CN102702457B - Preparation method of biologically degradable phase change material - Google Patents
Preparation method of biologically degradable phase change material Download PDFInfo
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- CN102702457B CN102702457B CN201210132563.7A CN201210132563A CN102702457B CN 102702457 B CN102702457 B CN 102702457B CN 201210132563 A CN201210132563 A CN 201210132563A CN 102702457 B CN102702457 B CN 102702457B
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Abstract
The invention relates to a preparation method of biologically degradable phase change material. The preparation method of biologically degradable phase change material includes: firstly, dissolving polyhydroxyalkanoate macromer, namely PHA-diol with hydroxy terminated to both ends, in organic solvent, sequentially adding acid-binding agent and acryloyl chloride under ice bath, allowing for reaction at 35 DEG C for 6-8 hours under protection of nitrogen, and adding precipitator for precipitation under ice bath after reaction to obtain crylic acid polyhydroxyalkanoate, namely PHA-diMA; and secondly, mixing acrylic polyoxyethylene ester and the PHA-diMA, adding into 1, 2-dichloroethane, adding ammonium persulfate, heating to 70-85 DEG C, and allowing for reaction for 2h-24h to obtain the biologically degradable phase change material. The biologically degradable phase change material prepared by the method is high in phase change enthalpy, high in thermal cyclicity, high in thermal stability and biologically degradable and meets the requirement for energy conservation and environment protection. The preparation method is simple in process and low in production cost and has promising application prospect.
Description
Technical field
The invention belongs to the preparation field of phase-changing energy storage material, particularly a kind of preparation method of biodegradable phase-changing energy storage material.
Background technology
Phase-changing energy storage material (PCM) refers to the heat that absorbs or discharge while utilizing himself structure and states of matter to change, and for the material of energy storage.PCM have energy storage density large, hold the advantages such as exothermic process approximately constant temperature, process be easy to control, can effectively change the distribution of the energy on time, space, thereby reach energy-conservation object.Can be used for solving the unbalance contradiction of heat energy Supply and Demand, improve efficiency of energy utilization and protection of the environment.
In order to expand the application potential of phase change material, investigator adopts the technology such as chemical method, microcapsule method to carry out immobilized to solid-liquid phase change material.It is raw material that Chinese invention patent CN 100595252 C be take trihydroxy-compound, diisocyanate compound, polyoxyethylene glycol compounds and aromatic diamine compounds, through first synthesizing branched macromolecule monomer, then through the method for graft copolymerization, prepared the solid-solid phase-change energy-storage material with three-dimensional highly dense pectination with small molecules.Patent of invention CN 1321734C discloses a kind ofly take inorganic hydrate as core, and vinyl and bi-vinyl type free base monomer are shell, adopts the method for polymers soln precipitation polymerization to carry out the technology of synthesizing inorganic microcapsules of storing energy through phase change.In order to guarantee energy storage temperature control and the working ability of phase change material, it is skeleton propping material that investigator adopts petroleum base compound in a large number, in energy-conservation, has but ignored the protection to environment.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of biodegradable phase-changing energy storage material, phase change material prepared by the method not only has higher enthalpy of phase change, good thermal cycling and thermostability, also have biodegradable, reached the requirement of energy-conserving and environment-protective; Preparation technology is simple, and production cost is low, has a good application prospect.
The preparation method of a kind of biodegradable phase-changing energy storage material of the present invention, comprising:
(1) the polyhydroxyalkanoate macromonomer PHA-diol that two ends is to terminal hydroxy group is dissolved in organic solvent, under condition of ice bath, add successively acid binding agent and acrylate chloride, under 35 ℃ and nitrogen protection, react 6～8 hours, after reaction finishes, in ice bath, with precipitation agent, precipitate, obtain vinylformic acid polyhydroxyalkanoates-diMA; Wherein the quality of PHA-diol and the volume ratio of organic solvent are 1g: 5.28ml, and the mol ratio of PHA-diol, acrylate chloride and acid binding agent is 1: 2: 0.67～1: 2: 1; (2) polyalkylene glycol acrylate ester and above-mentioned PHA-diMA are mixed to join in 1,2-ethylene dichloride, then add ammonium persulphate, temperature is risen to 70～85 ℃, reaction 2h～24h, obtains the phase change material PHA-co-PEG with network structure; Wherein the mass ratio of polyalkylene glycol acrylate ester and PHA-diMA is 1.5～9: 1, ammonium persulphate is 1% of reaction system quality, the mass volume ratio of reaction system quality and 1,2-ethylene dichloride is 1g: 1ml, and reaction system quality is the total mass of polyalkylene glycol acrylate ester and PHA-diMA.
Polyhydroxyalkanoate in described step (1) be poly butyric ester (PHB), poly-(3-hydroxybutyrate-co-3-hydroxypentanoic acid) (PHBV), poly-(3-hydroxybutyrate-co-4-hydroxybutyric acid) [P (3HB-co-4HB)] or poly-(3-hydroxybutyrate-co-3-hydroxycaproic acid) (PHBHHx).
Organic solvent in described step (1) is DMF, 1,2-ethylene dichloride, trichloromethane or diethylene glycol dimethyl ether.
Acid binding agent in described step (1) is sodium carbonate or triethylamine.
Precipitation agent in described step (1) is ether or ethanol.
The preparation method of polyalkylene glycol acrylate ester (PEGA) is shown in patent of invention-a kind of preparation method with double-key end group phase change monomer, application publication number CN 102093552A.
Beneficial effect
(1) skeleton of phase-changing energy storage material of the present invention is polyhydroxyalkanoate, and this framework material derives from biofermentation products, the white pollution that its phase change material of preparing can not cause petroleum base material to bring;
(2) the present invention carries out modification by polyhydroxyalkanoate, makes its molecular chain two ends all have unsaturated double-bond, has improved the reactive behavior of biological polyester;
(3) phase change material of preparing not only has higher enthalpy of phase change (reaching 108J/g), and good thermal cycling and thermostability also have biodegradable, have reached the requirement of energy-conserving and environment-protective; Preparation technology is simple, and production cost is low, has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the reaction skeleton symbol of the phase change material for preparing of the inventive method;
Fig. 2 is the infrared spectra of the phase change material for preparing of the inventive method;
Fig. 3 is the nucleus magnetic hydrogen spectrum of the phase change material for preparing of the inventive method;
Fig. 4 is the crystal polarizing microscope photo of the phase change material for preparing of the inventive method;
Fig. 5 is the DSC curve of the phase change material for preparing of the inventive method;
Fig. 6 is the thermogravimetric curve of the phase change material for preparing of the inventive method.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
In ice-water bath, PHBV-diol 24.62g is dissolved in after DMF 130ml, add acid binding agent sodium carbonate 1.30g, after logical nitrogen, toward system, add acrylate chloride 2.00ml; System temperature is risen to 35 ℃, under nitrogen protection, react 8 hours; Under ice-water bath, in reaction solution, add appropriate anhydrous diethyl ether, standing 10min, decompress filter obtains vinylformic acid PHBV ester; Vinylformic acid PHBV ester 0.30g, polyalkylene glycol acrylate ester 2.70g are dissolved in to 3ml 1, in 2-ethylene dichloride, add ammonium persulphate 0.03g, at 75 ℃, react 2h, obtain biodegradable PHBV-co-PEG phase change material, its preparation feedback formula is shown in Fig. 1.
PHBV-co-PEG, after acetone extract, tests its infrared spectra (Fig. 2).By spectrogram, can be found out, PHBV-co-PEG is at 1114cm
-1there is the charateristic avsorption band of C-O group in PEG in place, at 1730cm
-1the charateristic avsorption band that occurs C=O in PHBV.Because the nucleus magnetic hydrogen spectrum (Fig. 3) of PHBV-co-PEG is found out, at 1.21-1.31ppm place, there is the nuclear-magnetism absorption peak of methyl in PHBV segment (k), at 3.64-3.65ppm, there is the nuclear-magnetism absorption peak of methylene radical in PEG segment (n).Illustrate thus and successfully prepared biodegradable PHBV-co-PEG phase change material.
Polarizing microscope photo (Fig. 4) by PEG, PHBV and PHBV-co-PEG phase change material can be found out, the crystallization in the segment of PHBV of PEG segment, and also its spherocrystal is along the continued growth of PHBV spherocrystal outer rim.To PHBV-co-PEG phase change material differential scanning (Fig. 5), research is found, the melting enthalpy of biodegradable phase change material and crystallization enthalpy are respectively 126.8J/g and 107.7J/g, and Tc is 29.79 ℃.Illustrate that thus this phase change material enthalpy is higher, Tc meets the requirement in the fields such as weaving is taken, building heat preservation, can obtain in this field well application.PHBV-co-PEG phase change material thermal weight loss (Fig. 6) is analyzed known, there is very little weightlessness in the phase change material of preparation, illustrate that this material has good thermostability before 307.5 ℃.
Embodiment 2
In ice-water bath, PHB-diol 24.62g is dissolved in after trichloromethane 130ml, add acid binding agent sodium carbonate 1.30g, after logical nitrogen, toward system, add acrylate chloride 2.00ml; System temperature is risen to 35 ℃, under nitrogen protection, react 8 hours; Under ice-water bath, in reaction solution, add appropriate dehydrated alcohol, standing 10min, decompress filter obtains vinylformic acid PHB ester; Vinylformic acid PHB ester 1.20g, polyalkylene glycol acrylate ester 1.80g are dissolved in to 3m11, in 2-ethylene dichloride, add ammonium persulphate 0.03g, at 75 ℃, react 24h, obtain biodegradable PHB-co-PEG phase change material.
Embodiment 3
In ice-water bath, P (3HB-co-4HB)-diol 24.62g is dissolved in after 1,2-ethylene dichloride 130ml, add acid binding agent triethylamine 1.14ml, after logical nitrogen, toward system, add acrylate chloride 2.00ml; System temperature is risen to 35 ℃, under nitrogen protection, react 8 hours; Under ice-water bath, in reaction solution, add appropriate anhydrous diethyl ether, standing 10min, decompress filter obtains vinylformic acid P (3HB-co-4HB) ester; Vinylformic acid P (3HB-co-4HB) ester 0.60g, polyalkylene glycol acrylate ester 2.40g are dissolved in to 3ml1, in 2-ethylene dichloride, add ammonium persulphate 0.03g, at 75 ℃, react 2min, obtain biodegradable phase change material P (3HB-co-4HB)-co-PEG copolyesters.
Embodiment 4
In ice-water bath, PHBHHx-diol 24.62g is dissolved in after DMF 130ml, add acid binding agent triethylamine 1.14ml, after logical nitrogen, toward system, add acrylate chloride 2.00ml; System temperature is risen to 35 ℃, under nitrogen protection, react 6 hours; Under ice-water bath, in reaction solution, add appropriate dehydrated alcohol, standing 10min, decompress filter obtains vinylformic acid PHBHHx ester; Vinylformic acid PHBHHx ester 0.30g, polyalkylene glycol acrylate ester 2.70g are dissolved in to 3ml 1, in 2-ethylene dichloride, add ammonium persulphate 0.03g, at 75 ℃, react 2min, obtain biodegradable phase change material PHBHHx-co-PEG copolyesters.
Claims (4)
1. a preparation method for biodegradable phase-changing energy storage material, comprising:
(1) the polyhydroxyalkanoate macromonomer PHA-diol that two ends is to terminal hydroxy group is dissolved in organic solvent, under condition of ice bath, add successively acid binding agent and acrylate chloride, under 35 ℃ and nitrogen protection, react 6～8 hours, after reaction finishes, in ice bath, with precipitation agent, precipitate, obtain vinylformic acid polyhydroxyalkanoates-diMA; Wherein the quality of PHA-diol and the volume ratio of organic solvent are 1g:5.28ml, and the mol ratio of PHA-diol, acrylate chloride and acid binding agent is 1:2:0.67～1:2:1; Wherein polyhydroxyalkanoate is poly butyric ester, poly-(3-hydroxybutyrate ester-co-3-hydroxyl valerate) PHBV, poly-(3-hydroxybutyrate ester-co-4-butyric ester) [P (3HB-co-4HB)] or poly-(3-hydroxybutyrate ester-co-3-hydroxycaproic ester) PHBHHx;
(2) polyalkylene glycol acrylate ester and above-mentioned PHA-diMA are mixed to join in 1,2-ethylene dichloride, then add ammonium persulphate, temperature is risen to 70～85 ℃, reaction 2h～24h, obtains the phase change material PHA-co-PEG with network structure; Wherein the mass ratio of polyalkylene glycol acrylate ester and PHA-diMA is 1.5～9:1, ammonium persulphate is 1% of reaction system quality, the mass volume ratio of reaction system quality and 1,2-ethylene dichloride is 1g:1ml, and reaction system quality is the total mass of polyalkylene glycol acrylate ester and PHA-diMA.
2. the preparation method of a kind of biodegradable phase-changing energy storage material according to claim 1, is characterized in that: the organic solvent in described step (1) is DMF, 1,2-ethylene dichloride, trichloromethane or diethylene glycol dimethyl ether.
3. the preparation method of a kind of biodegradable phase-changing energy storage material according to claim 1, is characterized in that: the acid binding agent in described step (1) is sodium carbonate or triethylamine.
4. the preparation method of a kind of biodegradable phase-changing energy storage material according to claim 1, is characterized in that: the precipitation agent in described step (1) is ether or ethanol.
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Effective date of registration: 20220908 Address after: 100083 30 bungalow, building 3, a 5 Xueyuan Road, Haidian District, Beijing Patentee after: PIYUE (BEIJING) TECHNOLOGY CO.,LTD. Address before: 201620 No. 2999 North Renmin Road, Songjiang new town, Songjiang District, Shanghai. Patentee before: DONGHUA University |
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