CN111672436A - Flame-retardant phase-change microcapsule and preparation method and application thereof - Google Patents
Flame-retardant phase-change microcapsule and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of phase change energy storage materials, and particularly relates to a flame-retardant phase change microcapsule as well as a preparation method and application thereof. The invention leads the monomer and the cross-linking agent in the emulsion to generate polymerization reaction through the initiation of an initiator at a certain temperature, a polymerizable silane monomer with double bonds and the cross-linking agent form an organic shell layer on the surface of the microcapsule after polymerization, and silicon methoxyl or silicon ethoxyl of the polymerizable silane monomer generates sol-gel reaction condensation to form a silicon dioxide inorganic shell layer on the surface of the microcapsule.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage materials, and particularly relates to a flame-retardant phase change microcapsule as well as a preparation method and application thereof.
Background
In recent years, global energy is increasingly in shortage and the main energy used at present is not renewable, so that the sustainable development of economy is restricted. The heat storage technology utilizes the internal energy conversion of substances, collects, stores, transports and releases heat energy in a manual intervention mode, and further realizes reasonable regulation and control of heat energy supply and demand relations. The phase-change heat storage has the characteristics of high heat storage density, low cost, approximately constant temperature in the heat storage and release process and controllable heat storage and release, and is a heat storage technology with the most extensive application prospect. A phase change material refers to a substance that absorbs or emits a large amount of energy while undergoing a phase transition at a substantially constant temperature. The phase-change material is utilized to store energy (cool storage and heat storage), the mismatching of the distribution of time and space between the requirement and the supply of energy can be solved, and the use efficiency of the energy can be improved. The traditional solid-liquid phase change material is heated, melted and flowed, and can damage other parts. Therefore, in the practical application process, the phase-change material is encapsulated by adopting a microencapsulation method, so that the problems can be effectively solved, and the advantages of increasing the heat transfer area and controlling the volume change of the phase-change material are also achieved. In recent years, more and more phase-change microcapsules are prepared, and the phase-change microcapsules show good application prospects in the fields of buildings, energy conservation, textiles, military and the like, and the application field of phase-change materials is expanded. However, the phase-change material and the shell material of the current phase-change microcapsule are mainly organic combustible materials, which cannot meet the requirements of practical application in the industrial fields of batteries, pouring sealant and the like, and limit the popularization of the phase-change microcapsule in the application of other fields.
Chinese patent document CN 105542721a discloses a method for preparing a flame retardant phase change microcapsule, in which a flame retardant chlorinated paraffin is mixed into an organic phase change material to prepare the flame retardant phase change microcapsule, but the flame retardant chlorinated paraffin releases hydrogen chloride gas during combustion to cause serious pollution, and meanwhile, the shell layer of the microcapsule prepared by the method is a flammable organic polymer material, and the flammability problem of the microcapsule cannot be solved.
Chinese patent document CN 105112020a discloses another preparation method of a flame retardant phase change microcapsule, which is to polymerize a reactive phosphonate monomer and an acrylic acid monomer to obtain a polymer capsule wall with a certain flame retardant property, but the shell layer of the microcapsule is still an organic material, and the flame retardant problem of the microcapsule cannot be fundamentally solved.
Chinese patent document CN 109225085A discloses that a phosphorus-containing melamine-formaldehyde resin is used as a capsule wall material to improve the flame retardant property of a phase-change microcapsule, but the shell layer of the microcapsule is still an organic material and the flame retardant problem of the microcapsule cannot be fundamentally solved.
Although the inorganic shell layer should be used as the outermost layer of the microcapsule, the inorganic shell layer has better flame retardant property than the organic wall material, and has the outstanding advantages of corrosion resistance, strong firmness and the like, thereby improving the durability and having good support property. However, the material has complex preparation process, poor encapsulation performance and easy rupture of microcapsules. The composite of the outer inorganic layer and the inner organic layer can improve the flame retardant property of the microcapsule while keeping the stable structure of the microcapsule. Some patent documents report methods in which an inorganic reaction precursor, a styrene or acrylate organic resin monomer, a crosslinking agent, and an initiator are dissolved in a molten phase-change material, added to an emulsifier and water, and then dispersed to obtain an emulsion, and an inorganic/organic composite structure is obtained by polymerization. The method has the following problems: (1) because a large amount of monomers and inorganic substance reaction precursors, and inorganic substance reaction precursors and monomers are introduced into the phase-change material, the inorganic substance is difficult to be ensured to be completely transferred to the surface of the shell layer; (2) the phase-change material of the dispersed phase contains too many components, and the uniformity of the dispersed phase is not easy to realize in the batch production process; (3) a large amount of precursors and monomers are added into emulsion droplets, so that a large amount of volume is occupied, a capsule shell layer is easy to deform and collapse to form a bowl shape, and the microcapsule shell layer is easy to break at a position with serious deformation; (4) the phase change material of the microcapsule is a single organic combustible material.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a preparation method of a flame-retardant phase-change microcapsule, which comprises the following steps:
1) preparation of the dispersed phase: adding a polymerizable silane monomer, a cross-linking agent monomer and a flame retardant into the molten phase-change material to prepare the phase-change material;
2) preparation of the continuous phase: dissolving emulsifier in water;
3) preparing microcapsules: heating the continuous phase obtained in the step 2) to be above the melting point of the phase-change material, mixing the continuous phase with the dispersed phase obtained in the step 1), emulsifying and reacting;
wherein, the initiator is added into the dispersed phase or the continuous phase, or the initiator is added after the dispersed phase or the continuous phase is mixed.
4) Optionally, adding an inorganic precursor into the system after the reaction in the step 3) and continuing the reaction.
According to the embodiment of the invention, after the inorganic precursor is added, sol-gel can be continuously carried out on the surface of the microcapsule, so that the thickness of an inorganic shell layer is increased, and the aim of further improving the flame retardance of the microcapsule is fulfilled.
According to the embodiment of the invention, the phase change material in the step 1) is at least one selected from alcohol compounds with 4-50 carbon atoms, organic acid compounds with 4-50 carbon atoms, alkane or aromatic hydrocarbon compounds with 6-50 carbon atoms, or esters obtained by reacting the alcohol compounds with 4-50 carbon atoms with the organic acid compounds with 4-50 carbon atoms;
according to an embodiment of the present invention, the alcohol compound is at least one selected from alkyl alcohols having 4 to 50 carbon atoms, such as tetradecanol and hexadecanol;
according to the embodiment of the invention, at least one of alkyl acid with 4-50 carbon atoms, such as lauric acid;
according to an embodiment of the present invention, the alkane compound having 6 to 50 carbon atoms is selected from n-dodecane, paraffin, octadecane or n-eicosane.
According to an embodiment of the invention, the paraffin wax has a melting point of 10 ℃ to 90 ℃.
According to an embodiment of the invention, said ester is selected from butyl stearate.
According to an embodiment of the invention, the polymerizable silane monomer in step 1) is selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, styrene-dimethylsiloxane, styrene ethyltrimethylsiloxane, isobutylene triethoxysilane, 3-isobutylene propyltriethoxysilane, 3- (methacryloyloxy) propyltris (trimethylsiloxane) silane, and the like.
According to an embodiment of the present invention, the crosslinking agent monomer in step 1) is an unsaturated bond-containing crosslinking agent, for example, at least one of styrene derivatives such as divinylbenzene, styrene ethyltrimethicone, 1, 3-diisopropenylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, hexanediol dimethacrylate, and the like.
According to an embodiment of the present invention, the mass of the polymerizable silane monomer in step 1) accounts for 5% to 100% of the phase change material, for example, 6% to 50%, such as 7% to 40%.
According to an embodiment of the invention, the proportion of the mass of the cross-linker monomer in step 1) in the phase change material is between 0.5% and 50%, for example between 0.75% and 40%, such as between 0.8% and 30%.
According to an embodiment of the invention, the mass of initiator in step 1) is between 0.1% and 30%, for example between 0.4% and 20%, of the total mass of coupling agent monomer and crosslinking agent.
According to an embodiment of the present invention, the flame retardant in step 1) is selected from at least one of alkyl phosphates, aryl phosphates, inorganic flame retardants, nitrogen-based flame retardants, for example at least one selected from the group consisting of: tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, Pyrol99, tolylene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl) -diphenyl phosphate, red phosphorus, ammonium polyphosphate, diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony trioxide, molybdenum trioxide, melamine cyanurate, dicyandiamide, guanidine carbonate, guanidine phosphate, condensed guanidine phosphate, guanidine sulfamate, and the like.
According to an embodiment of the present invention, the flame retardant in step 1) accounts for 0.1% to 30% by mass of the phase change material, for example 0.2% to 20%, such as 0.25% to 10%.
According to an embodiment of the invention, the emulsifier in step 2) is selected from sodium salt hydrolysate of ethylene-maleic anhydride copolymer, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolysate of ethylene methyl ether-maleic anhydride copolymer, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, copolymer obtained by copolymerizing acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonic acid, polyoxyethylene octylphenol ether, polyoxyethylene octylphenyl ether X-100, sodium dodecylsulfate, sodium dodecylbenzenesulfonate, Tween 20, Tween60 (Tween60), Tween 80, and styrene, Span 60, span 65, span 80 and/or dioctyl sodium sulfosuccinate.
According to an embodiment of the invention, the mass proportion of emulsifier in the continuous phase in step 2) to the mass of water is between 0.05% and 5%, for example between 2% and 5%, such as between 2% and 4.5%.
According to an embodiment of the present invention, the initiator in step 3) is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, potassium persulfate, ammonium persulfate, potassium persulfate, sodium bisulfite, benzoyl peroxide, cumene hydroperoxide and other radical polymerization initiators.
According to an embodiment of the invention, the mass ratio of the dispersed phase to the continuous phase in step 3) is 1:1 to 1:50, such as 1:1 to 1:10, for example 1:1 to 1: 5.
According to an embodiment of the invention, said emulsification in step 3) is achieved by shear emulsification at a rotational speed in the range of 500 to 40000, such as 2000 to 15000 revolutions per minute; the shearing time is 1 to 300 minutes, such as 5 to 20 minutes.
According to the embodiment of the invention, the reaction temperature in the step 3) is 30-90 ℃, and the reaction time is 1-48 hours, preferably 6-12 hours.
According to an embodiment step of the present invention, the inorganic precursor in step 4) is selected from at least one of ethyl orthosilicate, epoxypropyltrimethoxysilane, phenyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltrimethoxysilane, n-octyltriethoxysilane, tetrabutyl stannate, NW-2 stannate coupling agent, tetrabutyl zirconate, triisopropyl aluminate, tribenzyl aluminate.
According to the steps of the embodiment of the invention, the reaction temperature in the step 4) is 20-90 ℃, and the reaction time is 1-48 hours, preferably 6-12 hours.
The invention also provides the flame-retardant phase-change microcapsule prepared by the method, which comprises a core and a shell, wherein the core contains a flame retardant and a phase-change material, and the shell is an organic/inorganic composite shell consisting of a silane polymer and silicon dioxide.
According to an embodiment of the invention, the shell is formed from a polymerizable silane monomer, a crosslinker monomer.
According to an embodiment of the invention, the particle size of the phase change microcapsules is 0.1 to 150 microns, such as 1 to 100 microns.
The invention also provides application of the phase change microcapsule as a flame retardant material in the fields of building, energy saving, textile and military.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
Where a range of numerical values is recited in the specification and claims of this application, and where the range is defined as "a number", it is understood that the two endpoints of the range and each number within the range are recited. For example, "4 to 50" means each number of 4, 5, 6, 7, 8, 9, 10 … … to 50.
Advantageous effects
The invention leads the monomer and the cross-linking agent in the emulsion to generate polymerization reaction through the initiation of an initiator at a certain temperature, a polymerizable silane monomer with double bonds and the cross-linking agent form an organic shell layer on the surface of the microcapsule after polymerization, and silicon methoxyl or silicon ethoxyl of the polymerizable silane monomer generates sol-gel reaction condensation to form a silicon dioxide inorganic shell layer on the surface of the microcapsule.
Specifically, the microcapsule of the present invention has the following advantages:
(1) can be prepared by a one-step method.
(2) Good appearance, regular spherical shape, no collapse and no obvious deformation.
(3) The leakage rate after heating and melting is extremely low, and the alloy can be subjected to tests of hundreds of thermal cycles without leakage.
(4) The inorganic component in the shell layer has adjustable thickness, and the inorganic component can further improve the flame retardant property of the microcapsule.
(5) The phase-change material is added with an environment-friendly flame retardant and releases halogen-free.
(6) The preparation process is simple, the cost is low, and the industrial production is easy to realize.
Drawings
FIG. 1 is a scanning electron microscope image of the flame-retardant phase-change microcapsule according to embodiment 1 of the present invention.
FIG. 2 is a DSC of the flame retardant phase change microcapsule of example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Unless otherwise specified, the size of the phase-change microcapsule dry powder in the following examples is measured by a scanning electron microscope; the phase change latent heat and the phase change temperature are obtained by performing integral calculation on a peak area and a DSC (differential scanning calorimetry) chart of the flame-retardant phase change microcapsule.
The heat fusion leak rate was tested by thermal cycling test in the following examples.
Testing of thermal cycling: 10g of phase change microcapsules are weighed and placed on filter paper, heated to 20 ℃ above the melting point of the phase change material for 30 minutes, then cooled to room temperature, and the filter paper is weighed to increase the weight. The heat-melting leakage rate is (filter paper weight gain/10) × 100%.
In addition, the inorganic precursor is added into the reaction system subsequently, sol-gel is continued on the surface of the microcapsule, the thickness of the inorganic shell layer is improved, the thickness of the inorganic component in the shell layer is adjustable, and the flame retardance of the microcapsule is further improved.
And (3) testing the flame retardant property: and testing the flame retardant property of the phase-change microcapsule by an alcohol burner combustion method. Putting the to-be-tested flame-retardant microcapsule powder on a medicine spoon, directly putting the to-be-tested flame-retardant microcapsule powder into an alcohol lamp to carry out flame heating, observing and recording the combustion time of the to-be-tested phase-change microcapsule powder, and evaluating the flame-retardant property by taking the time used for combustion as the flame-retardant time.
Example 1
10g of isobutylene triethoxysilane, 2g of hexanediol dimethacrylate, 10g of tributyl phosphate and 1g of benzoyl peroxide were taken, and 100g of molten sliced paraffin (phase transition temperature 25 ℃) was thoroughly mixed to obtain a dispersion phase. 2g of sodium dodecylbenzenesulfonate are added to 150g of water as a continuous phase and heated to 26 ℃. Adding the dispersed phase into the continuous phase, emulsifying by high-speed shearing for 20min at 7000rpm, transferring the obtained emulsion into a three-neck flask, reacting at 70 ℃ for 10 hours, cooling the system, adding 10g of epoxypropyl trimethoxy silane into the three-neck flask, and reacting at 35 ℃ for 12 hours. And separating the product by suction filtration, washing with deionized water, and drying in vacuum to obtain the phase change microcapsule dry powder.
The scanning electron micrograph of the flame-retardant phase-change microcapsule prepared in this example is shown in fig. 1. As can be seen from FIG. 1, the flame-retardant phase-change microcapsule prepared by the embodiment has the advantages of good appearance, regular spherical shape, no collapse, 1-20 microns in size and good coating effect.
FIG. 2 is a DSC of the flame retardant phase change microcapsule of example 1 of the present invention. The phase-change latent heat of the flame-retardant phase-change microcapsule prepared in the embodiment is 156.5J/g by integrating the peak area of FIG. 2.
The phase change temperature of the flame-retardant phase change microcapsule prepared by the embodiment is 26 ℃, the latent heat of phase change is 156.5J/g, the particle size is 1-20 micrometers, the heating melting leakage rate is 0.2%, and the combustion time of a flame-retardant test is 24 seconds.
A comparative sample was prepared in the same manner as described above except that 10g of tributyl phosphate and 10g of epoxypropyltrimethoxysilane were not added to the comparative sample, and the synthesis conditions were different from those in example 1.
The comparative samples had a flame test burn time of less than 2 seconds.
Example 2
10g of isobutylene triethoxysilane, 2g of hexanediol dimethacrylate, 10g of tributyl phosphate and 1g of benzoyl peroxide were taken, and 100g of molten sliced paraffin (phase transition temperature 25 ℃) was thoroughly mixed to obtain a dispersion phase. 2g of sodium dodecylbenzenesulfonate are added to 150g of water as a continuous phase and heated to 26 ℃. The dispersed phase was added to the continuous phase and emulsified by high speed shearing for 20min at 7000rpm, and then the resulting emulsion was transferred to a three-necked flask and reacted at 70 ℃ for 12 hours. And separating the product by suction filtration, washing with deionized water, and drying in vacuum to obtain the phase change microcapsule dry powder.
The phase-change temperature of the flame-retardant phase-change microcapsule prepared by the embodiment is 26 ℃, the phase-change latent heat is 171.3J/g, the appearance is good, the microcapsule is regular spherical and has no collapse, the particle size is 1-20 micrometers, the heating melting leakage rate is 0.4%, and the combustion time of a flame-retardant test is 9 seconds.
Example 3
3g of vinyltris (. beta. -methoxyethoxy) silane, 2g of butanediol dimethacrylate, 0.5g of aluminum hydroxide, 0.02g of benzoyl peroxide and 30g of melted tetradecanol (phase transition temperature 38 ℃ C.) were thoroughly mixed and used as a dispersed phase. 1g of sodium polyvinylbenzenesulfonate was added to 50g of water as continuous phase and heated to 39 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 30min at 10000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, and reacting for 12 hours at 140 ℃. And separating the product by filtering, washing by using deionized water, and drying in vacuum to obtain the phase-change microcapsule dry powder.
The phase-change temperature of the flame-retardant phase-change microcapsule prepared by the embodiment is 39 ℃, the latent heat of phase change is 194J/g, the microcapsule is regular spherical, collapse is avoided, the particle size is 0.2-20 micrometers, the heating melting leakage rate is 0.1%, and the combustion time in a combustion test is 5 seconds.
Example 4
4g of vinyltris (. beta. -methoxyethoxy) silane, 0.3g of ethylene glycol dimethacrylate, 0.2g of tributyl phosphate, 0.05g of azobisisobutyronitrile and 30g of molten n-eicosane (phase transition temperature 37 ℃) were thoroughly mixed and used as a dispersed phase. 1g of polyethylene glycol octyl phenyl ether X100(Triton X-100) was added to 50g of water as a continuous phase and heated to 38 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying at 3000rpm for 20min by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting at 70 ℃ for 12 hours, cooling the system, adding 2g of n-octyl triethoxysilane, and reacting at 25 ℃ for 12 hours. The product was separated by centrifugation at 12000rpm, washed with deionized water, and dried under vacuum to obtain dry powder of phase change microcapsules.
The phase transition temperature of the flame-retardant phase change microcapsule prepared by the embodiment is 37.5 ℃, the latent heat of phase change is 181J/g, the morphology is good, the microcapsule is regular spherical, no collapse is caused, the particle size is 20-100 micrometers, the heating melting leakage rate is 0.2%, and the combustion time of a flame-retardant test is 13 seconds.
Example 5
11.2g of 3- (methacryloyloxy) propyltris (trimethylsiloxane) silane, 8.4g of divinylbenzene, 8.4g of guanidine carbonate, 3.92g of azobisisoheptonitrile and 28g of melted hexadecanol (phase transition temperature 52 ℃ C.) were thoroughly mixed and used as the dispersed phase. 2.5g of span 80 were added to 50g of water as a continuous phase and heated to 53 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 5000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting for 12 hours at 70 ℃, cooling the system, adding 2g of methacryloxypropyl trimethoxysilane into the system, and reacting for 12 hours at 30 ℃. And separating the product by centrifugation at 3000rpm, washing with deionized water, and drying in vacuum to obtain the phase-change microcapsule dry powder.
The phase transition temperature of the flame-retardant phase change microcapsule prepared by the embodiment is 52.8 ℃, the latent heat of phase change is 105J/g, the morphology is good, the microcapsule is regular spherical, no collapse is caused, the particle size is 10-20 micrometers, the heating melting leakage rate is 0.1%, and the combustion time of a flame-retardant test is 16 seconds.
Example 6
3g of 3- (methacryloyloxy) propyltrimethoxysilane, 0.5g of divinylbenzene, 0.2g of tris (2, 3-dibromopropyl) phosphate, 0.05g of benzoyl oxide and 25g of molten n-eicosane (phase transition temperature 38 ℃) were thoroughly mixed and used as a dispersed phase. 0.25g of Tween60 was added to 50g of water as a continuous phase and heated to 39 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 13000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting for 12 hours at 70 ℃, cooling the system, adding 3g of tetraethoxysilane, and reacting for 12 hours at 30 ℃. The product was separated by centrifugation at 12000rpm, washed with deionized water, and dried under vacuum to obtain dry powder of phase change microcapsules.
The phase transition temperature of the flame-retardant phase change microcapsule prepared by the embodiment is 38.5 ℃, the phase transition latent heat is 169J/g, the shape is good, the microcapsule is regular spherical, no collapse is caused, the particle size is 0.1-10 micrometers, the heating melting leakage rate is 0.05%, and the combustion time of a flame-retardant test is 15 seconds.
Example 7
5g of vinyltris (. beta. -methoxyethoxy) silane, 0.5g of ethylene glycol dimethacrylate, 0.015g of guanidine sulfamate, 0.05g of azobisisobutyronitrile and 15g of molten lauric acid (phase transition temperature 44 ℃) were thoroughly mixed and used as a dispersed phase. 1g of sodium hydrolysate of an isobutene-maleic anhydride copolymer was added to 1028g of water as continuous phase and heated to 45 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 5min at 3000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting for 12 hours at 70 ℃, cooling the system, adding 2g of triisopropyl aluminate, and reacting for 10 hours at 30 ℃. The product was separated by centrifugation at 12000rpm, washed with deionized water, and spray dried to obtain dry powder of phase change microcapsules.
The phase-change temperature of the flame-retardant phase-change microcapsule prepared by the embodiment is 44 ℃, the phase-change latent heat is 158J/g, the microcapsule is good in appearance, is regular spherical, has no collapse, has the particle size of 30-100 micrometers, has the heating melting leakage rate of 0.1%, and has the flame-retardant test burning time of 12 seconds.
Flame-retardant phase-change microcapsules free of triisopropyl aluminate were also prepared according to the same method as above, and tested for flame-retardancy, with a burning time of 9 seconds.
Example 8
3g of 3- (methacryloyloxy) propyltrimethoxysilane, 0.3g of ethylene glycol dimethacrylate, 0.2g of silica, 0.03g of benzoyl peroxide and 35g of molten butyl stearate (phase transition temperature 19 ℃) were mixed thoroughly to give a disperse phase. 1g of styrene-maleic anhydride copolymer was added to 50g of water as a continuous phase and heated to 20 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying at 2000rpm for 5min by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting at 70 ℃ for 12 hours, cooling the system, adding 4g of phenyltriethoxysilane, and reacting at 40 ℃ for 10 hours. And separating the product by filtering, washing by using deionized water, and drying in vacuum to obtain the phase-change microcapsule dry powder.
The phase-change temperature of the flame-retardant phase-change microcapsule prepared by the embodiment is 19 ℃, the latent heat of phase change is 112J/g, the appearance is good, the microcapsule is regular spherical, collapse is avoided, the particle size is 20-200 micrometers, the heating melting leakage rate is 0.2%, and the combustion time of a flame-retardant test is 15 seconds.
Example 9
3g of vinyltrimethoxysilane, 1.5g of ethylene glycol dimethacrylate, 0.8g of melamine, 0.05g of benzoyl peroxide and 40g of melted octadecane (phase transition temperature 28 ℃) were mixed thoroughly as a dispersed phase. 2g of sodium lauryl sulfate were added to 45g of water as a continuous phase and heated to 29 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 15000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting for 36 hours at 50 ℃, cooling the system, adding 3g of triisopropyl aluminate, and reacting for 10 hours at 30 ℃. The product was separated by centrifugation at 12000rpm, washed with deionized water, and dried under vacuum to obtain dry powder of phase change microcapsules.
The phase-change temperature of the flame-retardant phase-change microcapsule prepared by the embodiment is 28 ℃, the latent heat of phase change is 214J/g, the appearance is good, the microcapsule is regular spherical, the microcapsule does not collapse, the particle size is 1-5 micrometers, the heating melting leakage rate is 0.02%, and the combustion time of a flame-retardant test is 13 seconds.
Example 10
3g of vinyltriethoxysilane, 0.3g of divinylbenzene, 0.1g of ammonium dihydrogen phosphate, 0.03g of benzoyl peroxide and 40g of molten n-eicosane (phase transition temperature 37 ℃) were thoroughly mixed and used as the dispersed phase. 1g of sodium lauryl sulfate was added to 45g of water as a continuous phase and heated to 38 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 4000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-necked bottle, reacting for 12 hours at 70 ℃, cooling the system, adding 2g of 3- (methacryloyloxy) propyl trimethoxy silane, and reacting for 10 hours at 40 ℃. And separating the product by suction filtration, washing with deionized water, and drying in vacuum to obtain the phase change microcapsule dry powder.
The phase transition temperature of the flame-retardant phase transition microcapsule prepared by the embodiment is 37 ℃, the latent heat of phase transition is 176J/g, the morphology is good, the microcapsule is regular spherical, no collapse is caused, the particle size is 1-10 micrometers, the heating melting leakage rate is 0.05%, and the combustion time of a flame-retardant test is 11 seconds.
Example 11
4g of vinyltris (. beta. -methoxyethoxy) silane, 0.3g of ethylene glycol dimethacrylate, 0.1g of antimony trioxide, 0.05g of azobisisoheptonitrile and 40g of molten n-eicosane (phase transition temperature 37 ℃) were mixed thoroughly to give a dispersion. 1.5g of acrylate were added to 50g of water as a continuous phase and heated to 38 ℃. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 3000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-neck flask, reacting for 12 hours at 70 ℃, cooling the system, adding 5g of tetraethoxysilane, and reacting for 10 hours at 20 ℃. And separating the product by filtering, washing by using deionized water, and spray drying to obtain the phase-change microcapsule dry powder.
The phase-change temperature of the flame-retardant phase-change microcapsule prepared by the embodiment is 37 ℃, the latent heat of phase change is 195J/g, the appearance is good, the microcapsule is regular spherical, the microcapsule does not collapse, the particle size is 10-50 micrometers, the heating melting leakage rate is 0.01%, and the combustion time of a flame-retardant test is 19 seconds.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant phase-change microcapsule is characterized by comprising the following steps of:
1) preparation of the dispersed phase: adding a polymerizable silane monomer, a cross-linking agent monomer and a flame retardant into the molten phase-change material to prepare the phase-change material;
2) preparation of the continuous phase: dissolving emulsifier in water;
3) preparing microcapsules: heating the continuous phase obtained in the step 2) to be above the melting point of the phase-change material, mixing the continuous phase with the dispersed phase obtained in the step 1), emulsifying and reacting;
wherein, the initiator is added into the dispersed phase or the continuous phase, or the initiator is added after the dispersed phase or the continuous phase is mixed.
4) Optionally, adding an inorganic precursor into the system after the reaction in the step 3) and continuing the reaction.
2. The method according to claim 1, wherein the phase change material in step 1) is at least one selected from the group consisting of C4-50 alcohol compounds, C4-50 organic acid compounds, C6-50 alkane or aromatic hydrocarbon compounds, and esters obtained by reacting the C4-50 alcohol compounds with C4-50 organic acid compounds;
preferably, the polymerizable silane monomer in step 1) is selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, at least one of 3- (N-allylamino) propyltrimethoxysilane, styrene-dimethylsiloxane, styrene ethyltrimethylsiloxane, isobutylene triethoxysilane, 3-isobutylene propyltriethoxysilane, 3- (methacryloyloxy) propyltris (trimethylsiloxane) silane polymerizable silane monomers having at least one double bond;
preferably, the crosslinking agent monomer in step 1) is an unsaturated bond-containing crosslinking agent, such as at least one of styrene derivatives such as divinylbenzene, styrene ethyltrimethicone, 1, 3-diisopropenylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, and hexanediol dimethacrylate.
Preferably, the mass of the polymerizable silane monomer in the step 1) accounts for 5-100% of that of the phase-change material;
preferably, the mass of the cross-linking agent monomer in the step 1) accounts for 0.5-50% of that of the phase-change material;
preferably, the mass of the initiator in the step 1) accounts for 0.1-30% of the total mass of the coupling agent monomer and the crosslinking agent;
preferably, the flame retardant in step 1) is selected from at least one of alkyl phosphate, aryl phosphate, inorganic flame retardant, nitrogen flame retardant, montmorillonite, talcum powder and silica, for example, at least one selected from the following: tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, Pyrol99, tolylene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl) -diphenyl phosphate, red phosphorus, ammonium polyphosphate, diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony trioxide, molybdenum trioxide, melamine cyanurate, dicyandiamide, guanidine carbonate, guanidine phosphate, condensed guanidine phosphate, guanidine sulfamate;
preferably, the mass ratio of the flame retardant in the step 1) to the phase-change material is 0.1-30%.
3. The method according to claim 1 or 2, wherein in step 2), the emulsifier is selected from sodium salt hydrolysate of ethylene-maleic anhydride copolymer, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolysate of ethylene methyl ether-maleic anhydride copolymer, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, copolymer obtained by copolymerizing acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylic ester, methacrylic ester or acrylonitrile, polyvinylbenzene sulfonic acid, sodium polyvinylbenzene sulfonate, octylphenol polyoxyethylene ether, polyethylene glycol octylphenyl ether X-100, sodium dodecylsulfate, sodium dodecylsulfonate, sodium dodecylbenzene sulfonate, At least one of Tween 20, Tween60 (Tween60), Tween 80, span 60, span 65, span 80 and dioctyl sodium sulfosuccinate;
preferably, the mass of the emulsifier in the continuous phase in the step 2) accounts for 0.05-5% of the mass of the water.
4. The method according to any one of claims 1 to 3, wherein in step 3), the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, potassium persulfate, ammonium persulfate, potassium persulfate, sodium bisulfite, benzoyl peroxide, cumene hydroperoxide and other radical polymerization initiators.
5. The process according to any one of claims 1 to 4, wherein the mass ratio of the dispersed phase to the continuous phase in step 3) is 1:1 to 1: 50.
6. The method according to any one of claims 1 to 5, wherein the reaction temperature in step 3) is 30 to 90 ℃.
7. The method according to any one of claims 1 to 6, wherein the inorganic precursor in step 4) is selected from at least one of ethyl orthosilicate, epoxypropyltrimethoxysilane, phenyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltrimethoxysilane, n-octyltriethoxysilane, tetrabutyl stannate, NW-2 stannate coupling agent, tetrabutyl zirconate, triisopropyl aluminate, and tribenzyl aluminate.
8. The flame-retardant phase-change microcapsule prepared by the method of any one of claims 1 to 7, which is characterized by comprising an inner core and an outer shell, wherein the inner core contains a flame retardant and a phase-change material, and the outer shell is an organic/inorganic composite shell consisting of silane polymer and silicon dioxide.
9. The fire-retardant phase-change microcapsule according to claim 8, wherein the particle size is 0.1 to 150 μm.
10. The phase-change microcapsule of claim 8, which is used as a flame-retardant material in the fields of construction, energy conservation, textile and military.
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