CN111804250A - Multifunctional double-layer shell microcapsule and preparation method thereof - Google Patents
Multifunctional double-layer shell microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multifunctional double-layer shell microcapsule and a preparation method thereof. The preparation method of the microcapsule comprises the following steps: preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier; step 2: adding polyamine into the composite core material emulsion, and preparing primary microcapsule emulsion through interfacial polymerization; and step 3: preparing a melamine resin prepolymer; and 4, step 4: and (3) preparing the microcapsule with the aromatic temperature-regulating composite function by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method. The microcapsule prepared by the invention has good thermal stability and compact package, overcomes the problems of leakage and the like of the phase-change material in the process of repeated use, has two functions of heat storage, temperature regulation and aromatic finishing, and has good development prospect in the fields of home textiles, clothing textiles and the like.
Description
Technical Field
The invention relates to a preparation method of a microcapsule with a composite function and a double-layer capsule wall, in particular to a microcapsule with a double-layer shell and a preparation method thereof, wherein the microcapsule has the composite functions of aromatic finishing, heat storage and temperature regulation.
Background
The microcapsule is a core-shell structure, and core materials are made into micro particles in a coating mode, so that the release and loss of the core materials are slowed down. The development of the microcapsule technology dates back to 60 years in the 20 th century, and the NASA in the United states applies the technology to aviation clothes so as to avoid physical injury of astronauts under huge temperature difference. The technology is widely applied to the fields of medicine, textile, food and the like.
According to different core material selections, the prepared microcapsules can have different functions, such as flame-retardant microcapsules, essence microcapsules and phase-change microcapsules, but the functions are relatively single, and the requirement of people on product diversification cannot be met. Chinese patent CN102827586A discloses a double-layer aromatic organic phase change material microcapsule and a preparation method thereof, the invention firstly prepares an organic phase change microcapsule taking urea resin as a capsule wall, then adsorbs essence on the surface of the microcapsule, and finally coats the urea resin organic phase change material microcapsule which adsorbs the essence by taking beta-cyclodextrin as an outer wall material. The process is complicated, and the essence is coated on the outer layer, so that the core material cannot be protected from loss in the repeated use process.
Chinese patent CN106351017A discloses a microcapsule with composite functions of mosquito repelling, antibiosis, heat storage and temperature regulation and a preparation method thereof, firstly, an emulsion taking a phase change material and plant essential oil with mosquito repelling, antibiosis and temperature regulation as a mixed capsule core is prepared, and a composite functional microcapsule taking melamine resin as a capsule wall is prepared by an in-situ polymerization method. The process is simple and can meet the requirement of composite function, but the coating of two core materials by a single capsule wall is easy to cause the defects of nonuniform coating, easy crushing and the like.
US20100087115a1 discloses a composite microcapsule containing a flame retardant and a phase change material, the flame retardancy being enhanced by the addition of the phase change material. US6835334B2 provides a method for preparing a sol of multiple microcapsules, which achieves product diversity by making multiple microcapsules into a suspension. In another two patents KR101331131B1 and US8329223B2, microcapsules with thermoplastic binder as outer shell are prepared by a double outer shell preparation method, and phase-change microcapsules and fibers are combined through covalent bonds in the process of finishing with fibers to achieve better washability.
The preparation methods are all used for meeting the requirements of people on product diversification and washability, but have the problems of complicated microcapsule preparation process, low coating efficiency, poor mechanical strength and the like. If the phase-change material and the essence are directly mixed to form a eutectic body, the temperature response of essence slow release can be realized, and the coating of essence microcapsule particles is facilitated. The double-layer capsule wall coating can solve the problem of low coating rate and poor mechanical strength and can improve the durability of the aromatic phase-change microcapsule.
Disclosure of Invention
The invention provides a preparation method of a double-shell microcapsule with the composite functions of aromatic finishing and heat storage and temperature regulation, the composite microcapsule meets the requirement of the market on product function diversification, the mechanical strength of the microcapsule can be improved by coating the double-shell microcapsule, and the problem of leakage of a capsule core material of the single-shell microcapsule in the process of repeated use is solved.
Therefore, the invention adopts the following technical scheme: a method for preparing a multifunctional double-shell microcapsule, comprising:
step 1: preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier;
step 2: adding polyamine into the composite core material emulsion, and preparing primary microcapsule emulsion through interfacial polymerization;
and step 3: preparing a melamine resin prepolymer;
and 4, step 4: and (3) preparing the microcapsule with the composite functions of aromatic finishing and heat storage and temperature regulation by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method.
The preparation of the multifunctional double-layer shell microcapsule comprises three steps, wherein one step is to prepare the composite multifunctional capsule core emulsion, and the preparation method is mainly to mix an organic phase-change material, isocyanate and essence, add the mixture into a water phase containing an emulsifier, and emulsify the mixture through high-speed shearing. And secondly, adding polyamine dropwise, and reacting the polyamine and isocyanate in the emulsion at the phase interface of the particle surface by adopting an interface polymerization method to generate polyurea resin serving as a first layer of microcapsule shell. Thirdly, preparing melamine resin prepolymer, dripping the prepolymer into primary microcapsule emulsion, and preparing the double-shell microcapsule with the composite functions of aromatic finishing, heat storage and temperature regulation by an in-situ polymerization method.
The microcapsule prepared by the method has two functions of heat storage, temperature regulation and aromatic finishing, and can be applied to the fields of household textiles, clothes textiles and the like.
Further, the high polymer emulsifier is a sodium salt of a styrene-maleic anhydride copolymer having a molecular weight of 3000-
One or more of solution (SMA for short), PVA and modified cellulose molecular emulsifier, and the dosage of the solution accounts for 0.2-5% of the total dosage of the composite core material emulsion.
Further, the phase change material is one or more of low-melting-point n-alkane, n-alkanol and fatty acid ester, wherein the low-melting-point n-alkane is n-hexadecane, n-octadecane or n-eicosane, and preferably n-octadecane; the n-alkanol is n-dodecanol or n-tetradecanol, preferably n-dodecanol; the fatty acid ester is butyl stearate, methyl palmitate or methyl myristate, preferably methyl palmitate.
Further, the essence with the fragrance finishing function is flower fragrance type essential oil or fruit fragrance type essence. The floral essential oil is rose, jasmine, lavender, folium artemisiae argyi, mint, green tea, vanilla and other floral essential oils. The fruit-flavor essence is lemon, apple, peach, sweet orange, etc.
Furthermore, the isocyanate is one or more of TDI, IPDI, HDI and HDI tripolymer, and the dosage of the isocyanate accounts for 3.0-8.0% of the total dosage of the composite core material emulsion.
Further, the preparation method of the composite core material emulsion comprises the following steps: mixing a high polymer emulsifier and deionized water for standby, and mixing a phase change material, isocyanate and essence according to a mass ratio of 1: 0.2-0.5:0.3-0.9, mixing at 30-45 ℃, uniformly stirring, adding into the standby mixed solution under high-speed shearing at 3000-12000r/min, emulsifying for 5-30min, and obtaining the composite core material emulsion.
Further, slowly dripping polyamine into the composite core material emulsion for 30-40min under the heat preservation state of 30-40 ℃, then raising the temperature to 60-80 ℃, and carrying out heat preservation reaction for 2-5 hours, wherein the polyamine is diamine or triamine, and the molar ratio of the dosage to isocyanate is 0.8: 1-0.95: 1.
further, the preparation method of the melamine resin prepolymer comprises the following steps: uniformly mixing melamine, formaldehyde and deionized water, adjusting the pH value to 8.0-9.5 by using liquid caustic soda, heating to 70-80 ℃, and carrying out heat preservation reaction for 30-60min to obtain a clear and transparent melamine resin prepolymer; the molar ratio of the formaldehyde to the melamine is 1.5-4.0: 1.0.
Further, the in-situ polymerization method in the step 4 comprises: heating the primary microcapsule emulsion obtained in the step 2 to 70-80 ℃, adjusting the pH value to 3.5-6.0 by using a formic acid solution, slowly dropwise adding the melamine resin prepolymer obtained in the step 3, finishing dropping for 40-60min, keeping the temperature for reaction for 2-5 h, adjusting the pH value to 7-8 by using liquid alkali, cooling to room temperature, washing, filtering and drying the obtained suspension emulsion to obtain the microcapsule with the composite functions of aromatic finishing and heat storage and temperature adjustment.
The invention also provides the multifunctional double-layer shell microcapsule prepared by the preparation method. The microcapsule prepared by the invention has good thermal stability and compact package, overcomes the problems of leakage and the like of the phase-change material in the process of repeated use, and simultaneously has two functions of heat storage, temperature regulation and aromatic finishing.
Compared with the prior art, the invention has the following advantages:
(1) the microcapsule with the composite function is prepared by combining the aromatic finishing function and the heat storage and temperature regulation function, so that the problem that the existing microcapsule has a single function is solved, and energy and time losses caused by multiple finishing are avoided.
(2) The double-layer shell microcapsule can improve the mechanical strength of the sphere and solve the problem of leakage of the core material of the single shell microcapsule in the repeated use process.
(3) The microcapsule prepared by the invention has good development prospect in the fields of home textiles, clothes textiles and the like.
Detailed Description
The invention is further illustrated below with reference to specific embodiments.
The preparation of the multifunctional double-layer shell microcapsule comprises the preparation of composite multifunctional capsule core emulsion, the preparation of primary microcapsule emulsion by an interface polymerization method and the preparation of a second-layer wall material by an in-situ polymerization method, and the specific description is as follows:
1. preparation of composite multifunctional capsule core emulsion
Mixing a high polymer emulsifier and deionized water in a water bath kettle for later use, and mixing a phase change material, isocyanate and essence according to a mass ratio of 1: 0.2-0.5:0.3-0.9, mixing at 30-45 ℃, uniformly stirring, adding into the standby mixed solution under high-speed shearing at 3000-12000r/min, emulsifying for 5-30min, and obtaining the composite core material emulsion.
Preferably, the high polymer is one or more of SMA (sodium salt solution of styrene-maleic anhydride copolymer), PVA and modified cellulose molecular emulsifier with molecular weight of 3000-20000, and the dosage of the high polymer accounts for 0.2-5% of the total dosage of the composite core emulsion.
Preferably, the isocyanate is one or more of TDI, IPDI, HDI and HDI tripolymer, and the dosage of the isocyanate accounts for 3.0-8.0% of the total dosage of the composite core material emulsion.
More preferably, the isocyanate is IPDI.
Preferably, the phase change is one or more of low-melting-point n-alkane, n-alkanol and fatty acid ester.
More preferably, the phase change material is n-hexadecane, n-octadecane, n-eicosane, n-dodecanol, n-tetradecanol, butyl stearate and methyl palmitate.
Preferably, the essence with the fragrance finishing function is any one of floral essential oils such as rose, jasmine, lavender, folium artemisiae argyi, mint, green tea and vanilla and fruit-flavored essences such as lemon, apple, peach and sweet orange.
2. Preparation of primary microcapsule emulsion by interfacial polymerization method
The interfacial polymerization method is to disperse one wall component and the core material in a continuous phase at the same time, and to add another wall component after emulsification. At this time, the two reaction monomers forming the wall material are respectively located in two immiscible media, only a layer of polymer film can be formed at the juncture of the two media, and the capsule core material is tightly coated by the generated high polymer. As the reaction proceeds, the polymer film prevents the two-phase monomer from contacting, thereby preventing the polymerization reaction from proceeding, and the wall material of the microcapsule prepared by the method is generally smaller in thickness.
The primary microcapsule emulsion is prepared through dropping polyamine slowly into composite core emulsion at 30-40 deg.c for 30-40min, heating to 60-80 deg.c and reaction for 2-5 hr. Polyurea resin microcapsules are produced by interfacial polymerization.
Preferably, the polyamine is diamine or triamine, and the molar ratio of the used amount to the isocyanate is 0.8: 1-0.95: 1.
more preferably, the polyamine is DETA.
3. In-situ polymerization method for preparing second-layer wall material
Micron-scale or even nano-scale capsules can be prepared by in-situ polymerization. The preparation steps mainly comprise: firstly, preparing a wall material prepolymer; secondly, emulsifying and dispersing the core material; and thirdly, wall forming stage, namely, the wall material prepolymer is subjected to polycondensation and crosslinking under the heat and acid environment to form a polymer, and the polymer is deposited on the surface of the core material.
The second layer of the wall material adopts melamine-formaldehyde resin, and the monomers of the melamine-formaldehyde resin and the melamine-formaldehyde resin are soluble, so that the generated polymer is insoluble. The initial reaction monomer is pre-polymerized to produce pre-polymer, and the pre-polymer is deposited on the surface of the primary microcapsule after increasing in size. With the progress of crosslinking and polymerization, the outermost shell of the microcapsule is finally formed.
The preparation method of the melamine resin prepolymer comprises the following steps: uniformly mixing melamine, 37% formaldehyde and deionized water, adjusting the pH value to 8.0-9.5 by using liquid caustic soda, heating to 70-80 ℃, and carrying out heat preservation reaction for 30-60min to obtain a clear and transparent melamine resin prepolymer. Heating the prepared primary microcapsule emulsion to 75 ℃, adjusting the pH value to 3.5-6.0 by using 10% formic acid solution, slowly dripping melamine resin prepolymer, finishing dripping after 40-60min, keeping the temperature for reacting for 2-5 h, adjusting the pH value to 7-8 by using liquid alkali, and cooling to room temperature; and washing, filtering and drying the obtained suspension emulsion to obtain the microcapsule with the fragrance temperature-regulating composite function.
The molar ratio of formaldehyde to melamine may be 1.5: 1-6: 1, but the more the formaldehyde is used, the lower the reaction activity of the generated methylol melamine is, the better the hydrophilicity is, the adverse effect is caused to the generation of melamine-formaldehyde prepolymer, and the washability of the prepared microcapsule is poor.
Thus, preferably, the molar ratio of formaldehyde to melamine is 1.5-4.0: 1.0.
Preferably, the particle size distribution of the microcapsule with the fragrance temperature-regulating composite function is 0.5-20 μm.
Example 1
A preparation method of microcapsules with an aromatic temperature-regulating composite function specifically comprises the following steps:
step 1, preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier.
Preparing an aqueous phase: weighing 1.8g of an emulsifier SMA (sodium salt solution of styrene-maleic anhydride copolymer) and 50g of deionized water in a reactor, heating to 40 ℃, and starting stirring at a stirring speed of 1000r/min until the solution is clear and transparent.
Preparing an oil phase: weighing 22.5g of organic phase change material octadecane, 7.5g of lavender essential oil and 7.8 g of IPDI (isophorone diisocyanate), and uniformly mixing in a water bath kettle at 40 ℃.
Thirdly, slowly adding the oil phase into a water phase reactor at 40 ℃, starting high-speed shearing for 5000r/min, emulsifying for 10min, and stopping stirring to obtain milk-white uniform emulsion.
Step 2: and adding polyamine into the composite core material emulsion, and preparing a primary microcapsule emulsion through interfacial polymerization.
Putting the emulsion prepared in the step 1 into a four-mouth flask, and keeping the temperature at 40 ℃.
② weighing polyamine DETA2.7g, dissolving in 10g deionized water, and loading into a separating funnel.
Thirdly, slowly dripping DETA aqueous solution by using a separating funnel, controlling the dripping speed, finishing dripping within 30min, keeping the temperature for half an hour, and then heating to 70 ℃ and keeping the temperature for 3 hours.
And step 3: preparing melamine resin prepolymer.
12.6g of melamine, 16.2g of 37% formaldehyde and 40g of deionized water are mixed uniformly.
Regulating the pH value of the system to 8.5 by using liquid alkali, starting to heat to 80 ℃, reacting for 40min to obtain melamine resin prepolymer, and cooling for later use.
And 4, step 4: and (3) preparing the microcapsule with the aromatic temperature-regulating composite function by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method.
The microcapsule emulsion of step 2 is adjusted to pH =5.5 using 10% wt formic acid solution and warmed up to 75 ℃ for use.
Secondly, slowly dripping the melamine resin prepolymer into the microcapsule emulsion, controlling the dripping speed, and finishing dripping within 40 min.
③ after keeping the temperature for reaction for 2 hours, adjusting the pH to be =8 by using 30% wt liquid alkali solution to terminate the reaction.
And fourthly, washing, filtering and drying the obtained suspension to obtain the microcapsule with the fragrance temperature-regulating composite function.
Example 2
A preparation method of microcapsules with an aromatic temperature-regulating composite function specifically comprises the following steps:
step 1, preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier.
Preparing an aqueous phase: weighing 1.8g of an emulsifier SMA (sodium salt solution of styrene-maleic anhydride copolymer) and 50g of deionized water in a reactor, heating to 40 ℃, and starting stirring at the stirring speed of 1000r/min until the solution is clear and transparent.
Preparing an oil phase: weighing 22.5g of organic phase change material octadecane, 7.5g of sweet orange fruit essential oil and 8.8 g of IPDI, and uniformly mixing in a water bath kettle at 40 ℃.
Thirdly, slowly adding the oil phase into a water phase reactor at 40 ℃, starting high-speed shearing at 6000r/min, emulsifying for 6min, and stopping stirring to obtain milk-white uniform emulsion.
Step 2: and adding polyamine into the composite core material emulsion, and preparing a primary microcapsule emulsion through interfacial polymerization.
Putting the emulsion prepared in the step 1 into a four-mouth flask, and keeping the temperature at 40 ℃.
② 2.7g of polyamine DETA is weighed and dissolved in 10g of deionized water, and the solution is loaded into a separating funnel.
Thirdly, slowly dripping DETA aqueous solution by using a separating funnel, controlling the dripping speed, finishing dripping within 30min, keeping the temperature for half an hour, and then heating to 70 ℃ and keeping the temperature for 3 hours.
And step 3: preparing melamine resin prepolymer.
7.56g of melamine, 12.16g of 37% formaldehyde and 40g of deionized water were mixed homogeneously.
Regulating the pH value of the system to 8.5 by using liquid alkali, starting to heat to 80 ℃, reacting for 40min to obtain melamine resin prepolymer, and cooling for later use.
And 4, step 4: and (3) preparing the microcapsule with the aromatic temperature-regulating composite function by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method.
The microcapsule emulsion of step 2 is adjusted to pH =5.5 using 10% wt formic acid solution and warmed up to 75 ℃ for use.
Secondly, slowly dripping the melamine resin prepolymer into the microcapsule emulsion, controlling the dripping speed, and finishing dripping within 40 min.
③ after keeping the temperature for reaction for 2 hours, adjusting the pH to be =8 by using 30% wt liquid alkali solution to terminate the reaction.
And fourthly, washing, filtering and drying the obtained suspension to obtain the microcapsule with the fragrance temperature-regulating composite function.
Example 3
A preparation method of microcapsules with an aromatic temperature-regulating composite function specifically comprises the following steps:
step 1: preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier.
Preparing an aqueous phase: 0.4g of an emulsifier SMA (sodium salt solution of styrene-maleic anhydride copolymer) and 50g of deionized water are weighed into a reactor, heated to 40 ℃, and stirred at the stirring speed of 1000r/min until the solution is clear and transparent.
Preparing an oil phase: weighing 11.33g of organic phase change material octadecane, 5.67g of wormwood essential oil and 2.27g of IPDI, and uniformly mixing in a water bath kettle at 40 ℃.
Thirdly, slowly adding the oil phase into a water phase reactor at 40 ℃, starting high-speed shearing at 8000r/min, emulsifying for 8min, and stopping stirring to obtain milk-white uniform emulsion.
Step 2: and adding polyamine into the composite core material emulsion, and preparing a primary microcapsule emulsion through interfacial polymerization.
Putting the emulsion prepared in the step 1 into a four-mouth flask, and keeping the temperature at 40 ℃.
② 0.95g of polyamine DETA is weighed and dissolved in 10g of deionized water, and the solution is loaded into a separating funnel.
Thirdly, slowly dripping DETA aqueous solution by using a separating funnel, controlling the dripping speed, finishing dripping within 30min, keeping the temperature for half an hour, and then heating to 70 ℃ and keeping the temperature for 3 hours.
And step 3: preparing melamine resin prepolymer.
3.78g of melamine, 3.66g of 37% formaldehyde and 40g of deionized water were mixed homogeneously.
Regulating the pH value of the system to 8.5 by using liquid alkali, starting to heat to 80 ℃, reacting for 40min to obtain melamine resin prepolymer, and cooling for later use.
And 4, step 4: and (3) preparing the microcapsule with the aromatic temperature-regulating composite function by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method.
The microcapsule emulsion of step 2 is adjusted to pH =6 using 10% wt formic acid solution and warmed to 75 ℃ for use.
Secondly, slowly dripping the melamine resin prepolymer into the microcapsule emulsion, controlling the dripping speed, and finishing dripping within 40 min.
③ after keeping the temperature for reaction for 2 hours, adjusting the pH to be =8 by using 30% wt liquid alkali solution to terminate the reaction.
And fourthly, washing, filtering and drying the obtained suspension to obtain the microcapsule with the fragrance temperature-regulating composite function.
Example 4
A preparation method of microcapsules with an aromatic temperature-regulating composite function specifically comprises the following steps:
step 1: preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier.
Preparing an aqueous phase: 0.34g of emulsifier PVA and 136g of deionized water are weighed into a reactor, heated to 40 ℃, and stirred at the stirring speed of 1000r/min until the solution is clear and transparent.
Preparing an oil phase: weighing 18g of organic phase change material hexadecane, 16g of green tea essential oil and 8.85g of HDI, and uniformly mixing in a water bath kettle at 40 ℃.
Thirdly, slowly adding the oil phase into a water phase reactor at 40 ℃, starting high-speed shearing for 5000r/min, emulsifying for 8min, and stopping stirring to obtain milk-white uniform emulsion.
Step 2: and adding polyamine into the composite core material emulsion, and preparing a primary microcapsule emulsion through interfacial polymerization.
Putting the emulsion prepared in the step 1 into a four-mouth flask, and keeping the temperature at 40 ℃.
② 5.15g of polyamine DETA is weighed and dissolved in 10g of deionized water, and the solution is loaded into a separating funnel.
Thirdly, slowly dripping DETA aqueous solution by using a separating funnel, controlling the dripping speed, finishing dripping within 40min, keeping the temperature for half an hour, and then heating to 70 ℃ and keeping the temperature for 3 hours.
And step 3: preparing melamine resin prepolymer.
10.08g of melamine, 25.95g of 37% formaldehyde and 100g of deionized water are mixed uniformly.
Regulating the pH value of the system to 8.5 by using liquid alkali, starting to heat to 80 ℃, reacting for 40min to obtain melamine resin prepolymer, and cooling for later use.
And 4, step 4: and (3) preparing the microcapsule with the aromatic temperature-regulating composite function by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method.
The microcapsule emulsion of step 2 is adjusted to pH =5 using 10% wt formic acid solution and warmed up to 75 ℃ for use.
Secondly, slowly dripping the melamine resin prepolymer into the microcapsule emulsion, controlling the dripping speed, and finishing dripping within 40 min.
③ after keeping the temperature for reaction for 2 hours, adjusting the pH to be =8 by using 30% wt liquid alkali solution to terminate the reaction.
And fourthly, washing, filtering and drying the obtained suspension to obtain the microcapsule with the fragrance temperature-regulating composite function.
Claims (10)
1. A preparation method of a multifunctional double-layer shell microcapsule is characterized by comprising the following steps:
step 1: preparing composite core material emulsion, wherein the composite core material emulsion contains a phase-change material, essence with an aromatic finishing function, isocyanate and a high polymer emulsifier;
step 2: adding polyamine into the composite core material emulsion, and preparing primary microcapsule emulsion through interfacial polymerization;
and step 3: preparing a melamine resin prepolymer;
and 4, step 4: and (3) preparing the microcapsule with the composite functions of aromatic finishing and heat storage and temperature regulation by using the primary microcapsule emulsion prepared in the step (2) and the melamine resin prepolymer prepared in the step (3) through an in-situ polymerization method.
2. The method according to claim 1, wherein the polymer emulsifier is one or more selected from the group consisting of sodium salt solution of styrene-maleic anhydride copolymer having molecular weight of 3000-.
3. The preparation method according to claim 1, wherein the phase change material is one or more of low-melting-point n-alkane, n-alkanol and fatty acid ester, wherein the low-melting-point n-alkane is n-hexadecane, n-octadecane or n-eicosane, the n-alkanol is n-dodecanol or n-tetradecanol, and the fatty acid ester is butyl stearate, methyl palmitate or methyl myristate.
4. The method of claim 1, wherein the essence having an aromatic finishing function is a floral type essential oil or a fruity type essence.
5. The method of claim 1, wherein the isocyanate is one or more of TDI, IPDI, HDI and HDI trimer, and the amount of the isocyanate is 3.0-8.0% of the total amount of the composite core emulsion.
6. The method of claim 1, wherein the method of preparing the composite core emulsion comprises: mixing a high polymer emulsifier and deionized water for standby, and mixing a phase change material, isocyanate and essence according to a mass ratio of 1: 0.2-0.5:0.3-0.9, mixing at 30-45 ℃, uniformly stirring, adding into the standby mixed solution under high-speed shearing at 3000-12000r/min, emulsifying for 5-30min, and obtaining the composite core material emulsion.
7. The preparation method of claim 1, wherein polyamine is slowly dropped into the composite core material emulsion for 30-40min under the condition of heat preservation at 30-40 ℃, and then the temperature is raised to 60-80 ℃ for heat preservation reaction for 2-5 hours, wherein the polyamine is diamine or triamine, and the molar ratio of the polyamine to isocyanate is 0.8: 1-0.95: 1.
8. the method of claim 1, wherein the melamine resin prepolymer is prepared by a method comprising: uniformly mixing melamine, formaldehyde and deionized water, adjusting the pH value to 8.0-9.5 by using liquid caustic soda, heating to 70-80 ℃, and carrying out heat preservation reaction for 30-60min to obtain a clear and transparent melamine resin prepolymer; the molar ratio of the formaldehyde to the melamine is 1.5-4.0: 1.0.
9. The method of claim 1, wherein the in-situ polymerization process in step 4 comprises: heating the primary microcapsule emulsion obtained in the step 2 to 70-80 ℃, adjusting the pH value to 3.5-6.0 by using a formic acid solution, slowly dropwise adding the melamine resin prepolymer obtained in the step 3, finishing dropping for 40-60min, keeping the temperature for reaction for 2-5 h, adjusting the pH value to 7-8 by using liquid alkali, cooling to room temperature, washing, filtering and drying the obtained suspension emulsion to obtain the microcapsule with the composite functions of aromatic finishing and heat storage and temperature adjustment.
10. The multifunctional double shell microcapsule prepared by the preparation method of any one of claims 1 to 9.
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