CN110052231B - Cu2Preparation method of O/polyacrylate composite phase change microcapsule - Google Patents
Cu2Preparation method of O/polyacrylate composite phase change microcapsule Download PDFInfo
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Abstract
The invention discloses a Cu2The preparation method of the O/polyacrylate composite phase-change microcapsule utilizes quaternization reaction of amphiphilic block copolymer and alkyl bromide to obtain amphiphilic block copolymer quaternary ammonium salt; mixing the obtained amphiphilic block copolymer quaternary ammonium salt with a phase-change material, an acrylate monomer, a cross-linking agent and deionized water, and performing ultrasonic dispersion to form an oil-in-water type pre-emulsion; placing the oil-in-water type pre-emulsion in a hot water bath for heating and continuously stirring, adding an initiator aqueous solution, and carrying out heat preservation reaction to obtain a polyacrylate coated phase change material microcapsule; mixing the obtained polyacrylate coated phase-change material microcapsule with copper sulfate, sodium hydroxide and a reducing agent, and carrying out precipitation reduction reaction to obtain Cu2O/polyacrylate composite phase change microcapsule. The invention can prepare the composite phase-change microcapsule with high coating rate, good heat conductivity, excellent thermal stability, proper phase-change temperature range, larger phase-change latent enthalpy and better antibacterial property.
Description
Technical Field
The invention belongs to the technical field of phase change microcapsule preparation methods, and particularly relates to Cu2A preparation method of an O/polyacrylate composite phase change microcapsule.
Background
With the rapid development of economy and society, the human beings depend on the energy generated by the combustion of fossil fuel excessively, which causes serious problems of energy exhaustion and environmental pollution, and simultaneously, the reasonable development and the effective utilization of energy and the sustainable development of the human society present great challenges. Phase change materials have attracted considerable attention in recent years in the field of latent heat storage due to high storage density and near-constant temperature endothermic/exothermic characteristics. However, the problems of fluidity, phase separation, supercooling and low thermal conductivity of the phase change material in a molten state limit the expansion of its application. Microencapsulation of phase-change materials is an effective method for solving these problems, and it is a phase-change microcapsule with a core-shell structure formed by coating a layer of organic polymer material or inorganic material on the periphery of the phase-change material by using microcapsule encapsulation technology.
At present, a commonly used phase change microcapsule wall material is an organic polymer material, polyacrylate enters the visual field of researchers due to excellent film forming property, weather resistance and bonding strength, but the low heat conductivity of polyacrylate enables the thermal response of the phase change microcapsule material to be delayed, and the requirement of real-time thermal response in practical application is not met. Cu2As a p-type semiconductor material, O has the advantages of high strength, high thermal stability and high thermal conductivity, has excellent optical performance due to typical local surface plasmon resonance, and is widely applied to the fields of photocatalysis, solar energy conversion, antifouling coating, gas sensing and the like. Thus, Cu2The wall material of the phase-change microcapsule compounded by O and polyacrylate can be Cu2The excellent thermal conductivity of O is combined with the good compactness of polyacrylate to prepare a photo-thermal conversion material with high thermal conductivity and high thermal stability, so that the renewable clean energy, namely solar energy, is fully utilized.
Patent document No. CN106675524A discloses a method for preparing microencapsulated phase change material with paraffin as core material and cuprous oxide as wall material, which significantly improves thermal conductivity and thermal stability; however, the compactness of the single inorganic functional wall material is obviously lower than that of the organic polymer material, so that the leakage of the phase-change core material can be caused in the recycling process, and the service life of the material is shortened.
Disclosure of Invention
The object of the present invention is to provide a Cu2O/polypropyleneThe preparation method of the olefine acid ester composite phase-change microcapsule adopts RAFT miniemulsion polymerization to prepare the difunctional phase-change energy-storage microcapsule with high encapsulation efficiency, good phase-change energy-storage temperature-adjusting performance and antibacterial property.
The technical scheme adopted by the invention is that Cu2The preparation method of the O/polyacrylate composite phase change microcapsule is implemented according to the following steps:
step 1, mixing the amphiphilic block copolymer with brominated alkane and a solvent, and carrying out quaternization reaction to obtain amphiphilic block copolymer quaternary ammonium salt;
step 2, mixing the amphiphilic block copolymer quaternary ammonium salt obtained in the step 1 with a phase-change material, an acrylate monomer, a cross-linking agent and deionized water, and performing ultrasonic dispersion to form an oil-in-water type pre-emulsion;
step 3, placing the oil-in-water type pre-emulsion obtained in the step 2 in a hot water bath for heating and continuously stirring, adding an initiator aqueous solution, and carrying out heat preservation reaction to obtain a polyacrylate coated phase change material microcapsule;
step 4, mixing the polyacrylate coated phase-change material microcapsule obtained in the step 3 with copper sulfate, sodium hydroxide and a reducing agent, and reacting at constant temperature to obtain Cu2O/polyacrylate composite phase change microcapsule.
The invention is also characterized in that:
the step 1 is implemented according to the following steps:
step 1.1, according to the mass ratio of (0.14-0.20): 1, respectively weighing an amphiphilic block copolymer and bromoalkane; weighing a solvent according to the total mass of the weighed monomers, wherein the mass ratio of the solvent to the monomers is (3-7): 1;
step 1.2, pouring the amphiphilic block copolymer, brominated alkanes and the solvent weighed in the step 1.1 into a container, placing the container in an oil bath at 35-50 ℃, and continuously stirring for 24-48 h at a stirring speed of 200-300 rpm to obtain an amphiphilic block copolymer quaternary ammonium salt;
and step 1.3, purifying the amphiphilic block copolymer quaternary ammonium salt obtained in the step 1.2 by using ethyl acetate, and drying in a vacuum oven at the temperature of 35-60 ℃ for 24-48 h.
The amphiphilic block copolymer consists of a hydrophilic block and a hydrophobic block, wherein the hydrophilic block is one or two of poly (tert-butylaminoethyl methacrylate), poly (dimethylaminoethyl methacrylate), poly (diethylaminoethyl methacrylate) and poly (4-vinylpyridine); the hydrophobic block is one or two of polystyrene, polymethyl methacrylate, poly tert-butyl methacrylate and polycyclohexyl methacrylate;
the bromoalkane is bromoethane, bromopropane or bromobutane with the purity of 98 percent;
the solvent is tetrahydrofuran or N, N-dimethylformamide.
The step 2 is implemented according to the following steps:
step 2.1, respectively weighing the following raw materials:
according to the mass ratio of 1: (0.25-4) respectively weighing normal alkane and stearate as phase change materials;
according to the mass ratio of 1: (0.5-4): (0.02-0.8): (0.035-0.3): (5-60) respectively weighing the phase-change material, the acrylate monomer, the cross-linking agent, the amphiphilic block copolymer quaternary ammonium salt obtained in the step (1) and deionized water;
step 2.2, uniformly mixing the phase-change material weighed in the step 2.1, an acrylate monomer, a cross-linking agent, an amphiphilic block copolymer quaternary ammonium salt and deionized water to obtain an oil-water mixture;
and 2.3, ultrasonically dispersing the oil-water mixture obtained in the step 2.2 for 5-30 min by using an ultrasonic cell crusher to obtain the oil-in-water type pre-emulsion.
The n-alkane is n-tetradecane, n-hexadecane, n-octadecane, n-nonadecane, n-eicosane or n-docosane;
the stearate is ethyl stearate, propyl stearate, butyl stearate or glyceryl stearate;
the acrylate monomer is two or three of methyl methacrylate, lauryl methacrylate, ethyl acrylate, butyl acrylate and hydroxyethyl acrylate which are mixed in any proportion;
the cross-linking agent is ethylene glycol dimethacrylate, N-methylene bisacrylamide, divinylbenzene, divinyl sulfone, pentaerythritol triacrylate or diethylene glycol diacrylate.
Step 3 is specifically implemented according to the following steps:
step 3.1, weighing a water-soluble initiator, wherein the mass ratio of the initiator to the acrylate monomer weighed in the step 2 is (0.002-0.016): 1;
weighing deionized water, wherein the mass ratio of the deionized water to the initiator is 1: (0.006-0.03);
dissolving an initiator in deionized water to obtain an initiator aqueous solution;
step 3.2, pouring the oil-in-water type pre-emulsion obtained in the step 2 into a three-neck flask, placing the three-neck flask in a hot water bath at the temperature of 60-90 ℃ for stirring, and controlling the stirring speed to be 200-500 rpm;
and 3.3, dropwise adding the initiator aqueous solution obtained in the step 3.1 into a three-neck flask within 0.5-1 h, then continuously stirring, and carrying out heat preservation reaction for 5-10 h to obtain the polyacrylate-coated phase-change material microcapsule.
The water-soluble initiator is azobisisobutylamidine hydrochloride or azobisisobutylimidazoline hydrochloride.
Step 4 is specifically implemented according to the following steps:
step 4.1, weighing copper sulfate, wherein the mass ratio of the copper sulfate to the amphiphilic block copolymer quaternary ammonium salt weighed in the step 2 is 1: (0.3 to 0.7); weighing sodium hydroxide and a reducing agent according to the weighed copper sulfate, wherein the mass ratio of copper sulfate, sodium hydroxide and the reducing agent is 1: (4-8): (0.4 to 0.7);
and 4.2, preparing a sodium hydroxide aqueous solution and a reducing agent aqueous solution, wherein the mass ratio of the deionized water to the sodium hydroxide and the reducing agent weighed in the step 4.1 is 1: (0.10-0.15): (0.03-0.08);
step 4.3, adding the copper sulfate weighed in the step 4.1 into the polyacrylate-coated phase-change material microcapsule emulsion obtained in the step 3, uniformly mixing at a stirring speed of 200-500 rpm, dropwise adding a sodium hydroxide aqueous solution and a reducing agent aqueous solution, and carrying out heat preservation reaction for 2 hours at 50-80 ℃ to obtain Cu2O/polyacrylate compositeAnd (4) synthesizing the phase change microcapsules.
The reducing agent is hydrazine hydrate, sodium borohydride, sodium sulfite, glucose, ascorbic acid or sodium hypophosphite.
The invention has the beneficial effects that:
(1) the invention adopts RAFT miniemulsion polymerization method to synthesize Cu core material of binary composite phase change material2The phase change energy storage microcapsule with O/polyacrylate as wall material; the phase-change microcapsule takes a binary composite phase-change material as a core material, so that on one hand, the phase-change temperature range can be enlarged and the application field of the material can be expanded by regulating the binary core mass ratio, and on the other hand, the compatibility of the phase-change core material and an acrylate monomer can be improved by selecting a proper phase-change material; simultaneously, Cu obtained by copper sulfate precipitation reduction is grafted on polyacrylate obtained by polymerizing acrylate monomers2O is used as the wall material of the phase change microcapsule, since Cu2O has excellent heat-conducting property, and the phase-change microcapsule is endowed with faster thermal response;
(2) in the preparation method, the traditional micromolecule emulsifier is not used for stabilizing the oil-in-water type pre-emulsion, so that the adverse effects of the micromolecule emulsifier on the phase change microcapsule and the environment are avoided; the amphiphilic block copolymer quaternary ammonium salt obtained by RAFT polymerization is used as an emulsifier, so that the structure and the morphology of the phase-change microcapsule can be regulated, more phase-change core materials are coated in a thinner shell layer, and the phase-change microcapsule has better energy storage and temperature regulation performance and faster thermal response;
(3) in the preparation method of the invention, Cu obtained by copper sulfate precipitation reduction is grafted on a polyacrylate shell2O, the heat conductivity and the thermal stability of the material are effectively improved on the basis of ensuring the coating efficiency of the phase change microcapsule, the problems of poor wall material strength, low heat conductivity efficiency and the like of the phase change microcapsule products in the market are solved, and the material has more obvious thermal response and longer service life;
(4) the phase change microcapsule prepared by the preparation method has an obvious core-shell structure and uniform particle size, and has better energy storage and temperature regulation performances and antibacterial property when being finished on fabrics.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to Cu2The preparation method of the O/polyacrylate composite phase change microcapsule is implemented according to the following steps:
step 1, mixing the amphiphilic block copolymer with brominated alkane and a solvent, and carrying out quaternization reaction to obtain amphiphilic block copolymer quaternary ammonium salt;
the method is implemented according to the following steps:
step 1.1, according to the mass ratio of (0.14-0.20): 1, respectively weighing an amphiphilic block copolymer and bromoalkane; weighing a solvent according to the total mass of the weighed monomers, wherein the mass ratio of the solvent to the monomers is (3-7): 1;
step 1.2, pouring the amphiphilic block copolymer, brominated alkanes and the solvent weighed in the step 1.1 into a container, placing the container in an oil bath at 35-50 ℃, and continuously stirring for 24-48 h at a stirring speed of 200-300 rpm to obtain an amphiphilic block copolymer quaternary ammonium salt;
step 1.3, purifying the amphiphilic block copolymer quaternary ammonium salt obtained in the step 1.2 by using ethyl acetate, and drying in a vacuum oven at the temperature of 35-60 ℃ for 24-48 h;
the amphiphilic block copolymer consists of a hydrophilic block and a hydrophobic block, wherein the hydrophilic block is one or two of poly (tert-butylaminoethyl methacrylate), poly (dimethylaminoethyl methacrylate), poly (diethylaminoethyl methacrylate) and poly (4-vinylpyridine); the hydrophobic block is one or two of polystyrene, polymethyl methacrylate, poly tert-butyl methacrylate and polycyclohexyl methacrylate;
the bromoalkane is bromoethane, bromopropane or bromobutane with the purity of 98 percent;
the solvent is tetrahydrofuran or N, N-dimethylformamide.
Step 2, mixing the amphiphilic block copolymer quaternary ammonium salt obtained in the step 1 with a phase-change material, an acrylate monomer, a cross-linking agent and deionized water, and performing ultrasonic dispersion to form an oil-in-water type pre-emulsion;
the method is implemented according to the following steps:
step 2.1, respectively weighing the following raw materials:
according to the mass ratio of 1: (0.25-4) respectively weighing normal alkane and stearate as phase change materials;
according to the mass ratio of 1: (0.5-4): (0.02-0.8): (0.035-0.3): (5-60) respectively weighing the phase-change material, the acrylate monomer, the cross-linking agent, the amphiphilic block copolymer quaternary ammonium salt obtained in the step (1) and deionized water;
step 2.2, uniformly mixing the phase-change material weighed in the step 2.1, an acrylate monomer, a cross-linking agent, an amphiphilic block copolymer quaternary ammonium salt and deionized water to obtain an oil-water mixture;
2.3, ultrasonically dispersing the oil-water mixture obtained in the step 2.2 for 5-30 min by using an ultrasonic cell crusher to obtain an oil-in-water type pre-emulsion;
the n-alkane is n-tetradecane, n-hexadecane, n-octadecane, n-nonadecane, n-eicosane or n-docosane;
the stearate is ethyl stearate, propyl stearate, butyl stearate or glyceryl stearate;
the acrylate monomer is two or three of methyl methacrylate, lauryl methacrylate, ethyl acrylate, butyl acrylate and hydroxyethyl acrylate which are mixed in any proportion;
the cross-linking agent is ethylene glycol dimethacrylate, N-methylene bisacrylamide, divinylbenzene, divinyl sulfone, pentaerythritol triacrylate or diethylene glycol diacrylate.
Step 3, placing the oil-in-water type pre-emulsion obtained in the step 2 in a hot water bath for heating and continuously stirring, adding an initiator aqueous solution, and carrying out heat preservation reaction to obtain a polyacrylate coated phase change material microcapsule;
the method is implemented according to the following steps:
step 3.1, weighing a water-soluble initiator, wherein the mass ratio of the initiator to the acrylate monomer weighed in the step 2 is (0.002-0.016): 1;
weighing deionized water, wherein the mass ratio of the deionized water to the initiator is 1: (0.006-0.03);
dissolving an initiator in deionized water to obtain an initiator aqueous solution;
step 3.2, pouring the oil-in-water type pre-emulsion obtained in the step 2 into a three-neck flask, placing the three-neck flask in a hot water bath at the temperature of 60-90 ℃ for stirring, and controlling the stirring speed to be 200-500 rpm;
step 3.3, dropwise adding the initiator aqueous solution obtained in the step 3.1 into a three-neck flask within 0.5-1 h, then continuously stirring, and carrying out heat preservation reaction for 5-10 h to obtain a polyacrylate-coated phase-change material microcapsule;
the water-soluble initiator is azobisisobutylamidine hydrochloride or azobisisobutylimidazoline hydrochloride.
Step 4, mixing the polyacrylate coated phase-change material microcapsule obtained in the step 3 with copper sulfate, sodium hydroxide and a reducing agent, and reacting at constant temperature to obtain Cu2O/polyacrylate composite phase change microcapsule;
the method is implemented according to the following steps:
step 4.1, weighing copper sulfate, wherein the mass ratio of the copper sulfate to the amphiphilic block copolymer quaternary ammonium salt weighed in the step 2 is 1: (0.3 to 0.7); weighing sodium hydroxide and a reducing agent according to the weighed copper sulfate, wherein the mass ratio of copper sulfate, sodium hydroxide and the reducing agent is 1: (4-8): (0.4 to 0.7);
and 4.2, preparing a sodium hydroxide aqueous solution and a reducing agent aqueous solution, wherein the mass ratio of the deionized water to the sodium hydroxide and the reducing agent weighed in the step 4.1 is 1: (0.10-0.15): (0.03-0.08);
step 4.3, adding the copper sulfate weighed in the step 4.1 into the polyacrylate-coated phase-change material microcapsule emulsion obtained in the step 3, uniformly mixing at a stirring speed of 200-500 rpm, dropwise adding a sodium hydroxide aqueous solution and a reducing agent aqueous solution, and carrying out heat preservation reaction for 2 hours at 50-80 ℃ to obtain Cu2O/polyacrylate composite phase change microcapsule;
the reducing agent is hydrazine hydrate, sodium borohydride, sodium sulfite, glucose, ascorbic acid or sodium hypophosphite.
Example 1
According to the mass ratio of 0.17: 1, respectively weighing an amphiphilic block copolymer (consisting of hydrophilic block poly (diethylaminoethyl methacrylate) and hydrophobic block polystyrene) and bromobutane; weighing tetrahydrofuran according to the total mass of the weighed monomers, wherein the mass ratio of the tetrahydrofuran to the monomers is 4: 1;
pouring the amphiphilic block copolymer, bromobutane and tetrahydrofuran into a container, putting the container in an oil bath at 40 ℃, and continuously stirring for 24 hours at a stirring speed of 250rpm to obtain amphiphilic block copolymer quaternary ammonium salt; purifying the amphiphilic block copolymer quaternary ammonium salt by using ethyl acetate, and drying in a vacuum oven at 40 ℃ for 24 hours;
according to the mass ratio of 1: 0.25 respectively weighing n-octadecane and butyl stearate as phase change materials; according to the mass ratio of 1: 1: 0.05: 0.045: 10 respectively weighing the phase-change material, an acrylate monomer (mixing methyl methacrylate, lauryl methacrylate and ethyl acrylate according to a mass ratio of 8: 1: 1), ethylene glycol dimethacrylate, amphiphilic block copolymer quaternary ammonium salt and deionized water; uniformly mixing a phase change material, an acrylate monomer, ethylene glycol dimethacrylate, amphiphilic block copolymer quaternary ammonium salt and deionized water to obtain an oil-water mixture; ultrasonically dispersing the oil-water mixture for 10min by using an ultrasonic cell crusher to obtain an oil-in-water type pre-emulsion;
weighing azodiisobutyl amidine hydrochloride, wherein the mass ratio of the azodiisobutyl amidine hydrochloride to the acrylate monomer is 0.008: 1; weighing deionized water, wherein the mass ratio of the deionized water to the azodiisobutyl amidine hydrochloride agent is 1: 0.018; dissolving azodiisobutyl amidine hydrochloride into deionized water to obtain an initiator aqueous solution; pouring the oil-in-water type pre-emulsion into a three-neck flask, placing the three-neck flask in a hot water bath at 70 ℃ for stirring, controlling the stirring speed to be 250rpm, dropwise adding an initiator aqueous solution (dropwise adding is completed within 1 h), and carrying out heat preservation reaction for 5h to obtain a polyacrylate coated phase-change material microcapsule;
weighing copper sulfate, wherein the mass ratio of the copper sulfate to the amphiphilic block copolymer quaternary ammonium salt is 1: 0.3; weighing sodium hydroxide and hydrazine hydrate according to the weighed mass of copper sulfate, wherein the mass ratio of copper sulfate to sodium hydroxide to hydrazine hydrate is 1: 5: 0.6; preparing a sodium hydroxide aqueous solution and a hydrazine hydrate aqueous solution, wherein the mass ratio of deionized water to sodium hydroxide to hydrazine hydrate is 1: 0.12: 0.05;
adding weighed copper sulfate into polyacrylate coated phase change material microcapsule emulsion, uniformly mixing at the stirring speed of 250rpm, dropwise adding sodium hydroxide aqueous solution and hydrazine hydrate aqueous solution, and carrying out heat preservation reaction for 2 hours at 70 ℃ to obtain Cu2O/polyacrylate composite phase change microcapsule.
TABLE 1 polyacrylate coated phase change material microcapsules and Cu2Phase change performance and antibacterial property of O/polyacrylate composite phase change microcapsule
Example 2
According to the mass ratio of 0.15: 1, respectively weighing an amphiphilic block copolymer (consisting of hydrophilic block poly (dimethylaminoethyl methacrylate) and hydrophobic block polystyrene) and bromobutane; weighing tetrahydrofuran according to the total mass of the weighed monomers, wherein the mass ratio of the tetrahydrofuran to the monomers is 5: 1; pouring the weighed amphiphilic block copolymer, bromobutane and tetrahydrofuran into a container, placing the container in an oil bath at 40 ℃, and continuously stirring for 24 hours at a stirring speed of 250rpm to obtain amphiphilic block copolymer quaternary ammonium salt; purifying the amphiphilic block copolymer quaternary ammonium salt by using ethyl acetate, and drying in a vacuum oven at 40 ℃ for 24-48 h;
according to the mass ratio of 1: 0.4 respectively weighing n-octadecane and butyl stearate as phase change materials; according to the mass ratio of 1: 2: 0.1: 0.065: 30 respectively weighing the phase-change material, an acrylate monomer (mixing methyl methacrylate, butyl acrylate and ethyl acrylate according to the mass ratio of 9: 0.5: 0.5), diethylene glycol diacrylate, amphiphilic block copolymer quaternary ammonium salt and deionized water; uniformly mixing the weighed phase change material, acrylate monomer, diethylene glycol diacrylate, amphiphilic block copolymer quaternary ammonium salt and deionized water to obtain an oil-water mixture;
ultrasonically dispersing the oil-water mixture for 10min by using an ultrasonic cell crusher to obtain an oil-in-water type pre-emulsion;
weighing azodiisobutyl imidazoline hydrochloride, wherein the mass ratio of the azodiisobutyl imidazoline hydrochloride to the acrylate monomer is 0.012: 1; weighing deionized water, wherein the mass ratio of the deionized water to the azobisisobutylimidazoline hydrochloride is 1: 0.015; dissolving azodiisobutyl imidazoline hydrochloride in deionized water to obtain an initiator aqueous solution; pouring the oil-in-water type pre-emulsion into a three-neck flask, placing the three-neck flask in a hot water bath at 70 ℃ for stirring, controlling the stirring speed to be 250rpm, dropwise adding an initiator aqueous solution (dropwise adding is completed within 1 h), and carrying out heat preservation reaction for 5h to obtain a polyacrylate coated phase-change material microcapsule;
weighing copper sulfate, wherein the mass ratio of the copper sulfate to the amphiphilic block copolymer quaternary ammonium salt is 1: 0.5; weighing sodium hydroxide and hydrazine hydrate according to the weighed mass of copper sulfate, wherein the mass ratio of copper sulfate to sodium hydroxide to hydrazine hydrate is 1: 6: 0.6; preparing a sodium hydroxide aqueous solution and a hydrazine hydrate aqueous solution, wherein the mass ratio of deionized water to sodium hydroxide to hydrazine hydrate is 1: 0.12: 0.05; adding copper sulfate into polyacrylate coated phase change material microcapsule emulsion, uniformly mixing at the stirring speed of 250rpm, dropwise adding sodium hydroxide aqueous solution and hydrazine hydrate aqueous solution, and reacting at the temperature of 70 ℃ for 2 hours to obtain Cu2O/polyacrylate composite phase change microcapsule.
TABLE 2 polyacrylate coated phase change material microcapsules and Cu2Phase change performance and antibacterial property of O/polyacrylate composite phase change microcapsule
Example 3
According to the mass ratio of 0.20: 1, respectively weighing an amphiphilic block copolymer (consisting of hydrophilic block dimethylaminoethyl methacrylate, hydrophobic block polystyrene and polymethyl methacrylate) and bromobutane; weighing N, N-dimethylformamide according to the total mass of the weighed monomers, wherein the mass ratio of the N, N-dimethylformamide to the monomers is 4: 1; pouring the weighed amphiphilic block copolymer, bromobutane and N, N-dimethylformamide into a container, placing the container in an oil bath at 40 ℃, and continuously stirring for 24 hours at a stirring speed of 250rpm to obtain amphiphilic block copolymer quaternary ammonium salt; purifying the amphiphilic block copolymer quaternary ammonium salt by using ethyl acetate, and drying in a vacuum oven at 60 ℃ for 24 hours;
according to the mass ratio of 1: 2, respectively weighing n-octadecane and butyl stearate as phase change materials; according to the mass ratio of 1: 3: 0.4: 0.1: 30 respectively weighing the phase-change material, an acrylate monomer (mixing methyl methacrylate, ethyl acrylate and hydroxyethyl acrylate according to the mass ratio of 9: 0.5: 0.5), pentaerythritol triacrylate, an amphiphilic block copolymer quaternary ammonium salt and deionized water; uniformly mixing the weighed phase-change material, acrylate monomer, pentaerythritol triacrylate, amphiphilic block copolymer quaternary ammonium salt and deionized water to obtain an oil-water mixture;
ultrasonically dispersing the oil-water mixture for 10min by using an ultrasonic cell crusher to obtain an oil-in-water type pre-emulsion;
weighing azodiisobutyl imidazoline hydrochloride, wherein the mass ratio of the azodiisobutyl imidazoline hydrochloride to the weighed acrylate monomer is 0.01: 1; weighing deionized water, wherein the mass ratio of the deionized water to the azobisisobutylimidazoline hydrochloride is 1: 0.02; dissolving azodiisobutyl imidazoline hydrochloride in deionized water to obtain an initiator aqueous solution; pouring the oil-in-water type pre-emulsion into a three-neck flask, placing the three-neck flask in a hot water bath at 70 ℃ for stirring, and controlling the stirring speed to be 250 rpm; dropwise adding an initiator aqueous solution into a three-neck flask within 1h, then continuously stirring, and carrying out heat preservation reaction for 5h to obtain a polyacrylate-coated phase-change material microcapsule;
weighing copper sulfate, wherein the mass ratio of the copper sulfate to the weighed amphiphilic block copolymer quaternary ammonium salt is 1: 0.4; weighing sodium hydroxide and glucose according to the weighed copper sulfate, wherein the mass ratio of copper sulfate to sodium hydroxide to glucose is 1: 5: 0.6; preparing sodium hydroxide aqueous solution and glucose aqueous solution, wherein the mass ratio of the deionized water to the weighed sodium hydroxide to the weighed glucoseIs 1: 0.10: 0.04; adding weighed copper sulfate into polyacrylate coated phase change material microcapsule emulsion, uniformly mixing at the stirring speed of 250rpm, dropwise adding sodium hydroxide aqueous solution and glucose aqueous solution, and carrying out heat preservation reaction for 2 hours at 70 ℃ to obtain Cu2O/polyacrylate composite phase change microcapsule.
TABLE 3 polyacrylate-coated phase-change material microcapsules and Cu2Phase change performance and antibacterial property of O/polyacrylate composite phase change microcapsule
The invention relates to Cu2The preparation method of the O/polyacrylate composite phase change microcapsule adopts an RAFT miniemulsion polymerization method to prepare the composite phase change microcapsule which has high coating rate, good thermal conductivity and good thermal stability, has a proper phase change temperature range and larger phase change latent enthalpy (the phase change temperature is 15-35 ℃, and the phase change latent enthalpy is 179.6J/g), and has obvious antibacterial property on staphylococcus aureus.
Claims (2)
1. Cu2The preparation method of the O/polyacrylate composite phase change microcapsule is characterized by comprising the following steps:
step 1, mixing the amphiphilic block copolymer with brominated alkanes and a solvent, and carrying out quaternization reaction to obtain the amphiphilic block copolymer quaternary ammonium salt, which comprises the following steps:
step 1.1, according to the mass ratio of (0.14-0.20): 1, respectively weighing an amphiphilic block copolymer and bromoalkane; weighing a solvent according to the total mass of the weighed monomers, wherein the mass ratio of the solvent to the monomers is (3-7): 1;
the amphiphilic block copolymer consists of a hydrophilic block and a hydrophobic block, wherein the hydrophilic block is one or two of poly (tert-butylaminoethyl methacrylate), poly (dimethylaminoethyl methacrylate), poly (diethylaminoethyl methacrylate) and poly (4-vinylpyridine); the hydrophobic block is one or two of polystyrene, polymethyl methacrylate, poly tert-butyl methacrylate and polycyclohexyl methacrylate;
the bromoalkane is bromoethane, bromopropane or bromobutane with the purity of 98 percent;
the solvent is tetrahydrofuran or N, N-dimethylformamide;
step 1.2, pouring the amphiphilic block copolymer, brominated alkanes and the solvent weighed in the step 1.1 into a container, placing the container in an oil bath at 35-50 ℃, and continuously stirring for 24-48 h at a stirring speed of 200-300 rpm to obtain an amphiphilic block copolymer quaternary ammonium salt;
step 1.3, purifying the amphiphilic block copolymer quaternary ammonium salt obtained in the step 1.2 by using ethyl acetate, and drying in a vacuum oven at the temperature of 35-60 ℃ for 24-48 h;
step 2, mixing the amphiphilic block copolymer quaternary ammonium salt obtained in the step 1 with a phase-change material, an acrylate monomer, a cross-linking agent and deionized water, and performing ultrasonic dispersion to form an oil-in-water type pre-emulsion, which comprises the following specific steps:
step 2.1, respectively weighing the following raw materials:
according to the mass ratio of 1: (0.25-4) respectively weighing normal alkane and stearate as phase change materials;
according to the mass ratio of 1: (0.5-4): (0.02-0.8): (0.035-0.3): (5-60) respectively weighing the phase-change material, the acrylate monomer, the cross-linking agent, the amphiphilic block copolymer quaternary ammonium salt obtained in the step (1) and deionized water;
step 2.2, uniformly mixing the phase-change material weighed in the step 2.1, an acrylate monomer, a cross-linking agent, an amphiphilic block copolymer quaternary ammonium salt and deionized water to obtain an oil-water mixture;
2.3, ultrasonically dispersing the oil-water mixture obtained in the step 2.2 for 5-30 min by using an ultrasonic cell crusher to obtain an oil-in-water type pre-emulsion;
the n-alkane is n-tetradecane, n-hexadecane, n-octadecane, n-nonadecane, n-eicosane or n-docosane;
the stearate is ethyl stearate, propyl stearate, butyl stearate or glyceryl stearate;
the acrylate monomer is two or three of methyl methacrylate, lauryl methacrylate, ethyl acrylate, butyl acrylate and hydroxyethyl acrylate which are mixed in any proportion;
the cross-linking agent is ethylene glycol dimethacrylate, N-methylene bisacrylamide, divinylbenzene, divinyl sulfone, pentaerythritol triacrylate or diethylene glycol diacrylate;
and 3, heating the oil-in-water type pre-emulsion obtained in the step 2 in a hot water bath, continuously stirring, adding an initiator aqueous solution, and carrying out heat preservation reaction to obtain the polyacrylate coated phase change material microcapsule, wherein the specific steps are as follows:
step 3.1, weighing a water-soluble initiator, wherein the mass ratio of the initiator to the acrylate monomer weighed in the step 2 is (0.002-0.016): 1;
weighing deionized water, wherein the mass ratio of the deionized water to the initiator is 1: (0.006-0.03);
dissolving an initiator in deionized water to obtain an initiator aqueous solution;
step 3.2, pouring the oil-in-water type pre-emulsion obtained in the step 2 into a three-neck flask, placing the three-neck flask in a hot water bath at the temperature of 60-90 ℃ for stirring, and controlling the stirring speed to be 200-500 rpm;
step 3.3, dropwise adding the initiator aqueous solution obtained in the step 3.1 into a three-neck flask within 0.5-1 h, then continuously stirring, and carrying out heat preservation reaction for 5-10 h to obtain a polyacrylate-coated phase-change material microcapsule;
step 4, mixing the polyacrylate coated phase-change material microcapsule obtained in the step 3 with copper sulfate, sodium hydroxide and a reducing agent, and reacting at constant temperature to obtain Cu2O/polyacrylate composite phase change microcapsule; the method comprises the following specific steps:
step 4.1, weighing copper sulfate, wherein the mass ratio of the copper sulfate to the amphiphilic block copolymer quaternary ammonium salt weighed in the step 2 is 1: (0.3 to 0.7); weighing sodium hydroxide and a reducing agent according to the weighed copper sulfate, wherein the mass ratio of copper sulfate, sodium hydroxide and the reducing agent is 1: (4-8): (0.4 to 0.7);
and 4.2, preparing a sodium hydroxide aqueous solution and a reducing agent aqueous solution, wherein the mass ratio of the deionized water to the sodium hydroxide and the reducing agent weighed in the step 4.1 is 1: (0.10-0.15): (0.03-0.08);
step 4.3, adding the copper sulfate weighed in the step 4.1 into the polyacrylate-coated phase-change material microcapsule emulsion obtained in the step 3, uniformly mixing at a stirring speed of 200-500 rpm, dropwise adding a sodium hydroxide aqueous solution and a reducing agent aqueous solution, and carrying out heat preservation reaction for 2 hours at 50-80 ℃ to obtain Cu2O/polyacrylate composite phase change microcapsule;
the reducing agent is hydrazine hydrate, sodium borohydride, sodium sulfite, glucose, ascorbic acid or sodium hypophosphite.
2. Cu according to claim 12The preparation method of the O/polyacrylate composite phase change microcapsule is characterized by comprising the following steps: the water-soluble initiator is azo diisobutyl amidine hydrochloride or azo diisobutyl imidazoline hydrochloride.
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| CN105056854A (en) * | 2015-07-27 | 2015-11-18 | 陕西科技大学 | Preparation method for nanometer TiO2 modified composite phase change microcapsule |
| CN106675524A (en) * | 2016-07-13 | 2017-05-17 | 北京化工大学 | Multifunctional phase change material microcapsule and preparation method thereof |
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| CN101501089A (en) * | 2006-08-03 | 2009-08-05 | 西巴控股有限公司 | Block copolymers of diallyldialkylammonium derivatives |
| CN105017469A (en) * | 2015-07-16 | 2015-11-04 | 陕西科技大学 | Preparation method of cationic type fluorine-containing soap-free emulsion |
| CN105056854A (en) * | 2015-07-27 | 2015-11-18 | 陕西科技大学 | Preparation method for nanometer TiO2 modified composite phase change microcapsule |
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