CN101709104A - Three-dimensional gel network carrier and form-stable phase change composite material - Google Patents
Three-dimensional gel network carrier and form-stable phase change composite material Download PDFInfo
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Abstract
The invention relates to a three-dimensional gel network carrier and a form-stable phase change composite material which adopt fatty acid (hydrocarbon), polyethylene glycol and other organic phase change materials as work material and use poly-(N-hydroxymethyl)-acrylamide heat-shrinkable interpenetration network as form-stable carrier. The preparation method of the phase change composite material comprises the following steps: firstly adopting low temperature eutectic method to select multiple components composite phase change material with proper phase change temperature, high phase change enthalpy and low cost, designing and determining the preparation method of the interpenetration network carrier and the addition mode of the composite phase change material and the combination mode of the carrier, preparing the form-stable phase change composite material based on multiple actions of bonding, physical adsorption and network confinement, cooling and grinding to obtain the form-stable heat storage functional particles. The form-stable phase change composite material containing 50%-75% of material can be prepared by the method, the maximum phase change enthalpy can be up to 110J/g, and the form-stable phase change composite material prepared by the method can be directly applied in the textile field, building field, military field, etc.
Description
Technical field
The invention belongs to novel shaping phase-change material field, relate to a kind of design preparation of novel three-dimensional network carrier specifically, serve as the preparation of the composite phase-change material of setting carrier with this three dimensional gel network.
Background technology
Along with developing rapidly of whole world industry, world energy sources day is becoming tight, and environmental pollution is more and more serious.Energy storage material has special energy memory function, has complied with energy-conservation this theme, is extensively come into one's own.Since 1930's, particularly be subjected to the influence of the energy dilemma eighties, the basic theory of phase-change thermal storage and application technical research are developed rapidly in developed country (as the U.S., Canada, Japan, Germany etc.).Condition has been created in interpenetrating to the research and the application of phase-change thermal storage of fields such as Materials science, sun power, spationautics, buildings, air-conditioning heating and industrial waste heat utilization.At present, the development thermal storage density is big, thermal conductivity is high, the NEW TYPE OF COMPOSITE phase change heat storage material of stable performance becomes the focus and the difficult point of this research field in the world.
We are divided into four kinds to the mode of phase changing energy storage usually: crystal formation-unformed, solid-liquid phase change, solid-gas phase change and liquid-gas phase become.Because back two kinds of phase transformation modes are attended by the existence of a large amount of gases in phase transition process, material volume is changed greatly, although it is therefore they have very big enthalpy of phase change, seldom selected in the process of practical application.There is bigger limitation in crystal formation-unformed phase change material as and transformation temperature scope few because of alternative materials is improper etc. aspect the material selection.So solid-liquid phase change becomes the object of primary study.In order to eliminate the flow problem of solid-liquid phase change material in phase transition process, research both at home and abroad in recent years mainly concentrates on compound solid-liquid phase change material aspect.Being operation material with the solid-liquid phase change material promptly, utilizing its phase transformation to store up, exoergic, adopt blend or encapsulation technology combination, is that immobilization carrier prepares stable phase change composite material with porous base inorganic particulate, microcapsule, montmorillonite carrier etc.But more or less all there is defective in existing technology, and is specific as follows.
(1) physisorphtion
Utilize capillary force that the phase change material of liquid state is drawn in the microvoid structure, form organic/inorganic compounding phase-change heat-storage material; Or utilize sol-gel method, the solid-liquid phase change material is embedded in the higher silica nanometer sheaf space of thermal conductivity.This method adsorptive capacity is limited, can't solve the contradiction of setting effect and enthalpy of phase change loss, and employing and adopt simple physical bond mode, and resistance to elevated temperatures is relatively poor.
(2) microcapsule method
Capsule wall provides stable enclosed environment, can effectively solve leakage, be separated and problem such as corrodibility, strengthens the stability of phase change material, makes solid-liquid phase change change the solid-solid phase-change that is as the criterion.The capsule body material mostly adopts polymer substance at present, and its thermal conductivity is lower, thereby has reduced the storage density and the thermal characteristics of phase change material.Also there are complex process, the higher problem that is not easy to suitability for industrialized production of cost.In addition, volume change is shunk the work-ing life that influence material with the meeting of expanding repeatedly up to more than 15% during capsule-core generation solid-liquid phase change, therefore should guarantee enough coating intensity.These all will certainly increase production cost and reduce heat retention, thereby make the application of capsule type phase-changing energy storage material be subjected to certain limitation.
(3) compound with macromolecular material
As paraffin and polymer substance (HDPE, LDPE, SBS) are heated blend by a certain percentage on warm-up mill.Polyoxyethylene glycol (PEG) is mixed with vinylformic acid and polymethylmethacrylate; PEG/ Cellulose diacetate (CDA) solid blend, PEG/ cellulose acetate fiber (CA) electrostatic spinning etc.Subject matter is oozing out of phase change material and volatilization problem.
(4) cross-linked polyolefin and crosslined polyacetal
Its principle is to be undertaken partial cross-linked by the method for radiation crosslinking the polyolefine of crystal type and polyacetal, between molecular chain, set up the chemically crosslinked point, make free-moving polyolefine of proper energy and polyacetal macromole lose the translation freedom, thereby show as the solid-state phase changes behavior.As HDPE120.Its transformation temperature height, but heat-conduction coefficient is too low, and crosslink density is difficult to control, and excessively the crosslinked thermosetting polymer that will become loses the phase-change thermal storage ability.
Summary of the invention
The objective of the invention is to choose well behaved carrier matrix, improve enthalpy of phase change, improve the setting effect, over-all propertieies such as the intensity of raising stable phase change composite material, thermotolerance.Searching technology is simple, the preparation path of the heat accumulation function material in fields such as with low cost being widely used in weaved, building.
One,
The contriver has invented a kind of novel thermal shrinkage type three-dimensional network gel carrier, and the research about network gel at present focuses mostly at N-N-isopropylacrylamide lattice reagent monomer, but has limited its research and development and used because of its price is very expensive.
The present invention is the lattice reagent monomer with pure N hydroxymethyl acrylamide first, N, and N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel.
Wherein
Linking agent and monomer mole ratio 1: 5～1: 11
Monomer and alcoholic acid mass ratio 1: 8～1: 12
It is 1.5%～3% that initiator accounts for monomeric massfraction
Reagent is weighed according to the above ratio, place flask then, wherein solvent adds at last, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonicly, in 70 ℃ of waters bath with thermostatic control, continue reaction, after reaction finishes, gel is placed constant temperature oven, at 30 ℃ of following cryodrying 8h, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole;
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3～5h.
The optimum reaction condition of orthogonal reaction method gained is: linking agent and monomer mole ratio are 1: 9; The mass ratio of monomer and water is 1: 10; It is 1.5% that initiator accounts for monomeric massfraction; All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3.5h.
Selection ethanol is solvent, and can make is that phase change material and the reagent for preparing gel network can both be dissolved in wherein, can guarantee that phase change material is dispersed in the reaction system, to guarantee good phase border contact, reaches satisfied setting effect.The phase change material massfraction of setting can reach 75%, and enthalpy of phase change reaches 110J/g.
The carrier that the technical solution used in the present invention makes possesses following outstanding advantage:
(1) heat storage capacity is strong.The enthalpy of phase change loss is few, and measured value reaches more than 92% of theoretical value.After the thermal cycling 10 times, enthalpy of phase change does not have loss substantially between room temperature to 80 ℃.
(2) setting is effective.The performance of multiple action synergistics such as physical adsorption, network confinement, high temperature pyrocondensation makes the setting effect very good.In constant temperature oil bath, be heated to far above 150 ℃ of the temperature of phase change material fusing point, do not observe any phenomenon of oozing out and volatilize.Phase change material has been realized by the transformation of solid-liquid phase change to solid-solid phase-change after by setting.
(3) intensity height, good heat resistance.Compare with other setting carrier, the three-dimensional network gel carrier is because cross-linked polymer, and intensity and thermotolerance are with the obvious advantage, during with 250 ℃ of gel carrier sample heating, does not observe variation yet on the fusing point instrument.Dried sample strength is very high, can bear such as processing conditionss such as the high-temperature fusion in the spinning process, powerful shearings.
(4) preparation technology is simple.Only need provide the water bath with thermostatic control condition of ultra-sonic dispersion and 70 ℃ to get final product during polyreaction, the reaction times only needs 3.5h.
(5) with low cost.Selected lattice reagent monomer N hydroxymethyl acrylamide is compared with other lattice reagent monomer, cost is quite cheap, and every kilogram only needs about 10 yuan, and the more lattice reagent N-N-isopropylacrylamide of research now really needs nearly 10000 yuan for every kilogram, differ and reach 1000 times, cost advantage is fairly obvious.Can be widely used in weaving, the preparation of the heat accumulation function material in field such as building.
(6) nontoxic.Polymerisate is nontoxic, can relievedly be applied to each field.Used monomer toxicity is very low, totally nontoxic after the polymerization, existing application in vivo.And the popular now lattice reagent N-N-isopropylacrylamide tool moderate toxicity of studying has hormesis to skin.
Two,
A kind of suitable temperature-regulation fabric stable phase change composite material that utilizes above-mentioned three dimensional gel network carrier to make makes like this:
(1) selection of operation material phase change material and pre-treatment
With lauric acid and two kinds of phase change materials of hexadecanol, it is compound to carry out binary.
Molar fraction is respectively 41% lauric acid and 59% hexadecanol is heated to 60 ℃, melt blending 30min under mechanical stirring prepares well-mixed eutectic mixture, after the seasoning, is ground to the following eutectic mixture of 200 orders; Recording transformation temperature with the cooling curve method is 34 ℃, and meeting temperature-regulating fiber should be 32 ℃～42 ℃ requirement with transformation temperature.
(2) be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, and above reagent is weighed in following ratio:
Linking agent and monomer mole ratio 1: 5～1: 11
Monomer and alcoholic acid mass ratio 1: 8～1: 12
Initiator accounts for monomeric massfraction 1.5%～3%
Place flask then, wherein solvent adds at last, add the following eutectic mixture of 200 orders that makes in the step (1) again, the massfraction that the following eutectic mixture add-on of this 200 order accounts for the reaction system total mass is 40%～75%, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonic, in 70 ℃ of waters bath with thermostatic control, continue reaction, reaction places constant temperature oven with gel, at 30 ℃ of following cryodrying 8h after finishing, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole;
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3～5h.
The optimum reaction condition of orthogonal reaction method gained is: linking agent and monomer mole ratio are 1: 9; The mass ratio of monomer and water is 1: 10; It is 1.5% that initiator accounts for monomeric massfraction; All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3.5h.
With co-blended spinning behind the heat accumulation function particle of interpolation 9% in the polypropylene, good spinning property, fibre strength is still higher, the enthalpy of phase change recoverable amount reaches 85% of theoretical value, heat storage capacity has exceeded the commercialization temperature-regulating fiber kind of existing maximum, the polyacrylonitrile fibre Outlastfiber (7.8J/g) of the material containing micro-capsule phase change that wet-spinning is shaped.Get virgin pp fiber and temperature adjustment polypropylene fibre sample, adopt the cooling curve method to heat up and the experiment of lowering the temperature, the result shows that tangible platform area or slow cooling district appear in the cooling curve of temperature adjustment polypropylene fibre, and regenerative effect is obvious.Succeeding in developing of the polypropylene temperature-regulating fiber of interpolation three-dimensional network shaping phase-change material with two creative achievements of realization, the one, realize that melt spinning method prepares temperature-regulating fiber; The 2nd, China's autonomous production commercialization temperature-regulating fiber will point the day and await for it.
Description of drawings
Fig. 1 takes for scanning electron microscope and presses the fracture morphology picture of the prepared support samples of embodiment 1 method, magnification is 4000 and 7000, can find out intuitively that carrier is a kind of three-dimensional net structure, the size of network hole is at 1～2 μ m, the diameter of hole and the distribution of hole are very even, and part forms the groove that runs through mutually between hole;
Fig. 2 is the stereoscan photograph of the stable phase change composite material of embodiment 2 gained;
See that from figure phase change material is evenly distributed in the hole of carrier, the three-dimensional network of carrier is given and good physical adsorption of phase change material and network confinement fixed effect;
Fig. 3 is the dsc analysis curve of the shaping phase-change material matrix material of embodiment 2 gained;
Fig. 4 is the dsc analysis curve after the thermal cycling between room temperature to 80 ℃ 10 times of embodiment 2 gained;
Fig. 5 takes for scanning electron microscope and presses the fracture morphology picture of the prepared support samples of embodiment 3 methods;
Fig. 6 is the dsc analysis curve of the shaping phase-change material matrix material of embodiment 4 gained.
Embodiment
The preparation of embodiment 1 gel carrier
With pure N hydroxymethyl acrylamide is the lattice reagent monomer, N, and N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, wherein
A. linking agent and monomer mole ratio are 1: 9
B. the mass ratio of monomer and solvent is 1: 10
C. initiator accounts for monomeric massfraction 1.5%
Reagent is weighed according to the above ratio, place flask then, wherein solvent adds at last, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonicly, in 70 ℃ of waters bath with thermostatic control, continue reaction, after reaction finishes, gel is placed constant temperature oven, at 30 ℃ of following cryodrying 8h, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3.5h.The gel network form of gained as shown in Figure 1.
Fig. 1 is the scanning electron microscope pictures taken, magnification is 4000 and 7000, can find out intuitively that carrier is a kind of three-dimensional net structure, and the size of network hole is at 1～2 μ m, the diameter of hole and the distribution of hole are very even, and part forms the groove that runs through mutually between hole.
Embodiment 2
(1) is fit to the preparation of temperature-regulation fabric with the binary phase change material of transformation temperature
Be respectively the hexadecanol blend preparation of 41% lauric acid and 59% by molar fraction, transformation temperature is 34 ℃.Detailed process is to get molar fraction to be respectively 41% lauric acid and 59% hexadecanol, join make it fusion in the water-bath of 60 ℃ of constant temperature after, constantly stir 30min.
(2) be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, and above reagent is weighed in following ratio:
A. linking agent and monomer mole ratio are 1: 9
B. the mass ratio of monomer and solvent is 1: 10
C. initiator accounts for monomeric massfraction 1.5%
Place flask then, wherein solvent adds at last, add the following eutectic mixture of 200 orders that makes in the step (1) again, the massfraction that the following eutectic mixture add-on of this 200 order accounts for the reaction system total mass is 50%, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonic, in 70 ℃ of waters bath with thermostatic control, continue reaction, reaction places constant temperature oven with gel, at 30 ℃ of following cryodrying 8h after finishing, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3.5h.
The stereoscan photograph of the stable phase change composite material of gained as shown in Figure 2.
See that from figure phase change material is evenly distributed in the hole of carrier, the three-dimensional network of carrier is given and good physical adsorption of phase change material and network confinement fixed effect.
Fig. 3 is the dsc analysis curve of shaping phase-change material matrix material.
By the tangent method mapping, determine that transformation temperature is 34.52 ℃, enthalpy of phase change is 72.14J/g.
The theoretical enthalpy of phase change of binary phase change material is 156.40J/g.Phase change material in the matrix material accounts for 50%, so due theoretical phase transformation enthalpy is 78.2J/g on phase change composite material, as seen this sample has reached 92% of theoretical value.Fig. 4 is the dsc analysis curve after the thermal cycling 10 times between room temperature to 80 ℃, and visible enthalpy of phase change not have to lose substantially.Illustrate that carrier is fine to the fixed effect of phase change material, and do not have influence on the phase transformation enthalpy of phase change material basically.
The preparation of embodiment 3 gel carriers
With pure N hydroxymethyl acrylamide is the lattice reagent monomer, N, and N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, wherein
A. linking agent and monomer mole ratio are 1: 5
B. the mass ratio of monomer and solvent is 1: 10
C. initiator accounts for monomeric massfraction 3%
Reagent is weighed according to the above ratio, place flask then, wherein solvent adds at last, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonicly, in 70 ℃ of waters bath with thermostatic control, continue reaction, after reaction finishes, gel is placed constant temperature oven, at 30 ℃ of following cryodrying 8h, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3h.
The gel network form of gained as shown in Figure 5.
As seen the network structure of three dimensional gel carrier is very clear, the size of network hole is at 1～2 μ m, the diameter of hole and the distribution of hole are very even, and all form the gutter channel that runs through mutually between hole, are the space that provides a large amount of that is written into of big content phase change material.
Embodiment 4
(1) preparation of the binary phase change material of suitable temperature-regulation fabric usefulness transformation temperature is with embodiment 2.
(2) be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, and above reagent is weighed in following ratio:
A. linking agent and monomer mole ratio are 1: 5
B. the mass ratio of monomer and solvent is 1: 10
C. initiator accounts for monomeric massfraction 3%
Place flask then, wherein solvent adds at last, add the following eutectic mixture of 200 orders that makes in the step (1) again, the massfraction that the following eutectic mixture add-on of this 200 order accounts for the reaction system total mass is 75%, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonic, in 70 ℃ of waters bath with thermostatic control, continue reaction, reaction places constant temperature oven with gel, at 30 ℃ of following cryodrying 8h after finishing, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3h.
The shaping phase-change material matrix material is carried out dsc analysis (see figure 6) result show that transformation temperature still is 34 ℃, the phase transformation enthalpy is 110J/g, has reached 93% of theoretical value.Loss through carrier setting back phase transformation enthalpy is considerably less.The loss of enthalpy of phase change is very little, illustrates that carrier is fine to the fixed effect of phase change material, and does not have influence on the phase transformation enthalpy of phase change material basically.
The application of three-dimensional network stable phase change composite material in temperature-regulating fiber:
(1) be crushed to below 200 orders embodiment 4 prepared phase change composite materials standby.
(2) preparation polypropylene (PP)/stable phase change composite material blend is as the heat accumulation function master batch.Concrete grammar is as follows:
The stable phase change composite material that takes by weighing matrix PP and certain mass stirs for some time with glass stick in beaker, phase change material is covered on the PP uniformly.The temperature of respectively distinguishing on the setpoint torque rheometer is 165 ℃ then, and rotating speed is 20rpm, begins to heat up, when temperature reaches set(ting)value, add PP/ phase change composite material blend, treat that curve tends to balance after, blend finishes, extrude, pelletizing obtains the heat accumulation function master batch.
(3), on the self-control screw extrusion press, adopt melt spinning process spinning polypropylene temperature-regulating fiber with heat accumulation function master batch and polypropene blended.
Concrete parameter is as follows:
The massfraction of stable phase change composite material: 9%
Spinning temperature: 200 ℃
Screw speed: 25rpm
Temperature-regulating fiber linear density: 2.6dtex
Temperature-regulating fiber phase transition temperature: 34 ℃
Temperature-regulating fiber enthalpy of phase change: 8.4J/g
Temperature-regulating fiber breaking tenacity: 29.25cN/dtex
With co-blended spinning behind the heat accumulation function particle of interpolation 9% in the polypropylene, good spinning property, fibre strength is still higher, the enthalpy of phase change recoverable amount reaches 85% of theoretical value, heat storage capacity has exceeded the commercialization temperature-regulating fiber kind of existing maximum, the polyacrylonitrile fibre Outlastfiber (7.8J/g) of the material containing micro-capsule phase change that wet-spinning is shaped.Get virgin pp fiber and temperature adjustment polypropylene fibre sample, adopt the cooling curve method to heat up and the experiment of lowering the temperature, the result shows that tangible platform area or slow cooling district appear in the cooling curve of temperature adjustment polypropylene fibre, and regenerative effect is obvious.Succeeding in developing of the polypropylene temperature-regulating fiber of interpolation three-dimensional network shaping phase-change material with two creative achievements of realization, the one, realize that melt spinning method prepares temperature-regulating fiber; The 2nd, China's autonomous production commercialization temperature-regulating fiber will point the day and await for it.
The preparation of embodiment 5 gel carriers
With pure N hydroxymethyl acrylamide is the lattice reagent monomer, N, and N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, wherein
A. linking agent and monomer mole ratio are 1: 11
B. the mass ratio of monomer and solvent is 1: 8
C. initiator accounts for monomeric massfraction 2%
Reagent is weighed according to the above ratio, place flask then, wherein solvent adds at last, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonicly, in 70 ℃ of waters bath with thermostatic control, continue reaction, after reaction finishes, gel is placed constant temperature oven, at 30 ℃ of following cryodrying 8h, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 5h.
Embodiment 6
(1) is fit to the preparation of temperature-regulation fabric with the binary phase change material of transformation temperature
Be respectively the hexadecanol blend preparation of 41% lauric acid and 59% by molar fraction, transformation temperature is 34 ℃.Detailed process is to get molar fraction to be respectively 41% lauric acid and 59% hexadecanol, join make it fusion in the water-bath of 60 ℃ of constant temperature after, constantly stir 30min.
(2) be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, and above reagent is weighed in following ratio:
A. linking agent and monomer mole ratio are 1: 11
B. the mass ratio of monomer and solvent is 1: 8
C. initiator accounts for monomeric massfraction 2%
Place flask then, wherein solvent adds at last, add the following eutectic mixture of 200 orders that makes in the step (1) again, the massfraction that the following eutectic mixture add-on of this 200 order accounts for the reaction system total mass is 40%, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonic, in 70 ℃ of waters bath with thermostatic control, continue reaction, reaction places constant temperature oven with gel, at 30 ℃ of following cryodrying 8h after finishing, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 5h.
The preparation of embodiment 7 gel carriers
With pure N hydroxymethyl acrylamide is the lattice reagent monomer, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, its by
A. linking agent and monomer mole ratio are 1: 11
B. the mass ratio of monomer and solvent is 1: 12
C. initiator accounts for monomeric massfraction 2.8%
Reagent is weighed according to the above ratio, place flask then, wherein solvent adds at last, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonicly, in 70 ℃ of waters bath with thermostatic control, continue reaction, after reaction finishes, gel is placed constant temperature oven, at 30 ℃ of following cryodrying 8h, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 4h.
Embodiment 8
(1) is fit to the preparation of temperature-regulation fabric with the binary phase change material of transformation temperature
Be respectively the hexadecanol blend preparation of 41% lauric acid and 59% by molar fraction, transformation temperature is 34 ℃.Detailed process is to get molar fraction to be respectively 41% lauric acid and 59% hexadecanol, join make it fusion in the water-bath of 60 ℃ of constant temperature after, constantly stir 30min.
(2) be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, and above reagent is weighed in following ratio:
A. linking agent and monomer mole ratio are 1: 11
B. the mass ratio of monomer and solvent is 1: 12
C. initiator accounts for monomeric massfraction 2.8%
Place flask then, wherein solvent adds at last, add the following eutectic mixture of 200 orders that makes in the step (1) again, the massfraction that the following eutectic mixture add-on of this 200 order accounts for the reaction system total mass is 60%, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonic, in 70 ℃ of waters bath with thermostatic control, continue reaction, reaction places constant temperature oven with gel, at 30 ℃ of following cryodrying 8h after finishing, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole.All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 4h.
Claims (4)
1. three dimensional gel network carrier is to be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, and N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, wherein
Linking agent and monomer mole ratio 1: 5～1: 11
Monomer and alcoholic acid mass ratio 1: 8～1: 12
It is 1.5%～3% that initiator accounts for monomeric massfraction
Reagent is weighed according to the above ratio, place flask then, wherein solvent adds at last, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonicly, in 70 ℃ of waters bath with thermostatic control, continue reaction, after reaction finishes, gel is placed constant temperature oven, at 30 ℃ of following cryodrying 8h, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole;
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3～5h.
2. three dimensional gel network carrier as claimed in claim 1 is characterized in that:
Described reagent proportioning is
Linking agent and monomer mole ratio are 1: 9
The mass ratio of monomer and water is 1: 10
It is 1.5% that initiator accounts for monomeric massfraction
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3.5h.
3. stable phase change composite material that utilizes the described three dimensional gel network carrier of claim 1 to make makes like this:
(1) selection of operation material phase change material and pre-treatment
Molar fraction is respectively 41% lauric acid and 59% hexadecanol is heated to 60 ℃, melt blending 30min under mechanical stirring prepares well-mixed eutectic mixture, after the seasoning, is ground to the following eutectic mixture of 200 orders;
(2) be the lattice reagent monomer with pure N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide is a linking agent, is initiator with the ammonium persulphate, is solvent with ethanol, carries out solution polymerization, generates the three-dimensional network gel, and above reagent is weighed in following ratio:
Linking agent and monomer mole ratio 1: 5～1: 11
Monomer and alcoholic acid mass ratio 1: 8～1: 12
Initiator accounts for monomeric massfraction 1.5%～3%
Place flask then, wherein solvent adds at last, add the following eutectic mixture of 200 orders that makes in the step (1) again, the massfraction that the following eutectic mixture add-on of this 200 order accounts for the reaction system total mass is 40%～75%, the ultra-sonic dispersion device is warming up to 70 ℃, flask is placed in the ultra-sonic dispersion device disperses, make all ingredients fusion and dispersion uniformly, after gel appears in the question response system, close ultrasonic, in 70 ℃ of waters bath with thermostatic control, continue reaction, reaction places constant temperature oven with gel, at 30 ℃ of following cryodrying 8h after finishing, the alcohol solvent of low surface tension is slowly volatilized, prevent the closure of gel network hole;
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3～5h.
4. the stable phase change composite material that three dimensional gel network carrier as claimed in claim 3 makes is characterized in that:
The proportioning of described reagent of weighing in proportion is
Linking agent and monomer mole ratio are 1: 9
The mass ratio of monomer and water is 1: 10
It is 1.5% that initiator accounts for monomeric massfraction
All ingredients is put into 70 ℃ ultrasonic water bath reaction beginning, and the time that finishes to the complete formation reaction of gel is 3.5h.
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