CN108467469A - A kind of photothermal conversion polyurethane energy storage thin-film material and preparation method thereof and film - Google Patents
A kind of photothermal conversion polyurethane energy storage thin-film material and preparation method thereof and film Download PDFInfo
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Abstract
The present invention relates to a kind of photothermal conversion polyurethane energy storage thin-film material in phase-changing energy storage material field and preparation method thereof and films.The photothermal conversion polyurethane energy storage thin-film material, by being prepared comprising following components：Polyethylene glycol, oligomer polyethers or polyester diol, diisocyanate, small molecule dihydric alcohol, double hydroxy dyes；The molecular weight of the polyethylene glycol is 2000~20000；The oligomer polyethers or the molecular weight of polyester diol are 500~3000；Double hydroxy dyes contain there are two free active hydroxyl groups, can absorb the visible light of 380~780nm；The polyurethane film of the present invention makes film have both photothermal conversion and thermal energy storage function, can effectively solve deformation, the leakage problem of organic phase change material by the heat accumulation characteristic of dyestuff and sizing phase-change material that covalent bond is keyed in；Polyurethane film phase transformation enthalpy provided by the invention is high, and performance is stablized, and synthesis technology is relatively easy, and raw material is easy to get, and has very wide application prospect.
Description
Technical field
The present invention relates to phase-changing energy storage material fields, furtherly, are related to a kind of photothermal conversion polyurethane energy storage film
Material and preparation method thereof and film.
Background technology
Currently, the greatest problem that energy shortage problem, which is today's society, to be faced, the development and utilization of new energy is currently to solve
A certainly important channel of energy problem, solar energy, water energy, tide energy etc. clean the reproducible energy and are widely paid close attention to,
But there is the shortcomings of intermittent, discontinuity and mismatch in these energy, offer energy can not continuing, stablizing
Amount, it is therefore desirable to which a kind of phase-changing energy storage material realizes the sustainable supply of energy.
The use of thermal energy is the most extensive in all energy utilization types, during most of energy use, is all
Meet the production and life of the mankind by the approach of thermal energy conversion.But there are a large amount of energy during heat energy utilization
Amount loss and the serious wasting of resources.In addition to this, the mismatch in the time of energy utilization and space also leads to the wave of resource
Take.Therefore, how thermal energy is efficiently utilized, is to solve the effective way that heat energy loss is big and utilization rate is low.Solar energy
Heat utilization is a kind of most simple, most direct, one of the most effective ways, has become the research heat that solar energy highly effective utilizes
Point, but since the energy density that solar radiation reaches earth surface is low, by the shadow of the natural causes such as season, weather, time
It rings so that direct utilize of solar energy receives many limitations, in order to solve these problems, needs a kind of effective energy storage dress
It sets and solar energy is stored, release when needed, to meet the needs of people.
Solar radiant energy is changed into thermal energy to be used, light trapping, photothermal conversion and energy stores is related generally to and waited
Journey, i.e. solar utilizing equipment include acquisition and reforming unit and the thermal energy storage device of solar radiant energy.It absorbs at present too
Positive radiation energy and the material for being converted to thermal energy include inorganic material, semiconductor and organic dyestuff etc..Organic dyestuff has light absorption
With the double grading of photothermal conversion, wherein organic dyestuff contains reactive active group, it is easy to phase-change material with chemistry
The mode of key combines, and is separated after overcoming the problems, such as photothermal conversion phase transformation and can prepare light extraction trapping, photothermal conversion and energy
Amount is stored in integrated material.
Phase-changing energy storage material is divided into inorganic phase-changing material, organic phase change material and composite phase-change material.Wherein organic setting
Phase-changing energy storage material has many advantages, such as small dimensionally stable, volume change, No leakage, corrosion-free, becomes grinding for phase-changing energy storage material
Study carefully one of hot spot.It is most representative as Material synthesis polyurethane phase-changing energy storage material using polyethylene glycol, such as Mu Siyang will
Polystyrene propylene cyanogen is grafted to and prepares a kind of novel solid-solid phase change material on polyethylene glycol, and phase transformation enthalpy is 68.3kJ/
Kg still keeps compared with high heat storage ability after 1000 cycles and has preferable thermal stability.Liu Zhineng etc. with
PEG4000 is phase-change material, and castor oil is skeleton, is linking group by MDI and HDI, and it is solid to synthesize novel polyurethane
Phase-change material, phase transformation enthalpy are 117.7J/g, have excellent thermal stability and reliability, have very in terms of solar energy heat-storage
Big application prospect.
Characteristic of the dyestuff to light absorption and photothermal conversion so that it is more and more wider that dyestuff is introduced into the research in phase-change material
It is general, a kind of Introduction To Cn Patent of the Publication No. CN 102532945A more block macromoleculars of photothermal conversion organic fixed phase changes
Dyestuff, the dyestuff are using polyethylene glycol as soft segment, and dyestuff is more block type polymer dyestuffs of hard section, may not only be applied to solar energy
Photothermal conversion and storage, can be also used for dyeing and stamp.The Chinese patent of Publication No. CN106047305A discloses one
The preparation method of kind photothermal conversion type organic/inorganic composite energy-storage material, using polyethylene glycol as phase transformation component, by dyestuff with chemistry
The form of key is attached on silica backing material, prepares the composite phase-change material of photothermal conversion and energy stores one,
Its energy storage density is big, and clad ratio is high.But the energy storage material prepared is powder, and phase-change material is existed in the form of being wrapped by
In energy storage material, there are the danger of leakage.
Invention content
In order to solve the above-mentioned problems in the prior art, the present invention proposes a kind of photothermal conversion polyurethane energy storage film
Material.Relate in particular to a kind of photothermal conversion polyurethane energy storage thin-film material and preparation method thereof and film.The photo-thermal turns
Change polyurethane energy storage film be it is a kind of with light trapping, photothermal conversion and thermal energy storage in the polyurethane energy storage film of one, this
Kind film is using polyethylene glycol, oligomer polyester or polyether Glycols as soft segment, with double hydroxy dyes, diisocyanate, small molecule
Dihydric alcohol is hard section, and wherein dyestuff can absorb visible light and carry out photothermal conversion, and polyethylene glycol is phase-change accumulation energy component；This hair
The bright polyurethane film for having both photothermal conversion and thermal energy storage passes through the heat accumulation of dyestuff and sizing phase-change material that covalent bond is keyed in
Characteristic makes film have both photothermal conversion and thermal energy storage function, can effectively solve deformation, the leakage problem of organic phase change material,
And synthesis technology is relatively easy, using convenient.
One of the object of the invention is to provide a kind of photothermal conversion polyurethane energy storage thin-film material, by including polyethylene glycol, low
Component including polymers polyethers or polyester diol, diisocyanate, double hydroxy dyes, small molecule dihydric alcohol is prepared, institute
Stating the structural formula of photothermal conversion polyurethane energy storage thin-film material can be：
Wherein：R is diisocyanate component, R2For oligomer diol component, Dye is dyestuff, and n is by peg molecule
Amount determines, may generally be 2000~20000.
The two of the object of the invention are to provide the preparation method of the photothermal conversion polyurethane energy storage thin-film material, it may include
Following steps：
(1) polyethylene glycol and oligomer polyethers or polyester diol are dried in vacuo, remove moisture；It specifically can be true
60~80 DEG C of 2~3h of processing in empty drying box, to remove the moisture contained in raw material；
(2) by treated polyethylene glycol and oligomer polyethers or polyester diol and the diisocyanate according to
The amount is dissolved in n,N-Dimethylformamide, and the dosage of n,N-Dimethylformamide is fully to dissolve component, in nitrogen
Atmosphere under reacted, reaction temperature be 30~40 DEG C, the reaction time can be 2~3h, obtain base polyurethane prepolymer for use as；
(3) double hydroxy dyes are dissolved in solvent by the dosage, the solvent dosage of addition is that dyestuff is fully molten
Solution is then added in base polyurethane prepolymer for use as, is increased temperature and is reacted to 60~70 DEG C, the reaction time can be 1~2h；Institute
It states solvent and is selected from least one of N,N-dimethylformamide (DMF), acetone or dichloromethane；
(4) it is eventually adding small molecule glycol chain extender, increases temperature and reacted to 80~90 DEG C, the reaction time can be
2~3h obtains polyurethane solutions, the as described photothermal conversion polyurethane energy storage thin-film material.
Further, the photothermal conversion polyurethane energy storage thin-film material (polyurethane solutions) can be poured into polytetrafluoro mold
In, mold is dried, mold can be specifically placed in 60~80 DEG C of baking ovens and dry 8~10h to get to the poly- ammonia of the photothermal conversion
Ester energy storage film.
Wherein,
The oligomer polyethers or polyester diol are (0~15) with the molar ratio of polyethylene glycol：1, preferably (0~8)：1；
Molar ratio of the molal quantity summation of the polyethylene glycol, oligomer polyethers or polyester diol with small molecule dihydric alcohol
It is 1：(0.5~10), preferably 1：(0.7~5)；
Hydroxyl summation in the polyethylene glycol, oligomer polyethers or polyester diol is the same as the isocyanic acid in diisocyanate
Ester group molar ratio is 1：(1~7), preferably 1：(2~5)；
The same diisocyanate of hydroxyl summation in the polyethylene glycol, oligomer polyethers or polyester diol, small molecule dihydric alcohol
Isocyanate group molar ratio in ester is (1~2)：1, preferably (1~1.5)：1.
The molecular weight of the polyethylene glycol is 2000~20000, preferably 4000~10000；
The oligomer polyethers or the molecular weight of polyester diol are 500~3000, preferably 1000~2500；
The diisocyanate be selected from 4,4 '-methyl diphenylene diisocyanates (MDI), isophorone diisocyanate,
At least one of toluene di-isocyanate(TDI).
The oligomer polyethers or polyester diol can be selected from polypropylene glycol, polytetrahydrofuran ether glycol, polyadipate fourth
At least one of glycol esterdiol, polyethylene glycol adipate glycol；
The small molecule dihydric alcohol is selected from least one of ethylene glycol, 1,4- butanediols, 1,6-HD.
Double hydroxy dye dosages account for polyethylene glycol, oligomer polyethers or polyester diol, diisocyanate, small molecule
The 0.1%~3% of dihydric alcohol quality summation, preferably 0.2%~1%.
Double hydroxy dyes are containing there are two the azo dyes of activity hydroxy or anthraquinone dyes.
The azo dyes can be selected from least one of dyestuff A, dyestuff B, dyestuff C, dyestuff D；
The structure of the wherein described dyestuff A is structural formula (1)：
R is H, Cl, CN, NO in formula (1)2, CONHR' or COOR'；Wherein R' is H, CnH2n+1Straight chain saturated alkyl, and 1
≤ n≤18, n are integer；
The structure of the wherein described dyestuff B is structural formula (2)：
R is H, Cl, CN, NO in formula (2)2, OR', CONHR' or COOR'；Wherein R' is H, CnH2n+1Straight chain be saturated alkane
Base, and 1≤n≤18, n are integer；
The structure of the wherein described dyestuff C is structural formula (3)：
R is CH in formula (3)2CH3、CH2CH2CN or CH2COOR'；Wherein R' is H or CnH2n+1Straight chain saturated alkyl, and 1
≤ n≤18, n are integer；
Wherein the structure of dyestuff D is structural formula (4)：
R is CH in formula (4)2CH3、CH2CH2CN or CH2COOR', wherein R' are H, CnH2n+1Straight chain saturated alkyl, and 1
≤ n≤18, n are integer.
The anthraquinone dye can be selected from least one of dyestuff E, dyestuff F, dyestuff G, dyestuff H；
Wherein the structure of dyestuff E is structural formula (5)：
R in formula (5)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2For H,
Cl、CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain be saturated alkane
Base, and 1≤n≤18, n are integer.X is OH or NH2；The integer that k is 1~3；
Wherein the structure of dyestuff F is structural formula (6)：
R in formula (6)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2For H,
Cl、CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain be saturated alkane
Base, and 1≤n≤18, n are integer.X is OH or NH2；The integer that k is 1~3；
Wherein the structure of dyestuff G is structural formula (7)：
R in formula (7)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2、R3For H,
Cl、CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain be saturated alkane
Base, and 1≤n≤18, n are integer.
Wherein the structure of dyestuff H is structural formula (8)：
R in formula (8)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2、R3For H,
Cl、CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5.Wherein R' is H, CnH2n+1Straight chain be saturated alkane
Base, and 1≤n≤18, n are integer.
The three of the object of the invention are to provide a kind of photothermal conversion polyurethane energy storage film.The film can be by including following step
Rapid method is prepared：The photothermal conversion polyurethane energy storage thin-film material is poured into polytetrafluoro mold, mold is dried,
Obtain the photothermal conversion polyurethane energy storage film.
The photothermal conversion polyurethane energy storage film of the present invention, accesses dyestuff in polyurethane, using covalent bond by dyestuff and
Sizing phase-change material is organically combined, and by adjusting raw material proportioning, soft or hard film appropriate can be made, by changing dyestuff product
Kind, the visible light of 380~780nm in sunlight can be trapped and carry out photothermal conversion, it will using polyethylene glycol
Amount stores, and realizes light trapping, photothermal conversion and energy stores.Compared with traditional doping formula, this film durability
Good, compatibility and stability greatly improve.Prepared thin film phase change enthalpy is high, and performance is stablized, and synthesis technology is relatively easy, former
Material is easy to get, and has very wide application prospect, such as can be used for the fields such as intelligent clothing, food packaging, agricultural greenhouse.
Description of the drawings
Fig. 1 is the DSC curve of the photothermal conversion polyurethane energy storage film of embodiment 9；
Fig. 2 is the uv absorption spectra of dyestuff B in embodiment 9；
Fig. 3 is the photothermal conversion polyurethane energy storage thin film photo-thermal transformation curve of embodiment 9；
Fig. 4 is that the cycle thermal stability of embodiment 9 tests DSC curve.
Specific implementation mode
With reference to embodiment, further illustrate the present invention.But the present invention is not restricted by the embodiments.
Experimental method shown in the following example is unless otherwise specified this field conventional method；The reagent
And material is commercially available unless otherwise specified.
Polyethylene glycol and oligomer polyethers or polyester diol are handled into 2~3h for 60~80 DEG C in vacuum drying chamber, it is standby
With.
Embodiment 1
10g polyethylene glycol 2000s, 10g polyester diol PBA2000 and 40mL N, N- dimethyl are added into four-hole boiling flask
Formamide (DMF), is passed through nitrogen, is heated to 40~50 DEG C of dissolvings, and then cooling degree is added is dissolved in 40mL thereto to 35 DEG C
4,4 '-methyl diphenylene diisocyanate (MDI) 5.5g, 1~2h of insulation reaction of n,N-Dimethylformamide (DMF).Then
R=H (structures in dyestuff the B 0.13g, dyestuff B for being dissolved in 20mL n,N-Dimethylformamide (DMF) are added into reaction system
It is shown in Table 1), increases temperature to 65 DEG C, react 1~2h.1.2g 1,4-butanediol is finally added into system, is warming up to after adding
85 DEG C, the reaction was continued 2~3h, obtain polyurethane solutions.10mL solution is taken to be put into 15cm × 10cm × 1cm PolyTHF moulds
In tool, 60 DEG C of drying, obtain the photothermal conversion polyurethane energy storage film in drying box.
Embodiment 2
The present embodiment other content with embodiment 1, the difference is that：The dosage of Macrogol 6000 is 9.6g,
The dosage of PBA2000 is 16.8g, and the dosage of dyestuff B is 0.16g, R=H in dyestuff B (structure is shown in Table 1).
Embodiment 3
The present embodiment other content with embodiment 1, the difference is that：The dosage of PEG 8000 is 13.6g,
The dosage of PBA2000 is 16.6g, and the dosage of dyestuff B is 0.16g, R=H in dyestuff B (structure is shown in Table 1).
Embodiment 4
The present embodiment other content with embodiment 1, the difference is that：The dosage of polyethylene glycol 10000 is 14g,
The dosage of PBA2000 is 17.2g, and the dosage of dyestuff B is 0.18g, R=H in dyestuff B (structure is shown in Table 1).
Embodiment 5
The present embodiment other content with embodiment 1, the difference is that：The dosage of PEG 20000 is 14g,
The dosage of PBA2000 is 18.6g, and the dosage of dyestuff B is 0.16g, R=H in dyestuff B (structure is shown in Table 1).
Embodiment 6
The present embodiment other content with embodiment 1, the difference is that：The dosage of polyethylene glycol 10000 is 10g,
The dosage of PBA2000 is 6g, and the dosage of MDI is 3g, and the dosage of dyestuff B is 0.09g, R=H (structure is shown in Table 1) in dyestuff B, 1,
4- butanediol dosages are 0.8g.
Embodiment 7
The present embodiment other content with embodiment 1, the difference is that：The dosage of polyethylene glycol 10000 is 10g,
The dosage of PBA2000 is 3g, and the dosage of MDI is 3.13g, and the dosage of dyestuff B is 0.08g, R=H (structure is shown in Table 1) in dyestuff B,
1,4- butanediol dosages are 1.0g.
Embodiment 8
The present embodiment other content with embodiment 1, the difference is that：The dosage of polyethylene glycol 10000 is 10g,
The dosage of PBA2000 is 2g, and the dosage of MDI is 2g, and the dosage of dyestuff B is 0.06g, R=H (structure is shown in Table 1) in dyestuff B, 1,
4- butanediol dosages are 0.55g.
Embodiment 9
It takes 10g polyethylene glycol 10000 in four mouthfuls of flask, is passed through nitrogen, the DMF that 40mL is added is molten at 40~50 DEG C
Solution reduces temperature to 35 DEG C after being completely dissolved, the MDI for then weighing 1.75g is dissolved in the DMF of 20mL, is added at one time
In flask, 1~2h is reacted, flask is added it to after being completely dissolved with DMF dissolvings 0.065g the dyestuff B, wherein R=H of 20mL
In, temperature is increased to 65 DEG C, 1~2h is reacted, is eventually adding the 1,4-butanediol of 0.55g, and increasing temperature, the reaction was continued 2 to 85 DEG C
~3h, obtains polyurethane solutions, takes 10mL solution to be put into 15cm × 10cm × 1cm PolyTHF molds, in drying box
In 60 DEG C of solvent evaporateds, obtain photothermal conversion polyurethane energy storage film.
The fusion and crystallizing points and enthalpy of material, the result is shown in Figure 1 are measured according to GB/T 19466.3-2004.
The absorbing wavelength that dye solution is measured according to GB/T 19267.2-2008, is as a result shown in Fig. 2.
According to document：The synthesis of the bright photothermal conversions polyether-based setting phase change energy storage materials of Wang Yun and performance study [D] are big
Even Polytechnics, 2013, measure the photothermal conversion and energy storage capability of film, as a result see Fig. 3.
Fig. 4 is the DSC comparison diagrams that material irradiates material before and after 100 times repeatedly under simulated solar irradiation.
As can be seen from Figure 1 the phase transformation enthalpy of the heating-cooling of material is respectively 116.20J/g, 104.65J/g, phase transformation
Temperature is 65.89 DEG C, 24.39 DEG C, illustrates that material has very high energy storage density, can achieve the effect that storage and release heat.
From figure 2 it can be seen that the maximum absorption wavelength of dyestuff B is counted in 504nm according to the absorption law formula of light
The maximum molar absorption coefficient for calculating the dyestuff is 31449Lmol-1·cm-1, illustrate that the dyestuff has higher absorption to light
Intensity.
From figure 3, it can be seen that as light application time extends, the temperature of film gradually rises, and reaches heating in 15min or so
Platform, after removing light source, rapid drop in temperature, but Cooling events occur at 25 DEG C or so, material is by luminous energy before this explanation
It is transformed to thermal energy and using phase transformation component storage, after leaving light source, this partial heat energy slowly releases, form one
Cooling events.
From fig. 4, it can be seen that after carrying out 100 illumination down cycles experiments to material, material phase transformation enthalpy decreases,
But whole to be no more than 10%, phase transition temperature variation is little, illustrates that the stability of prepared photothermal conversion energy storage material is good.
Embodiment 10
The present embodiment other content with embodiment 9, the difference is that：Dyestuff is A (structure is shown in Table 1), and dosage is
0.069g。
Embodiment 11
The present embodiment other content with embodiment 9, the difference is that：Dyestuff is B (structure is shown in Table 1), and dosage is
0.066g。
Embodiment 12
The present embodiment other content with embodiment 9, the difference is that：Dyestuff is E (structure is shown in Table 1), and dosage is
0.065g。
Embodiment 13
The present embodiment other content with embodiment 9, the difference is that：Dyestuff is F (structure is shown in Table 1), and dosage is
0.063g。
Dyestuff concrete structure formula used in 1 embodiment of table
Claims (10)
1. a kind of photothermal conversion polyurethane energy storage thin-film material, it is characterised in that structural formula is as follows：
Wherein：R is diisocyanate component, R2For oligomer diol component, Dye is dyestuff,
N=2000~20000.
2. the preparation method of photothermal conversion polyurethane energy storage thin-film material according to claim 1, it is characterised in that including
Following steps：
(1) polyethylene glycol, oligomer polyethers or polyester diol are dried in vacuo, remove moisture；
(2) treated polyethylene glycol, oligomer polyethers or polyester diol and diisocyanate are dissolved in N, N- diformazans
Base formamide, is reacted under nitrogen atmosphere, and reaction temperature is 30~40 DEG C, obtains base polyurethane prepolymer for use as；
(3) double hydroxy dyes are dissolved in solvent, are then added in the base polyurethane prepolymer for use as, increase temperature to 60~70 DEG C into
Row reaction；The solvent is selected from least one of N,N-dimethylformamide, acetone or dichloromethane；
(4) it is eventually adding small molecule glycol chain extender, increases temperature and reacted to 80~90 DEG C, obtain polyurethane solutions,
The as photothermal conversion polyurethane energy storage thin-film material.
3. the preparation method of photothermal conversion polyurethane energy storage thin-film material according to claim 2, it is characterised in that：
The oligomer polyethers or polyester diol are (0~15) with the molar ratio of the polyethylene glycol：1, preferably (0~8)：1；
The molal quantity summation of the polyethylene glycol, oligomer polyethers or polyester diol is 1 with the molar ratio of small molecule dihydric alcohol：
(0.5~10), preferably 1：(0.7~5).
4. the preparation method of photothermal conversion polyurethane energy storage thin-film material according to claim 2, it is characterised in that：
Hydroxyl summation in the polyethylene glycol, oligomer polyethers or polyester diol is the same as the isocyanate group in diisocyanate
Molar ratio is 1：(1~7), preferably 1：(2~5)；
Hydroxyl summation is the same as in diisocyanate in the polyethylene glycol, oligomer polyethers or polyester diol, small molecule dihydric alcohol
Isocyanate group molar ratio be (1~2)：1, preferably (1~1.5)：1.
5. photothermal conversion polyurethane energy storage thin-film material according to claim 2, it is characterised in that：
The molecular weight of the polyethylene glycol is 2000~20000, preferably 4000~10000；
The oligomer polyethers or the molecular weight of polyester diol are 500~3000, preferably 1000~2500；
The diisocyanate is selected from 4,4 '-methyl diphenylene diisocyanates, isophorone diisocyanate, toluene diisocyanate
At least one of acid esters.
6. photothermal conversion polyurethane energy storage thin-film material according to claim 2, it is characterised in that：
The oligomer polyethers or polyester diol, selected from polypropylene glycol, polytetrahydrofuran ether glycol, poly adipate succinic acid ester
At least one of glycol, polyethylene glycol adipate glycol；
The small molecule dihydric alcohol is selected from least one of ethylene glycol, 1,4- butanediols, 1,6-HD.
7. photothermal conversion polyurethane energy storage thin-film material according to claim 2, it is characterised in that：
Double hydroxy dye dosages account for polyethylene glycol, oligomer polyethers or polyester diol, diisocyanate, small molecule binary
The 0.1%~3% of alcohol quality summation, preferably 0.2%~1%；
Double hydroxy dyes are containing there are two the azo dyes of activity hydroxy or anthraquinone dyes.
8. photothermal conversion polyurethane energy storage thin-film material according to claim 7, it is characterised in that：
The azo dyes is selected from least one of dyestuff A, dyestuff B, dyestuff C, dyestuff D；
The structure of the wherein described dyestuff A is structural formula (1)：
R is H, Cl, CN, NO in formula (1)2, CONHR' or COOR'；Wherein R' is H, CnH2n+1Straight chain saturated alkyl, and 1≤n
≤ 18, n are integer；
The structure of the wherein described dyestuff B is structural formula (2)：
R is H, Cl, CN, NO in formula (2)2, OR', CONHR' or COOR'；Wherein R' is H, CnH2n+1Straight chain saturated alkyl, and 1
≤ n≤18, n are integer；
The structure of the wherein described dyestuff C is structural formula (3)：
R is CH in formula (3)2CH3、CH2CH2CN or CH2COOR'；Wherein R' is H or CnH2n+1Straight chain saturated alkyl, and 1≤n≤
18, n be integer；
Wherein the structure of dyestuff D is structural formula (4)：
R is CH in formula (4)2CH3、CH2CH2CN or CH2COOR', wherein R' are H, CnH2n+1Straight chain saturated alkyl, and 1≤n≤
18, n be integer.
9. photothermal conversion polyurethane energy storage thin-film material according to claim 7, it is characterised in that：
The anthraquinone dye is selected from least one of dyestuff E, dyestuff F, dyestuff G, dyestuff H；
Wherein the structure of dyestuff E is structural formula (5)：
R in formula (5)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2For H, Cl, CH3、
OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain saturated alkyl, and 1≤
N≤18, n are integer；X is OH or NH2；The integer that k is 1~3；
Wherein the structure of dyestuff F is structural formula (6)：
R in formula (6)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2For H, Cl, CH3、
OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain saturated alkyl, and 1≤
N≤18, n are integer；X is OH or NH2；The integer that k is 1~3；
Wherein the structure of dyestuff G is structural formula (7)：
R in formula (7)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2、R3For H, Cl,
CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain saturated alkyl,
And 1≤n≤18, n are integer；
Wherein the structure of dyestuff H is structural formula (8)：
R in formula (8)1For H, Cl, CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；R2、R3For H, Cl,
CH3、OCH3、OC2H5、OH、NHR'、CN、CONH2、COOCH3Or COOC2H5；Wherein R' is H, CnH2n+1Straight chain saturated alkyl,
And 1≤n≤18, n are integer.
10. photothermal conversion polyurethane energy storage thin-film material according to claim 1 or according to any of claim 2~9
Film made of photothermal conversion polyurethane energy storage thin-film material made from preparation method described in, it is characterised in that by include with
Method including lower step is made：The photothermal conversion polyurethane energy storage thin-film material is poured into polytetrafluoro mold, by mold
Drying is to get to the photothermal conversion polyurethane energy storage film.
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