matter, filtering, washing and drying to obtain the isocyanate microcapsule.
Further, in the step (1), the heating temperature is the melting point temperature of the low-melting-point compound;
in the step (2), the pH value of the dispersion medium is 2-7;
in the step (3), the rotating speed of the stirring is 600-3000 rpm/min;
in the step (4), the temperature reduction rate of the temperature reduction treatment is 0.5-5 ℃/min, and the temperature is reduced to be below the freezing point of the low-melting-point organic matter. The cooling rate of the invention is properly controlled, the cooling rate is too fast, the molecular moving rate is less than the cooling rate, the microcapsule encapsulation condition is poor, the encapsulation efficiency is low, and the appearance is irregular; the preparation efficiency is reduced due to the excessively low cooling rate.
Compared with the prior art, the invention has the beneficial effects that:
the isocyanate microcapsule takes low-melting organic matter as a capsule wall and isocyanate as a micro-core; the isocyanate microcapsule can improve the stability of isocyanate, prolong the working life of the isocyanate, prevent the reaction with active ingredients, solidify liquid isocyanate, control and release the isocyanate and improve the added value of the isocyanate; meanwhile, the microcapsule has higher activity, is easy to break, can be controlled to release, and can be used as a repairing agent to endow the substrate with self-repairing capability.
The isocyanate microcapsule is prepared by melting, condensing and condensing low-melting-point organic matters in a dispersion medium, condensing and precipitating the low-melting-point organic matters after melting, coating isocyanate and condensing under an acidic environment, so that the isocyanate microcapsule can inhibit the side reaction of the isocyanate and active hydrogen.
Furthermore, the cyanate ester microcapsule of the present invention has high activity, and according to the data in the examples, it can be known that the isocyanate microcapsule of the present invention has a — NCO group content (active group) as high as 23% (when the — NCO content in the isocyanate used is 29%), is in the form of dispersed spherical particles, has a controllable particle size, and has the advantages of convenient use, transportation, storage, etc.
Drawings
FIG. 1 is a scanning electron microscope photograph of isocyanate microcapsules prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example 1
The isocyanate microcapsule is characterized in that isocyanate is used as a micro core, a low-melting-point organic matter is used as a capsule wall to coat the micro core, and the isocyanate microcapsule comprises the following raw material components in percentage by mass:
67% of dispersion medium, 12% of low-melting-point organic matter, 2% of emulsifier, 18% of isocyanate and 1% of acidic stabilizer.
Wherein the dispersion medium is water; the low-melting-point organic matter is stearic acid; the emulsifier is sodium carboxymethylcellulose; the isocyanate is polymethylene polyphenyl polyisocyanate (PAPI); the acidic stabilizer is hydrochloric acid.
The specific preparation method of the isocyanate microcapsule is as follows:
(1) heating stearic acid to be molten at 72 ℃, and then adding polymethylene polyphenyl polyisocyanate to be uniformly mixed to obtain a dispersed phase;
(2) uniformly mixing sodium carboxymethylcellulose, hydrochloric acid and water, and heating to 72 ℃ to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, and mechanically stirring (1200rpm) to obtain emulsion;
(4) and (3) continuously stirring the emulsion, cooling (5 ℃/min), filtering when the temperature is reduced to be below the solidifying point of stearic acid, washing and drying to obtain the isocyanate microcapsule.
FIG. 1 is a scanning electron microscope photograph of isocyanate microcapsules prepared in example 1 of the present invention; as can be seen from the figure, the isocyanate microcapsules prepared by the invention present a spherical shape with smooth surface.
Example 2
The isocyanate microcapsule is characterized in that isocyanate is used as a micro core, a low-melting-point organic matter is used as a capsule wall to coat the micro core, and the isocyanate microcapsule comprises the following raw material components in percentage by mass:
60% of dispersion medium, 12% of low-melting-point organic matter, 2% of emulsifier, 25% of isocyanate and 1% of acid stabilizer.
Wherein the dispersion medium is dimethyl silicone oil; the low-melting-point organic matter is solid wax; the emulsifier is sodium dodecyl sulfate; the isocyanate is toluene-2, 4-diisocyanate; the acidic stabilizer is formic acid.
The specific preparation method of the isocyanate microcapsule is as follows:
(1) heating the solid wax to be molten at 70 ℃, and then adding toluene-2, 4-diisocyanate to be uniformly mixed to obtain a dispersed phase;
(2) mixing sodium dodecyl sulfate, formic acid and dimethyl silicone oil uniformly, and heating to 70 ℃ to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, and mechanically stirring (1600rpm) to obtain emulsion;
(4) and (3) continuously stirring the emulsion, cooling (5 ℃/min), filtering when the temperature is reduced to be below the freezing point of the solid wax, washing and drying to obtain the isocyanate microcapsule.
Example 3
The isocyanate microcapsule is characterized in that isocyanate is used as a micro core, a low-melting-point organic matter is used as a capsule wall to coat the micro core, and the isocyanate microcapsule comprises the following raw material components in percentage by mass:
60% of dispersion medium, 12% of low-melting-point organic matter, 2% of emulsifier, 25% of isocyanate and 1% of acid stabilizer.
Wherein the dispersion medium is liquid paraffin; the low-melting-point organic substance is stearyl alcohol; the emulsifier is castor oil polyoxyethylene ether; the isocyanate is polymethylene polyphenyl polyisocyanate; the acidic stabilizer is phosphoric acid.
The specific preparation method of the isocyanate microcapsule is as follows:
(1) heating stearyl alcohol to melt at 60 ℃, and then adding polymethylene polyphenyl polyisocyanate to mix uniformly to obtain a dispersed phase;
(2) uniformly mixing polymethylene polyphenyl polyisocyanate, phosphoric acid and liquid paraffin, and heating to 60 ℃ to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, and mechanically stirring (1600rpm) to obtain emulsion;
(4) and (3) continuously stirring the emulsion, cooling (3 ℃/min), filtering, washing and drying when the temperature is reduced to be below the solidifying point of the stearyl alcohol to obtain the isocyanate microcapsule.
Example 4
The isocyanate microcapsule is characterized in that isocyanate is used as a micro core, a low-melting-point organic matter is used as a capsule wall to coat the micro core, and the isocyanate microcapsule comprises the following raw material components in percentage by mass:
60% of dispersion medium, 12% of low-melting-point organic matter, 2% of emulsifier, 25% of isocyanate and 1% of acid stabilizer.
Wherein the dispersion medium is perfluorotributylamine; the low-melting-point organic matter is solid wax; the emulsifier is polyvinyl alcohol; the isocyanate is toluene-2, 4-diisocyanate; the acidic stabilizer is hydrochloric acid.
The specific preparation method of the isocyanate microcapsule is as follows:
(1) heating stearyl alcohol to melt at 70 ℃, then adding toluene-2, 4-diisocyanate and uniformly mixing to obtain a dispersed phase;
(2) uniformly mixing polyvinyl alcohol, hydrochloric acid and perfluorotributylamine, and heating to 70 ℃ to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, and mechanically stirring (2000rpm) to obtain emulsion;
(4) and (3) continuously stirring the emulsion, cooling (3 ℃/min), filtering, washing and drying when the temperature is reduced to be below the freezing point of low stearyl alcohol to obtain the isocyanate microcapsule.
Example 5
The isocyanate microcapsule is characterized in that isocyanate is used as a micro core, a low-melting-point organic matter is used as a capsule wall to coat the micro core, and the isocyanate microcapsule comprises the following raw material components in percentage by mass:
60% of a dispersion medium, 14% of a low-melting-point organic matter and 26% of isocyanate.
Wherein the dispersion medium is perfluorotributylamine; the low-melting-point organic matter is solid wax; the isocyanate is toluene-2, 4-diisocyanate.
The specific preparation method of the isocyanate microcapsule is as follows:
(1) heating the solid wax to be molten at 70 ℃, and then adding toluene-2, 4-diisocyanate to be uniformly mixed to obtain a dispersed phase;
(2) heating perfluorotributylamine to 70 ℃ to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, and mechanically stirring (1600rpm) to obtain emulsion;
(4) and (3) continuously stirring the emulsion, cooling (5 ℃/min), filtering, washing and drying when the temperature is reduced to be below the freezing point of the solid wax to obtain the isocyanate microcapsule.
As can be seen from the above examples, the isocyanate microcapsule of the present invention uses low-melting organic substance as the capsule wall and isocyanate as the capsule core, and is a low-melting organic substance-coated isocyanate microcapsule, which can improve the stability of isocyanate, prolong the pot life of isocyanate, block the reaction with active ingredients, solidify liquid isocyanate, and controllably release isocyanate, thereby improving the added value thereof; in addition, the wall used for preparing the microcapsule is prepared by melting, condensing and condensing, and different from other preparation methods, the method can be used for preparing the isocyanate microcapsule by using water as a dispersion medium or using a non-aqueous dispersion medium, has better stability, and can have good coating effect without adding an emulsifier or an acid stabilizer.
The isocyanate microcapsule prepared by adopting a melting condensation method has high activity, the-NCO% content is as high as 22.5% (when the-NCO% of the used isocyanate is 29%), the isocyanate microcapsule is basically odorless, is spherical particles which are dispersed and have smooth outer surfaces, the particle size is controllable, and the isocyanate microcapsule has the advantages of convenience in use, transportation and storage and the like.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The isocyanate microcapsule is characterized in that isocyanate is used as a micro core, a low-melting-point organic matter is used as a capsule wall to coat the micro core, and the isocyanate microcapsule comprises the following raw material components in percentage by mass:
30-87% of a dispersion medium, 5-40% of isocyanate and 1-30% of a low-melting-point organic matter.
2. An isocyanate microcapsule according to claim 1 wherein: the dispersion medium is at least one of water, dimethyl silicone oil, liquid paraffin, C5-18-perfluoroalkyl, hexadecyl fluoro heptane and perfluorotributylamine.
3. An isocyanate microcapsule according to claim 2 wherein: when the dispersion medium is water or a mixture of water and at least one of simethicone, liquid paraffin, C5-18-perfluoroalkyl, hexadecyl fluoro heptane and perfluorotributylamine, the isocyanate microcapsule further comprises an emulsifier and an acidic stabilizer, and the isocyanate microcapsule consists of the following raw material components in percentage by mass:
30-87% of a dispersion medium, 0.1-7% of an emulsifier, 5-40% of isocyanate, 1-30% of a low-melting-point organic matter and 0.1-3% of an acidic stabilizer.
4. An isocyanate microcapsule according to claim 2 wherein: when the dispersion medium is at least one of simethicone, liquid paraffin, C5-18-perfluoroalkyl, hexadecafluoroheptane and perfluorotributylamine, the isocyanate microcapsule comprises the following raw material components in percentage by mass:
30-87% of a dispersion medium, 0-7% of an emulsifier, 5-40% of isocyanate, 1-30% of a low-melting-point organic matter and 0-3% of an acidic stabilizer.
5. An isocyanate microcapsule according to claim 4 wherein: the isocyanate microcapsule comprises the following raw material components in percentage by mass:
30-87% of a dispersion medium, 5-40% of isocyanate and 1-30% of a low-melting-point organic matter.
6. An isocyanate microcapsule according to claim 3 or 4 wherein: the emulsifier is at least one of castor oil polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, sodium carboxymethyl cellulose, polyvinyl alcohol, tween and span;
the acidic stabilizer is at least one of formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, ammonium chloride and ammonium sulfate.
7. An isocyanate microcapsule according to any one of claims 1 to 5 wherein: the low-melting-point organic matter is an organic matter with a melting point of 40-90 ℃, and the number of active functional groups contained in molecules of the low-melting-point organic matter is not more than 1; wherein the active functional group is one or more than two of amino, hydroxyl, carboxyl and carboxyl.
8. An isocyanate microcapsule according to claim 7 wherein: the low-melting-point organic matter is at least one of solid wax, stearic acid, stearyl alcohol, glyceryl monostearate, glyceryl tristearate and solid alkane.
9. A process for the preparation of isocyanate microcapsules according to any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) heating and melting the low-melting-point organic matter, and then adding isocyanate and uniformly mixing to obtain a dispersed phase;
(2) uniformly mixing an emulsifier, a dispersion medium and an acid stabilizer, and heating to the melting temperature of the low-melting-point organic matter to obtain a continuous phase;
(3) adding the dispersed phase into the continuous phase, mixing, stirring and dispersing to obtain a mixed solution;
(4) and cooling the low-melting-point organic matter, filtering, washing and drying to obtain the isocyanate microcapsule.
10. The method for preparing isocyanate microcapsules of claim 9, wherein: in the step (1), the heating temperature is the melting point temperature of the low-melting-point compound;
in the step (2), the pH value of the dispersion medium is 2-7;
in the step (3), the rotating speed of the stirring is 600-3000 rpm/min;
in the step (4), the cooling rate of the cooling treatment is 0.5-5 ℃/min.
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| JPH05310950A (en) * | 1992-05-01 | 1993-11-22 | Kyokuto Internatl Corp | Isocyanate compound-including capsule and its production |
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| CN109692635A (en) * | 2019-01-22 | 2019-04-30 | 东北林业大学 | A kind of isocyanate microcapsule and preparation method thereof |
| CN112226208A (en) * | 2019-07-15 | 2021-01-15 | 北京态金科技有限公司 | Low-melting-point metal phase change microcapsule and preparation method and application thereof |
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|---|---|---|---|---|
| JPH05310950A (en) * | 1992-05-01 | 1993-11-22 | Kyokuto Internatl Corp | Isocyanate compound-including capsule and its production |
| JPH0724302A (en) * | 1993-07-14 | 1995-01-27 | Kyokuto Internatl Corp | Capsule containing isocyanate-based compound and production thereof |
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