CN108893096A - A kind of hairless protein microcapsules of storing energy through phase change slurry and the preparation method and application thereof - Google Patents
A kind of hairless protein microcapsules of storing energy through phase change slurry and the preparation method and application thereof Download PDFInfo
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- CN108893096A CN108893096A CN201810602023.8A CN201810602023A CN108893096A CN 108893096 A CN108893096 A CN 108893096A CN 201810602023 A CN201810602023 A CN 201810602023A CN 108893096 A CN108893096 A CN 108893096A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
A kind of hairless protein microcapsules of storing energy through phase change slurry and the preparation method and application thereof, microcapsules slurry include the microcapsules that Average Particle Diameters are 1 μm~3 μm, and microcapsules are made of wall material shell, wall material inner casing and core material with phase transition function.Preparation method includes first to wool oxidation pre-treatment, wool is put into heating stirring in liquor zinci chloridi, it is completely dissolved to wool, solvent type hairless protein liquid is obtained by filtration, addition emulsifier obtains the solvent type hairless protein liquid to emulsify composite phase-change material, by end hydroxy butadiene-isocyanate prepolymer and phase-change material mixed dissolution, obtain composite phase-change liquid, into composite phase-change liquid, the solvent type hairless protein liquid to emulsify composite phase-change material is added in stirring again, obtain microcapsule suspensions, eventually form wall material inner casing and shell, by being centrifuged and filtering, obtain hairless protein microcapsules of storing energy through phase change slurry.Microcapsules slurry of the present invention blended can prepare phase-change energy-storage fibre, be also applied for the modification of flexible textile material.
Description
Technical field
The invention belongs to material engineering field, be related to a kind of hairless protein microcapsules of storing energy through phase change slurry and preparation method thereof with
Using.
Background technique
Phase-changing energy storage material refers to the material with certain energy storage, exothermicity, that is, has and be lower than phase transformation in environment temperature
Heat release when point, higher than transformation temperature when the feature absorbed heat.Phase-changing energy storage material shows good answer in terms of temperature regulation
Use prospect.Such as：By the building inner decorative material that phase-changing energy storage material is fabricated to just have the effect of it is cool in summer and warm in winter, using phase transformation
Fiber, fabric and the clothes of material preparation have the function of intelligent thermoregulating etc..
As the improvement of people's living standards, requirement of the people to garment material is also higher and higher, this also accelerates phase transformation
The development of temperature-regulating fiber, the developmental research of phase-changing and temperature-regulating fiber come into a completely new field.Microcapsules are prepared at present
Technology has two methods of physics cladding and interfacial polymerization, prepares phase-change microcapsule using physics coating technology, i.e., using wool and
The resolvability energy of other animal ceratins or fibroin in hydrophilic solvent, using water-insoluble phase transition compound as core
Then the heart comes out albumen precipitation with the non-solvent of albumen, form the shell of phase-change material, and then phase-change microcapsule is made, adopt
The special middle microcapsules containing paraffin or polyglycol microcapsule can be prepared with interfacial polymerization method, but the structure of product is all
It is not sufficiently stable.
Research in terms of wool dissolution and keratin are extracted for a long time, common dissolving method have oxidizing process,
A, B, C method of reduction, ion-solubility method and metal salt method etc..Wherein metal salt method mainly use salt, potassium chloride, saltcake or
Magnesium sulfate etc. dissolves wool, but discovery swelling only occurs now wool in the event of high temperatures in the preparation
As there is no dissolve.It is more stable and spare capsule slurry and its preparation can be sealed up for safekeeping therefore, it is necessary to develop a kind of structure
Method.
Summary of the invention
It is an object of the invention to be directed to above-mentioned the problems of the prior art, a kind of hairless protein microcapsules of storing energy through phase change is provided
Slurry and the preparation method and application thereof can be completely dissolved wool in preparation process, and obtained microcapsules size performance is stablized, easily
In sealing up for safekeeping.
To achieve the goals above, hairless protein microcapsules of storing energy through phase change slurry of the present invention：It is 1 μm including Average Particle Diameters
~3 μm of microcapsules, the microcapsules are made of wall material shell, wall material inner casing and core material with phase transition function.
The wall material inner casing is the shell that polyurethane-urea is formed, and polyurethane-urea is by end hydroxy butadiene-isocyanates
Prepolymer reacts generation with water；The wall material shell is the shell formed in hairless protein flocculation sedimentation to wall material inner casing；
The core material uses the n-alkane paraffin of carbon 18-20.
The hairless protein is water-insoluble hairless protein, accounts for the 9.6%~9.9% of microcapsules slurry gross mass, hairless protein
Molecular weight be 40KD-60KD.According to mass fraction meter, the core material in microcapsules accounts for 63.5%~65.3%, wall material inner casing
21.3%~21.8% is accounted for, wall material shell accounts for 9.6%~9.9%, and water accounts for 3%~5.6%.
The preparation method of hairless protein microcapsules of storing energy through phase change slurry of the present invention, includes the following steps：
A. oxidation pre-treatment is carried out to wool；
B. wool is put into heating stirring in liquor zinci chloridi, until wool is completely dissolved, solvent type hair egg is obtained by filtration
White liquor；
C. emulsifier is added into solvent type hairless protein liquid, obtains the solvent type hairless protein to emulsify composite phase-change material
Liquid；
D. by end hydroxy butadiene-isocyanate prepolymer and phase-change material mixed dissolution, composite phase-change liquid is obtained, then
Into composite phase-change liquid, the solvent type hairless protein liquid to emulsify composite phase-change material is added in stirring, obtains microcapsule suspensions；
E. end hydroxy butadiene-isocyanate prepolymer is reacted sufficiently with water by stirring and heating, form wall material
Inner casing；
F. microcapsules flocculation is precipitated in the pH value for adjusting microcapsule suspensions, forms wall material shell；
G. by centrifugation and filtering, hairless protein microcapsules of storing energy through phase change slurry is obtained.
The step a specifically includes following steps：The oxidizing agent solution that mass concentration is 25%~35% is prepared, oxidation
Hydrogen peroxide, potassium permanganate, Peracetic acid or sodium carbonate peroxide are selected in agent；It is arrived using the pH value that PH regulator 831 adjusts solution
7-9 is 1 by wool weight and strong oxidant solution volume ratio:(10~15), wool are put into oxidizing agent solution, at 60 DEG C
Lower holding 50min~70min, takes out rinse wool well later, dries at 80 DEG C~100 DEG C stand-by.
The step b specifically includes following steps：Preparation mass concentration is 58%~65% liquor zinci chloridi, by chlorination
Zinc solution volume and wool weight ratio are (10~15):1, the wool after oxidation pre-treatment is shredded and is scattered in zinc chloride
In solution, first in 85 DEG C~95 DEG C of at a temperature of holding 55min~65min, taking out stirring 3min~5min, constant temperature is kept again
55min~65min further takes out stirring 3min~5min, until wool is completely dissolved, solvent type hairless protein just liquid is obtained by filtration,
At a temperature of low-temperature bake by liquid at the beginning of solvent type hairless protein at 50 DEG C~60 DEG C obtains the solvent type hair that solid content is 2%~3%
Protein liquid.
The step c specifically includes following steps：Use HLB value for 10 emulsifier, by emulsifier 85 DEG C~100
It is melted into Transparent color at DEG C, is 1 by the mass ratio of emulsifier and hairless protein:(1.1~1.3) are mixed, and are with revolving speed
300r/min-500r/min is stirred emulsifier, and solvent type hairless protein liquid is added while stirring, prepares to emulsify
The solvent type hairless protein liquid of composite phase-change material, it is stand-by in 60 DEG C -65 DEG C of at a temperature of constant temperature.
In step d, 1) prepare end hydroxy butadiene-isocyanate prepolymer：By the hydroxyl in end hydroxy butadiene
Ratio with the isocyano in isocyanates is 1:1.05 are mixed, the hydroxyl value of the end hydroxy butadiene 1 to 0.8 it
Between, 18h~for 24 hours is stood after mixing, sufficiently obtains end hydroxy butadiene-isocyanate prepolymer after reaction；2) it makes
Standby composite phase-change liquid：It is 1 by the mass ratio of end hydroxy butadiene-isocyanate prepolymer and phase-change material:(2.7~3.5)
It is mixed, is dissolved under 40 DEG C of constant temperatures, be uniformly mixed with the revolving speed of 45r/min-50r/min, obtain compound phase
Become liquid；3) at 40 DEG C, composite phase-change liquid is stirred with the revolving speed of 300r/min-500r/min, is added to emulsify compound phase
The solvent type hairless protein liquid for becoming material, makes composite phase-change liquid be emulsified into microparticle in solvent type hairless protein liquid, forms micro- glue
Capsule suspension.
By microcapsule suspensions under constant temperature conditions repeatedly with the revolving speed of 300r/min-500r/min in the step e
20min~30min is stirred, then constant temperature stands 20h~30h at 60 DEG C, completes end hydroxy butadiene-isocyanate prepolymer
With sufficiently reacting for water；The pH values of microcapsule suspensions is first adjusted in the step f to 3-4, then adjust pH value make to 4-5 it is micro-
Capsule flocculation is precipitated；5min is centrifuged with the speed of 2500r/min in the step g, filtering uses mesh for 1 μm~3 μm
Filter paper, filter paper upper layer are hairless protein microcapsules of storing energy through phase change slurry.
Hairless protein microcapsules of storing energy through phase change slurry of the present invention can directly with polymer substance it is blended prepare phase-change accumulation energy fibre
Dimension can also be suitable for the modification of flexible textile material.
Compared with prior art, the microcapsules in hairless protein microcapsules of storing energy through phase change slurry of the invention by wall material shell,
Wall material inner casing and core material composition with phase transition function, the properties of microcapsules of double-shell structure are stablized, can be sealed up for safekeeping for a long time standby
With.
Compared with prior art, the preparation method of hairless protein microcapsules of storing energy through phase change slurry of the present invention is in combination with interface
Polymerization and flocculation cladding two kinds of technologies, wool is subjected to oxidation pre-treatment first, opens the disulfide bond on wool surface layer, then with
Liquor zinci chloridi is that solvent dissolves pretreated wool, and solvent type hairless protein liquid is obtained by filtration after being completely dissolved, leads to
It crosses and mixes the solvent type hairless protein liquid with emulsifier, prepare the solvent type hairless protein to emulsify composite phase-change material
Liquid.Again by end hydroxy butadiene-isocyanate prepolymer and phase-change material mixed dissolution, composite phase-change liquid is obtained.To multiple
The solvent type hairless protein liquid with emulsifier is gradually added in the case where closing phase-transition liquid high-speed stirred, is there is composite phase-change liquid
It is emulsified into microparticle in the solvent type hairless protein liquid of emulsifier, makes the microparticle finally by corresponding temperature, time conditions
Interfacial polymerization and flocculation cladding occurs, forms double-shell microcapsule, centrifugal filtration obtains hairless protein microcapsules of storing energy through phase change slurry.
The preparation method simple process of hairless protein microcapsules of storing energy through phase change slurry of the present invention, easily operated and preparation cost are lower.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below.
Hairless protein microcapsules of storing energy through phase change slurry of the invention, the microcapsules for being 1 μm~3 μm including Average Particle Diameters,
Microcapsules are made of wall material shell, wall material inner casing and core material with phase transition function.Wall material inner casing is what polyurethane-urea was formed
Shell, polyurethane-urea react generation with water by end hydroxy butadiene-isocyanate prepolymer；Wall material shell is macromolecular hair egg
The shell formed in white flocculation sedimentation to wall material inner casing；Core material uses the n-alkane paraffin of carbon 18-20.Macromolecular hairless protein is
Water-insoluble hairless protein accounts for the 9.6%~9.9% of microcapsules slurry gross mass, molecular weight 40KD-60KD.According to quality point
Number meter, core material account for 63.5%~65.3%, and wall material inner casing accounts for 21.3%~21.8%, and wall material shell accounts for 9.6%~9.9%, water
Account for 3%~5.6%.
Embodiment 1
The preparation method of hairless protein microcapsules of storing energy through phase change slurry of the present invention, includes the following steps：
A. oxidation pre-treatment is carried out to wool；The oxidizing agent solution that mass concentration is 25% is prepared, oxidant selects dioxygen
Water, potassium permanganate, Peracetic acid or sodium carbonate peroxide；The pH value of solution is transferred to 7 using PH regulator 831, by wool heavy
Amount is 1 with strong oxidant solution volume ratio:10, wool is put into oxidizing agent solution, 50min, Zhi Houqu are kept at 60 DEG C
Wool is rinsed well out, it is stand-by in 80 DEG C of at a temperature of drying.
B. preparing mass concentration is 58% liquor zinci chloridi, is 10 by liquor zinci chloridi volume and wool weight ratio:1,
Wool after oxidation pre-treatment is shredded and is scattered in liquor zinci chloridi, first 85 DEG C at a temperature of keep 55min, take out
Stirring 3min, constant temperature keeps 55min again, further takes out stirring 3min until wool is completely dissolved and solvent type hairless protein is obtained by filtration
First liquid, the at a temperature of low-temperature bake by liquid at the beginning of solvent type hairless protein at 50 DEG C obtain the solvent type hairless protein that solid content is 2%
Liquid.
C. it uses HLB value for 10 emulsifier, emulsifier is melted into Transparent color at 85 DEG C, by emulsifier and hairless protein
Quality than ratio be 1:1.1 mixing are that 300r/min is stirred emulsifier with revolving speed, and solvent type is added in stirring while
Hairless protein liquid prepares the solvent type hairless protein liquid to emulsify composite phase-change material, stand-by in 60 DEG C of at a temperature of constant temperature.
D. by end hydroxy butadiene-isocyanate prepolymer and phase-change material mixed dissolution, composite phase-change liquid is obtained, then
Into composite phase-change liquid, the solvent type hairless protein liquid to emulsify composite phase-change material is added in stirring, obtains microcapsule suspensions；
It specifically includes：1) end hydroxy butadiene-isocyanate prepolymer is prepared：By the hydroxyl in end hydroxy butadiene
Ratio with the isocyano in isocyanates is 1:1.05 are mixed, the hydroxyl value of end hydroxy butadiene between 1 to 0.8,
18h is stood after mixing, sufficiently obtains end hydroxy butadiene-isocyanate prepolymer after reaction；2) compound phase is prepared
Become liquid：It is 1 by the mass ratio of end hydroxy butadiene-isocyanate prepolymer and phase-change material:2.7 are mixed, at 35 DEG C
Constant temperature under dissolve, be uniformly mixed with the revolving speed of 45r/min, obtain composite phase-change liquid；3) 35 DEG C at a temperature of,
Composite phase-change liquid is stirred with the revolving speed of 300r/min, the solvent type hairless protein liquid to emulsify composite phase-change material is added, makes
Composite phase-change liquid is emulsified into microparticle in solvent type hairless protein liquid, forms microcapsule suspensions.
E. microcapsule suspensions are stirred into 20min under constant temperature conditions with the revolving speed of 300r/min, then with 300r/min's
Revolving speed stirs 20min, and constant temperature stands 20h at 60 DEG C, completes the abundant of end hydroxy butadiene-isocyanate prepolymer and water
Reaction forms wall material inner casing；
F. the pH value of microcapsule suspensions is first adjusted to 3-4, and microcapsules is made slowly to flocculate precipitation, surface coats completely, then
PH value is adjusted to 4-5, so that microcapsules is largely flocculated precipitations, completes the process for preparing wall material shell；
G. the microcapsule suspensions formed by interfacial polymerization and flocculation cladding are centrifuged with the speed of 2500r/min
5min is filtered by the filter paper that mesh is 1 μm again later, and filter paper upper layer is hairless protein microcapsules of storing energy through phase change slurry.
Embodiment 2
The preparation method of hairless protein microcapsules of storing energy through phase change slurry of the present invention, includes the following steps：
A. oxidation pre-treatment is carried out to wool；The oxidizing agent solution that mass concentration is 35% is prepared, oxidant selects dioxygen
Water, potassium permanganate, Peracetic acid or sodium carbonate peroxide；The pH value of solution is transferred to 9 using PH regulator 831, by wool heavy
Amount is 1 with strong oxidant solution volume ratio:15, wool is put into oxidizing agent solution, 70min, Zhi Houqu are kept at 65 DEG C
Wool is rinsed well out, is dried at 100 DEG C stand-by.
B. preparing mass concentration is 65% liquor zinci chloridi, is 15 by liquor zinci chloridi volume and wool weight ratio:1,
Wool after oxidation pre-treatment is shredded and is scattered in liquor zinci chloridi, first 95 DEG C at a temperature of keep 65min, take out
Stirring 5min, constant temperature keeps 65min again, further takes out stirring 5min until wool is completely dissolved and solvent type hairless protein is obtained by filtration
First liquid, the at a temperature of low-temperature bake by liquid at the beginning of solvent type hairless protein at 60 DEG C obtain the solvent type hairless protein that solid content is 3%
Liquid.
C. it uses HLB value for 10 emulsifier, emulsifier is melted into Transparent color at 100 DEG C, by emulsifier and hair egg
White mass ratio is 1:1.3 are mixed, and are that 500r/min is stirred emulsifier with revolving speed, stirring while is added molten
Dosage form hairless protein liquid prepares the solvent type hairless protein liquid to emulsify composite phase-change material, waits in 65 DEG C of at a temperature of constant temperature
With.
D. by end hydroxy butadiene-isocyanate prepolymer and phase-change material mixed dissolution, composite phase-change liquid is obtained, then
Into composite phase-change liquid, the solvent type hairless protein liquid to emulsify composite phase-change material is added in stirring, obtains microcapsule suspensions；
It specifically includes：1) end hydroxy butadiene-isocyanate prepolymer is prepared：By the hydroxyl in end hydroxy butadiene
Ratio with the isocyano in isocyanates is 1:1.05 are mixed, the hydroxyl value of end hydroxy butadiene between 1 to 0.8,
It stands after mixing for 24 hours, sufficiently obtains end hydroxy butadiene-isocyanate prepolymer after reaction；2) compound phase is prepared
Become liquid：It is 1 by the mass ratio of end hydroxy butadiene-isocyanate prepolymer and phase-change material:3.5 are mixed, at 40 DEG C
It dissolves under constant temperature, is uniformly mixed with the revolving speed of 50r/min, obtain composite phase-change liquid；3) at 40 DEG C, by compound phase
Become liquid to stir with the revolving speed of 500r/min, adds the solvent type hairless protein liquid to emulsify composite phase-change material, make composite phase-change
Liquid is emulsified into microparticle in solvent type hairless protein liquid, forms microcapsule suspensions.
E. microcapsule suspensions are stirred into 30min under constant temperature conditions with the revolving speed of 500r/min, then with 500r/min's
Revolving speed stirs 30min, and constant temperature stands 30h at 65 DEG C, completes the abundant of end hydroxy butadiene-isocyanate prepolymer and water
Reaction forms wall material inner casing；
F. the pH value of microcapsule suspensions is first adjusted to 3-4, and microcapsules is made slowly to flocculate precipitation, surface coats completely, then
PH value is adjusted to 4-5, so that microcapsules is largely flocculated precipitations, completes the process for preparing wall material shell；
G. the microcapsule suspensions formed by interfacial polymerization and flocculation cladding are centrifuged with the speed of 2500r/min
5min is filtered by the filter paper that mesh is 3 μm again later, and filter paper upper layer is hairless protein microcapsules of storing energy through phase change slurry.
Embodiment 3
Wool is uniformly mixed according to a certain percentage with 30% hydrogen peroxide solution, using PH regulator 831 by solution
PH is transferred to 8, bath raio 1:10,60 DEG C of constant temperature 1h, taking-up is rinsed clean to wool surfaces later, is placed into 100 DEG C of baking oven
Drying.Wool Jing Guo oxidation processes is shredded and is scattered in the liquor zinci chloridi clock that solid content is 60%, bath raio 1:15,90 DEG C
Constant temperature 4h takes out stirring 5min followed by constant temperature per hour, and discovery wool is completely dissolved after constant temperature 4h, is taken out filtering, is passed through baking
The hairless protein liquor zinci chloridi that drying standby hairless protein solid content is 2%, 60 DEG C of constant temperature are stand-by.
The specific emulsifier of 0.19g is taken to dissolve in 80 DEG C of water-baths, to specific emulsification under with the revolving speed of 300r/min
The solvent type hairless protein liquid of 13.5 grams of constant temperature is slowly added in agent, is stirred for 3min later, by the solvent type containing emulsifier
Hairless protein liquid is cooled to 60 DEG C, and constant temperature is stand-by.
Take the n-alkane paraffin of 0.48g end hydroxy butadiene-isocyanate prepolymer Yu 1.42g carbon 18-20,40 DEG C
Constant temperature is slowly added under with the revolving speed of 300r/min into phase-transition liquid later with being uniformly mixed under the revolving speed of 300r/min
Enter the solvent type hairless protein liquid containing emulsifier, continues to stir 20min after the completion of being added, be stirred again with the revolving speed of 50r/min later
30min is mixed, deaeration is for 24 hours under room temperature.
The liquid is distributed in the deionized water of PH=3 with drop-wise after deaeration, the pH value of solution is adjusted to 4 after 20min,
There is a large amount of microcapsules flocculation to be precipitated, mixed liquor is put into a centrifuge, 5min is centrifuged with the speed of 2500r/min, takes out with slow
After fast filter paper filtering, filter paper upper layer is hairless protein microcapsules of storing energy through phase change slurry.
Embodiment 4
Wool is uniformly mixed according to a certain percentage with 30% liquor potassic permanganate, bath raio 1:15,60 DEG C of constant temperature 1h,
It is clean to wool surfaces that flushing is taken out later, is placed into 100 DEG C of baking oven and is dried.Wool Jing Guo oxidation processes is shredded point
Dissipate the liquor zinci chloridi clock for being 60% in solid content, bath raio 1:10,95 DEG C of constant temperature 3.5h take out stirring 3min per hour and connect again
Constant temperature, discovery wool is completely dissolved after constant temperature 3.5h, takes out filtering, prepares the hair that hairless protein solid content is 2% by drying
Albumen liquor zinci chloridi, 60 DEG C of constant temperature are stand-by.
The specific emulsifier of 1.2g is taken to dissolve in 100 DEG C of water-baths, to specific emulsification under with the revolving speed of 400r/min
The solvent type hairless protein liquid of 85.3g constant temperature is slowly added in agent, is stirred for 3-5min later, by the solvent type containing emulsifier
Hairless protein liquid is cooled to 60 DEG C, and constant temperature is stand-by.
Take the n-alkane paraffin of 3.03g end hydroxy butadiene-isocyanate prepolymer Yu 9.01g carbon 18-20,50 DEG C
Constant temperature is slowly added under with the revolving speed of 400r/min into phase-transition liquid later with being uniformly mixed under the revolving speed of 400r/min
Enter the solvent type hairless protein liquid containing emulsifier, continues to stir 25min after the completion of being added, be stirred again with the revolving speed of 40r/min later
25min is mixed, deaeration 20h under room temperature.
The liquid is distributed in the deionized water that pH value is 3 with drop-wise after deaeration, is adjusted to the pH value of solution after 20min
4, there is a large amount of microcapsules flocculation to be precipitated, mixed liquor is put into a centrifuge, 5min is centrifuged with the speed of 2500r/min, taken out and use
After slow filter paper filtering, filter paper upper layer is hairless protein microcapsules of storing energy through phase change slurry.
Claims (10)
1. a kind of hairless protein microcapsules of storing energy through phase change slurry, it is characterised in that：It is 1 μm~3 μm micro- including Average Particle Diameters
Capsule, the microcapsules are made of wall material shell, wall material inner casing and core material with phase transition function.
2. hairless protein microcapsules of storing energy through phase change slurry according to claim 1, it is characterised in that：The wall material inner casing is
The shell that polyurethane-urea is formed, polyurethane-urea react generation with water by end hydroxy butadiene-isocyanate prepolymer；
The wall material shell is that molecular weight is the shell formed in hairless protein flocculation sedimentation to wall material inner casing；
The core material uses the n-alkane paraffin of carbon 18-20.
3. hairless protein microcapsules of storing energy through phase change slurry according to claim 2, it is characterised in that：The hairless protein is non-
Water-soluble hairless protein, accounts for the 9.6%~9.9% of microcapsules slurry gross mass, and the molecular weight of hairless protein is 40KD-60KD.
4. hairless protein microcapsules of storing energy through phase change slurry according to claim 2, it is characterised in that：According to mass fraction meter,
Core material accounts for 63.5%~65.3%, and wall material inner casing accounts for 21.3%~21.8%, and wall material shell accounts for 9.6%~9.9%, and water accounts for 3%
~5.6%.
5. a kind of preparation method of hairless protein microcapsules of storing energy through phase change slurry, which is characterized in that include the following steps：
A. oxidation pre-treatment is carried out to wool；
B. wool is put into heating stirring in liquor zinci chloridi, until wool is completely dissolved, solvent type hairless protein liquid is obtained by filtration；
C. emulsifier is added into solvent type hairless protein liquid, obtains the solvent type hairless protein liquid to emulsify composite phase-change material；
D. by end hydroxy butadiene-isocyanate prepolymer and phase-change material mixed dissolution, composite phase-change liquid is obtained, then to again
The solvent type hairless protein liquid for stirring and being added to emulsify composite phase-change material in phase-transition liquid is closed, microcapsule suspensions are obtained；
E. end hydroxy butadiene-isocyanate prepolymer is reacted sufficiently with water by stirring and heating, form wall material inner casing；
F. microcapsules flocculation is precipitated in the pH value for adjusting microcapsule suspensions, forms wall material shell；
G. by centrifugation and filtering, hairless protein microcapsules of storing energy through phase change slurry is obtained.
6. the preparation method of hairless protein microcapsules of storing energy through phase change slurry according to claim 5, which is characterized in that the step
Rapid a specifically includes following steps：The oxidizing agent solution that mass concentration is 25%~35% is prepared, oxidant selects hydrogen peroxide, height
Potassium manganate, Peracetic acid or sodium carbonate peroxide；Arrive 7-9 using the pH value that PH regulator 831 adjusts solution, by wool weight and
Strong oxidant solution volume ratio is 1:(10~15), wool are put into oxidizing agent solution, 60 DEG C -65 DEG C at a temperature of keep
50min~70min takes out rinse wool well later, dries at 80 DEG C~100 DEG C stand-by.
7. the preparation method of hairless protein microcapsules of storing energy through phase change slurry according to claim 5, which is characterized in that the step
Rapid b specifically includes following steps：Preparation mass concentration is 58%~65% liquor zinci chloridi, by liquor zinci chloridi volume and wool
Weight ratio is (10~15):1, the wool after oxidation pre-treatment is shredded and is scattered in liquor zinci chloridi, first at 85 DEG C
55min~65min is kept at a temperature of~95 DEG C, taking out stirring 3min~5min, constant temperature keeps 55min~65min again, then takes
3min~5min is stirred out, until wool is completely dissolved, solvent type hairless protein just liquid is obtained by filtration, by liquid at the beginning of solvent type hairless protein
In 50 DEG C~60 DEG C of at a temperature of low-temperature bake, the solvent type hairless protein liquid that solid content is 2%~3% is obtained；
The step c specifically includes following steps：Use HLB value for 10 emulsifier, by emulsifier at 85 DEG C~100 DEG C
It is melted into Transparent color, is 1 by the mass ratio of emulsifier and hairless protein:(1.1~1.3) are mixed, and are 300r/ with revolving speed
Min-500r/min is stirred emulsifier, and solvent type hairless protein liquid is added while stirring, prepares compound to emulsify
The solvent type hairless protein liquid of phase-change material, it is stand-by in 60 DEG C -65 DEG C of at a temperature of constant temperature.
8. the preparation method of hairless protein microcapsules of storing energy through phase change slurry according to claim 5, which is characterized in that step d tool
Body includes：1) end hydroxy butadiene-isocyanate prepolymer is prepared：By the hydroxyl and isocyanates in end hydroxy butadiene
In isocyano ratio be 1:1.05 are mixed, and for the hydroxyl value of the end hydroxy butadiene between 1 to 0.8, mixing is equal
Even rear standing 18h~for 24 hours, sufficiently end hydroxy butadiene-isocyanate prepolymer is obtained after reaction；2) composite phase-change is prepared
Liquid：It is 1 by the mass ratio of end hydroxy butadiene-isocyanate prepolymer and phase-change material:(2.7~3.5) are mixed,
It dissolves under 35 DEG C -40 DEG C of constant temperature, is uniformly mixed with the revolving speed of 45r/min-50r/min, obtain composite phase-change liquid；
3) at 35 DEG C -40 DEG C, composite phase-change liquid is stirred with the revolving speed of 300r/min-500r/min, is added to emulsify compound phase
The solvent type hairless protein liquid for becoming material, makes composite phase-change liquid be emulsified into microparticle in solvent type hairless protein liquid, forms micro- glue
Capsule suspension.
9. the preparation method of hairless protein microcapsules of storing energy through phase change slurry according to claim 5, which is characterized in that step e will
Microcapsule suspensions repeatedly stir 20min~30min under constant temperature conditions with the revolving speed of 300r/min-500r/min, then 60
Constant temperature stands 20h~30h at DEG C -65 DEG C, completes sufficiently reacting for end hydroxy butadiene-isocyanate prepolymer and water；Step
Rapid f first adjusts the pH values of microcapsule suspensions to 3-4, then adjusting pH value is precipitated microcapsules flocculation to 4-5；Step g with
2500r/min is centrifuged 5min, and filtering uses mesh for 1 μm~3 μm of filter paper, and filter paper upper layer is hairless protein microcapsules of storing energy through phase change
Slurry.
10. it is a kind of based on hairless protein microcapsules of storing energy through phase change slurry described in any one of claim 1-4 in blended preparation
Phase-change energy-storage fibre and the application in flexible textile material is modified.
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