CN110938201A - Comb-shaped bio-based polycarbonate phase-change material and preparation method thereof - Google Patents
Comb-shaped bio-based polycarbonate phase-change material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a comb-shaped bio-based polycarbonate phase-change material and a preparation method thereof. The material is bio-based polycarbonate; preparation method of epoxy monomer and greenhouse gas CO synthesized by using biological hyaluronic acid2The comb-shaped bio-based polycarbonate phase-change material is prepared by polymerization and is completely biodegradable; and different sulfydryl functional monomers are grafted by double bonds in a polymer side chain, so that the multi-stage heat storage and temperature regulation can be performed on the phase-change material. The raw materials are natural, green and renewable, and the cost is low; the prepared phase-change energy storage material not only has higher phase-change enthalpy and good thermal cyclicity and thermal stability, but also has complete biodegradability, is environment-friendly and has good application prospect.
Description
Technical Field
The invention belongs to the field of preparation of phase change energy storage materials, and particularly relates to a comb-shaped bio-based polycarbonate phase change material and a preparation method thereof.
Background
Due to the rapid consumption of fossil fuel resources and the increasing global energy demand, an effective method for reducing the dependence on fossil fuels and meeting the increasing global energy demand has been sought. Phase change materials as an environmentally-friendly energy storage carrier have been listed as one of the important sequences for national energy research and development. The phase-change material is a substance which can store energy by utilizing the heat absorbed or released when the structure and the state of the phase-change material change. The comb-shaped polymer phase-change material takes a comb-shaped polymer as a structural unit, and realizes the phase-change functionalization of the polymer by changing the type of a side chain. As an organic energy storage material with a novel structure, the comb-shaped polymer phase change material has high enthalpy value, stable thermal performance and solid-solid phase transition characteristic, and thus has attracted extensive attention.
The Chinese patent CN 100595252C uses trihydroxy compounds, diisocyanate compounds, polyethylene glycol compounds and aromatic diamine compounds as raw materials, and prepares the solid-solid phase change energy storage material with three-dimensional high-density comb shape by firstly synthesizing branched chain macromonomers and then carrying out graft copolymerization with micromolecules. The invention patent CN 102516471B discloses a preparation method of a comb-shaped high polymer phase-change energy storage material, wherein, acrylic acid polyethylene glycol monomethyl ether ester is prepared by the reaction of polyethylene glycol monomethyl ether and acryloyl chloride, and the comb-shaped acrylic acid phase-change energy storage material is further synthesized by a free radical polymerization method. The invention patent CN 108285502A uses acrylonitrile and maleic anhydride or acrylic acid as raw materials to prepare a polymer main chain skeleton, and then the polymer main chain skeleton is grafted and copolymerized with n-alkanol, polyethylene glycol or n-alkyl mercaptan to prepare the comb-shaped polymer phase-change material. In order to ensure the energy storage temperature control and the processing capacity of the phase-change material, researchers mostly adopt petroleum-based compounds as framework supporting materials, and the materials do not meet the development requirements of environmental protection and low carbon while saving energy, and do not have sustainable application prospects.
Disclosure of Invention
The invention aims to solve the problems that most of phase change energy storage materials in the prior art are petroleum-based and are not environment-friendly enough, and provides a preparation method of a comb-shaped bio-based polycarbonate phase change energy storage material. The material is bio-based polycarbonate; preparation method of epoxy monomer and greenhouse gas CO synthesized by using biological hyaluronic acid2The comb-shaped bio-based polycarbonate phase-change material is prepared by polymerization (the bio-based polycarbonate is applied to the phase-change material for the first time), and is completely biodegradable; and different sulfydryl functional monomers are grafted by double bonds in a polymer side chain, so that the multi-stage heat storage can be performed on the phase-change materialAnd (5) adjusting the temperature. The raw materials are natural, green and renewable, and the cost is low; the prepared phase-change energy storage material not only has higher phase-change enthalpy and good thermal cyclicity and thermal stability, but also has complete biodegradability, is environment-friendly and has good application prospect.
The technical scheme of the invention is as follows:
the comb-shaped bio-based polycarbonate phase-change material is prepared by taking biomass epoxy fatty acid ester as a raw material and CO2Gas polymerization to obtain bio-based polycarbonate; the content of carbonate units of the bio-based polycarbonate is 20-100%, the number average molecular weight is 1.0-50.0 kg/mol, and the molecular weight distribution is 1.10-5.60; reacting the bio-based polycarbonate with a thiol functional monomer to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the molar ratio of the double bonds of the side chain of the bio-based polycarbonate to the thiol functional monomer is 1: 0.1-1.0; the phase transition temperature is-20 to 150 ℃, and the phase transition enthalpy is 30 to 320J/g;
the biomass epoxy fatty acid ester is obtained by reacting biological hyaluronic acid and epoxy chloropropane, wherein the molar ratio of the biological hyaluronic acid to the epoxy chloropropane is 1: 0.5-1.5.
The biological hyaluronic acid is carboxylic acid compounds taken from animals and plants, and is preferably selected from one or more of saturated fatty acid, monoenoic acid, dienoic acid, trienic acid, methyl substituted acid, oxidized acid, ring substituted acid, acetylenic acid and isomerized terminal olefine acid; further preferably one or more selected from the group consisting of butyric acid, lauric acid, palmitic acid, cerotic acid, oleic acid, erucic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, linoleic acid, linolenic acid, isovaleric acid, keto acid, ricinoleic acid, cyclopropenoic acid, cyclopentenic acid, furan acid, tallic acid and behenic acid.
The chemical general formula of the mercapto functional monomer is R (CH)2)nCH2SH and R are methyl, ester group, carboxylic acid, thiophene, furan and the like, wherein n is 0-25, and the compound is preferably selected from methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, and decadecyl mercaptanOne or more of hexanethiol, heptadecanethiol, octadecanethiol, furfurylthiol, 3-mercaptopropionic acid, thioglycolic acid, 2-mercaptothiophene, methyl thioglycolate, 3-mercaptobenzoic acid, 1, 2-ethanedithiol and 1, 3-propanedithiol.
The preparation method of the comb-shaped bio-based polycarbonate phase-change material comprises the following steps:
(1) reacting biological hyaluronic acid, a catalyst A and epoxy chloropropane at 50-140 ℃ for 1-6 h, cooling to 20-80 ℃, adding sodium hydroxide to react for 1-12 h, and performing column chromatography to obtain a biological epoxy monomer;
wherein the molar ratio of the biomass acid to the sodium hydroxide to the catalyst A to the epichlorohydrin is 1: 1-2: 0.001-0.01: 3-10; the catalyst A is a phase transfer catalyst and is one of polyethers, quaternary ammonium salts, cyclic crown ethers, tertiary amines and quaternary phosphonium salts; the biological hyaluronic acid is carboxylic acid compounds taken from animals and plants;
(2) putting the catalyst B into a high-pressure autoclave, vacuum drying, adding the bio-based epoxy monomer and filling CO2Reacting at 25-140 ℃ for 1-48 h, and washing in methanol to obtain bio-based polycarbonate;
wherein the catalyst B is double metal cyanide, a Salen metal complex catalyst, an organic acid zinc catalyst or a porphyrin metal complex; the molar ratio of the catalyst B to the bio-based epoxy monomer is 1: 60000-100;
(3) stirring the bio-based polycarbonate, the mercapto functional monomer, the photoinitiator and the solvent for 5-60 min in the dark, then placing the mixture in ultraviolet light for irradiating for 5-180 min, and then separating out the mixture in a precipitator to obtain the comb-shaped bio-based polycarbonate phase change material;
wherein the molar ratio of the bio-based polycarbonate to the mercapto functional monomer to the photoinitiator to the solvent is 1: 0.1-5.0: 0.01-0.001: 1-4; the photoinitiator is one or more of benzoin and derivatives, benzil, acyl phosphorus oxide, benzophenone and alkyl benzophenone; the chemical general formula of the mercapto functional monomer is R (CH)2)nCH2SH, R is methyl, ester group, carboxylic acid, thiophene or furan, and n is 0-25;
the biological acid in the step (1) is preferably one or more selected from saturated fatty acid, monoenoic acid, dienoic acid, trienoic acid, methyl substituted acid, oxidized acid, ring substituted acid, acetylenic acid and isomerized terminal olefine acid; further preferably one or more selected from the group consisting of butyric acid, lauric acid, palmitic acid, cerotic acid, oleic acid, erucic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, linoleic acid, linolenic acid, isovaleric acid, keto acid, ricinoleic acid, cyclopropenoic acid, cyclopentenic acid, furan acid, tallic acid and behenic acid.
The catalyst A in the step (1) is preferably one selected from benzyltriethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium chloride, trioctylmethylammonium chloride, cyclodextrin, pyridine, tributylamine and chain polyethylene glycol.
The mobile phase for column chromatography in the step (1) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 2-30, preferably 1: 5-20.
The catalyst B in the step (2) is preferably one or more selected from the group consisting of zinc cobalt cyanide, zinc ferricyanide, zinc nickel cyanide, SalencOx catalyst, SalencRX catalyst, SalenAlX catalyst, porphyrin cobalt catalyst, porphyrin chromium catalyst, porphyrin aluminum catalyst, zinc glutarate catalyst, zinc pimelate catalyst and zinc benzoate catalyst.
The vacuum drying temperature in the step (2) is 60-100 ℃.
CO charging in the step (2)2The pressure is 1.0-7.0 MPa.
The mercapto functional monomer in step (3) is preferably one or more selected from the group consisting of methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, ren mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, hexadecyl mercaptan, heptadecyl mercaptan, octadecyl mercaptan, furfuryl mercaptan, 3-mercaptopropionic acid, thioglycolic acid, 2-mercaptothiophene, methyl thioglycolate, 3-mercaptobenzoic acid, 1, 2-ethanedithiol and 1, 3-propanedithiol.
The photoinitiator in the step (3) is preferably one or more selected from benzoin dimethyl ether, benzoin isopropyl ether, α -hydroxyalkyl benzophenone, α -aminoalkyl benzophenone, 2, 4-dihydroxy benzophenone and diphenylethanone.
The solvent in the step (3) is one or more of tetrahydrofuran, dichloromethane, toluene and N, N-dimethylformamide.
And (3) the precipitator in the step (3) is one or more of n-hexane, diethyl ether, methanol, ethanol and water.
The invention has the substantive characteristics that:
the existing comb-shaped phase change material is prepared from petroleum-based compounds such as polyethylene glycol, diisocyanate, acrylonitrile and the like, and the prepared comb-shaped phase change material is prepared from an epoxy monomer synthesized by biological hyaluronic acid and greenhouse gas CO2Bio-based polycarbonate prepared by polymerization.
The invention has the beneficial effects that:
1. the raw materials selected by the invention are biological hyaluronic acid and greenhouse gas CO2All belong to green renewable resources; the raw material source of the biological hyaluronic acid is wide, and the biological hyaluronic acid can be suitable for various animal and plant carboxylic acid compounds such as butyric acid, palmitic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, isovaleric acid, keto acid, ricinoleic acid, cyclopropenoic acid, furan acid, talmic acid and the like, so that the cost for producing the bio-based polycarbonate phase change material is greatly reduced.
2. Double bonds still remain in the side chain of the bio-based polycarbonate prepared by the invention, and sites are provided for further modification; through click reaction of double bonds and sulfydryl, a multi-stage heat storage and temperature regulation function can be realized by using sulfydryl functional monomers with various carbon atom numbers or different functional groups, and then a series of different phase change materials are obtained, so that the application of different environments and conditions is met, for example, in the embodiment 9-17, different sulfydryl functional monomers are grafted, the phase change temperature is changed within the range of-6 to 84 ℃, and the phase change enthalpy is changed within the range of 105 to 226J/g.
3. The comb-shaped bio-based polycarbonate phase-change energy storage material prepared by the invention not only has higher phase-change enthalpy (up to 226J/g), good thermal cyclicity and thermal stability, but also has complete biodegradability (inherent attribute of carbon dioxide-based polycarbonate), accords with the development of environmental protection and low carbon, and has good application prospect.
Detailed Description
The foregoing summary of the invention is described in further detail below with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention as described above, according to the common technical knowledge and conventional means in the field, and the scope of the invention is covered.
The zinc cobalt cyanide, the zinc ferricyanide, the zinc nickel cyanide, the SalenCoX catalyst, the SalenCrX catalyst, the SalenAlX catalyst, the porphyrin cobalt catalyst, the porphyrin chromium catalyst, the porphyrin aluminum catalyst, the glutaric acid zinc catalyst, the pimelic acid zinc catalyst and the benzoic acid zinc catalyst are all materials. Among them, zinc cobalt cyanide, zinc ferricyanide and zinc nickel cyanide, preparation method reference CN 106459399A; the SalenCoX catalyst, the SalenCrX catalyst and the salenlx catalyst, preparation method reference CN 108636456A; the preparation method of the porphyrin cobalt catalyst, the porphyrin chromium catalyst and the porphyrin aluminum catalyst is disclosed in a reference CN 105111426A; the zinc glutarate catalyst, the zinc pimelate catalyst and the zinc benzoate catalyst are disclosed in a preparation method reference CN 105745017A.
Example 1
(1) 0.25mol of lauric acid, 1.65mol of epichlorohydrin and 0.0015mol of tetrabutylammonium bromide are reacted for 2 hours at 110 ℃; after the mixture is cooled to 30 ℃, 0.35mol of sodium hydroxide is added and stirred for 6 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:5 as a mobile phase to obtain a biological epoxy monomer;
(2) 0.01mol of zinc-nickel double metal cyanide is put into a high-pressure reaction kettle, after vacuum pumping is carried out for 2 hours at the temperature of 60 ℃, ice water is cooled in CO2Under protection, 18.71mol of bio-based epoxy monomer is added and 4MPa of CO is filled2Reacting for 2h at 100 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain the bio-based polycarbonate.
The performance of the prepared comb-shaped bio-based polycarbonate phase-change material is tested according to the following method:
the nuclear magnetic hydrogen spectrum is determined by Bruker 400 type nuclear magnetic resonance wavefront-specific, the scanning frequency is 400Mhz, the scanning range is 0-12ppm, and the solvent is deuterated chloroform (CDCl)3) By testing the prepared bio-based epoxy monomers1H-NMR 1.50-1.20(t, 10H), 1.75-1.50(t, 2H), 2.15-1.90(q, 2H), 2.45-2.20(t, 2H), 2.70-2.55(q, 1H), 2.90-2.75(t, 1H), 3.30-3.05(m, 1H), 3.95-3.80(q, 1H), 4.50-4.30(d, 1H); the carbonate content of the bio-based polycarbonate was 85%.
The relative molecular weights and their distributions were determined by gel permeation chromatography model PL-GPC220 of Polymer Lab, Germany, with tetrahydrofuran as the mobile phase, and the bio-based polycarbonate prepared by the test had a number average molecular weight of 15.2kg/mol and a molecular weight distribution of 2.08.
Adopting a differential scanning calorimeter, under the protection of nitrogen, the temperature testing range is-30 ℃ to 150 ℃, and the heating and cooling rate is 10 ℃/min. The melting temperature of the comb-shaped bio-based polycarbonate phase-change material prepared by the test is 55 ℃, the enthalpy value is 129J/g, the crystallization temperature is 37 ℃, and the enthalpy value is 128J/g.
Example 2
(1) 0.25mol of palmitic acid, 9.30mol of epichlorohydrin and 0.0042mol of dodecyl trimethyl ammonium chloride are reacted for 3 hours at the temperature of 100 ℃; after the mixture is cooled to 30 ℃, 0.25mol of sodium hydroxide is added and stirred for 2 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:15 as a mobile phase to obtain a biological epoxy monomer;
(2) 0.01mol of zinc cobalt cyanide catalyst is taken to be put in a high-pressure reaction kettle, after vacuum pumping is carried out for 2 hours at the temperature of 60 ℃, ice water is cooled in CO2Adding 56.83mol of bio-based epoxy monomer under protection and charging 4MPa of CO2Reacting for 10h at 70 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain the bio-based polycarbonate, wherein the content of the carbonate is 65 percent, the number average molecular weight is 9.2kg/mol, the molecular weight distribution is 3.20, the melting temperature is 75 ℃,the enthalpy value is 139J/g, the crystallization temperature is 60 ℃, and the enthalpy value is 138J/g.
Example 3
(1) 0.25mol of cerotic acid, 6.21mol of epichlorohydrin and 0.005mol of tetrabutylammonium hydrogen sulfate are reacted for 2 hours at 120 ℃; after the mixture is cooled to 80 ℃, 0.35mol of sodium hydroxide is added and stirred for 1 hour; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:20 as a mobile phase to obtain a biological epoxy monomer;
(2) 0.01mol of Salenc C catalyst is put in a high-pressure reaction kettle, after vacuum pumping is carried out for 2 hours at the temperature of 60 ℃, ice water is cooled in CO2Adding 8.35mol of bio-based epoxy monomer under protection and charging 2MPa of CO2Reacting for 4 hours at 60 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain the bio-based polycarbonate, wherein the content of the carbonate is 95%, the number average molecular weight is 7.2kg/mol, the molecular weight distribution is 1.20, the melting temperature is 95 ℃, the enthalpy value is 169J/g, the crystallization temperature is 67 ℃, and the enthalpy value is 163J/g.
Example 4
(1) 0.25mol of oleic acid, 5.37mol of epichlorohydrin and 0.0025mol of trioctylmethylammonium chloride are reacted for 2 hours at 120 ℃; after the mixture is cooled to 80 ℃, 0.29mol of sodium hydroxide is added and stirred for 2 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:15 as a mobile phase to obtain a biological epoxy monomer;
(2) 0.01mol of zinc benzoate is taken in a high-pressure reaction kettle, after vacuum pumping is carried out for 2 hours at the temperature of 60 ℃, ice water is cooled in CO2Adding 3.76mol of bio-based epoxy monomer under protection and charging 4MPa of CO2Reacting for 4 hours at 90 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain the bio-based polycarbonate, wherein the content of the carbonate is 85 percent, the number average molecular weight is 7.4kg/mol, the molecular weight distribution is 4.24, the melting temperature is 65 ℃, the enthalpy value is 123J/g, the crystallization temperature is 37 ℃, and the enthalpy value is 118J/g.
Example 5
(1) 0.25mol of 10-undecylenic acid, 8.25mol of epichlorohydrin and 0.0027mol of ammonium pyridine are reacted for 5 hours at the temperature of 80 ℃; after the mixture is cooled to 60 ℃, 0.21mol of sodium hydroxide is added and stirred for 5 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:10 as a mobile phase to obtain a biological epoxy monomer;
(2) 0.01mol of SalenCrCl catalyst is put into a high-pressure reaction kettle, after vacuum pumping is carried out for 2 hours at the temperature of 60 ℃, ice water is cooled in CO2Adding 7.45mol of bio-based epoxy monomer under protection and charging 4MPa of CO2Reacting for 6 hours at 100 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain bio-based polycarbonate, wherein the content of the carbonate is 65%, the number average molecular weight is 6.4kg/mol, and the molecular weight distribution is 2.21;
(3) stirring 0.0003mol of 2, 4-dihydroxy benzophenone, 0.01mol of bio-based polycarbonate, 0.03mol of octadecanol and 0.02mol of toluene for 45min in dark place, then exposing the mixture to ultraviolet light for 20min, precipitating and washing the mixture in methanol, and carrying out vacuum drying at 60 ℃ to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the melting temperature is 78 ℃, the enthalpy value is 143J/g, the crystallization temperature is 56 ℃, and the enthalpy value is 141J/g.
Example 6
(1) 0.25mol of 12-tridecenoic acid, 5.95mol of epichlorohydrin and 0.0079mol of tributylamine react for 5 hours at 80 ℃; after the mixture is cooled to 60 ℃, 0.35mol of sodium hydroxide is added and stirred for 7 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:20 as a mobile phase to obtain a biological epoxy monomer;
(2) taking 0.01mol of cobalt porphyrin catalyst in a high-pressure reaction kettle, vacuumizing for 2h at 60 ℃, cooling with ice water in CO2Adding 6.93mol of bio-based epoxy monomer under protection and charging 2MPa of CO2Reacting for 20 hours at 30 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain bio-based polycarbonate, wherein the content of the carbonate is 92%, the number average molecular weight is 11.2kg/mol, and the molecular weight distribution is 3.56;
(3) stirring 0.00021mol of benzoin isopropyl ether, 0.01mol of bio-based polycarbonate, 0.02mol of furfuryl mercaptan and 0.02mol of tetrahydrofuran for 35min in dark, then exposing the mixture to ultraviolet light for 30min, precipitating and washing the mixture in methanol, and carrying out vacuum drying at 60 ℃ to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the melting temperature is 56 ℃, the enthalpy value is 123J/g, the crystallization temperature is 37 ℃, and the enthalpy value is 118J/g.
Example 7
(1) 0.25mol of linoleic acid, 7.43mol of epichlorohydrin and 0.00012mol of tetrabutylammonium bromide are reacted for 2 hours at 110 ℃; after the mixture is cooled to 20 ℃, 0.26mol of sodium hydroxide is added and stirred for 6 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:15 as a mobile phase to obtain a biological epoxy monomer;
(2) 0.01mol of SalenAlCl catalyst is put in a high-pressure reaction kettle, after vacuum pumping is carried out for 2 hours at the temperature of 60 ℃, ice water is cooled in CO2Adding 5.61mol of bio-based epoxy monomer under protection and charging 5MPa of CO2Reacting for 8 hours at 80 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain bio-based polycarbonate, wherein the content of the carbonate is 63 percent, the number average molecular weight is 15.2kg/mol, and the molecular weight distribution is 2.78;
(3) stirring 0.00031mol g of benzophenone, 0.01mol of bio-based polycarbonate, 0.03mol of 3-mercaptopropionic acid and 0.02mol of tetrahydrofuran for 75min in dark, then exposing to ultraviolet light for 60min, precipitating and washing in diethyl ether, and carrying out vacuum drying at 60 ℃ to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 46 ℃, the enthalpy value is 127J/g, the crystallization temperature is 35 ℃, and the enthalpy value is 125J/g.
Example 8
(1) 0.25mol of cyclopropenoic acid, 7.22mol of epichlorohydrin and 0.00045mol of tetrabutylammonium hydrogen sulfate are reacted for 6 hours at 40 ℃; after the mixture is cooled to 40 ℃, 0.35mol of sodium hydroxide is added and stirred for 8 hours; filtering, rotary-steaming and recovering excessive epichlorohydrin, and performing column chromatography and purification by using ethyl acetate and petroleum ether with the volume ratio of 1:5 as a mobile phase to obtain a biological epoxy monomer;
(2) taking 0.01mol of porphyrin chromium catalyst in a high-pressure reaction kettle, vacuumizing for 2h at 60 ℃, cooling with ice water in CO2Under protection, 12.31mol of bio-based epoxy monomer is added and 6MPa of CO is filled2Reacting for 24h at 30 ℃ under magnetic stirring, washing the crude product with methanol, and drying in vacuum at 60 ℃ to obtain the bio-based polycarbonate containingThe amount was 56%, the number average molecular weight was 11.9kg/mol, the molecular weight distribution was 1.27;
(3) stirring 0.0009mol of α -amine alkyl benzophenone, 0.01mol of bio-based polycarbonate, 0.015mol of thioglycolic acid and 0.02mol of toluene for 45min in dark place, then exposing the mixture to ultraviolet light for 60min, precipitating and washing the mixture in methanol, and carrying out vacuum drying at 60 ℃ to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the melting temperature is 56 ℃, the enthalpy value is 163J/g, the crystallization temperature is 39 ℃, and the enthalpy value is 162J/g.
Example 9
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) keeping other conditions in the example 6(3) unchanged, and replacing furfuryl mercaptan with methyl mercaptan to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is-6 ℃, the enthalpy value is 105J/g, the crystallization temperature is-15 ℃, and the enthalpy value is 104J/g.
Example 10
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) keeping other conditions in the example 6(3) unchanged, and replacing furfuryl mercaptan with butyl mercaptan to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 13 ℃, the enthalpy value is 128J/g, the crystallization temperature is 5 ℃, and the enthalpy value is 126J/g.
Example 11
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) and (3) keeping other conditions unchanged in the embodiment 6 and (3), replacing furfuryl mercaptan with hexanethiol mercaptan to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 43 ℃, the enthalpy value is 153J/g, the crystallization temperature is 36 ℃, and the enthalpy value is 152J/g.
Example 12
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) and (3) keeping other conditions unchanged in the embodiment 6 and (3), replacing furfuryl mercaptan with octyl mercaptan to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 65 ℃, the enthalpy value is 174J/g, the crystallization temperature is 45 ℃, and the enthalpy value is 175J/g.
Example 13
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) and (3) keeping other conditions unchanged in the example 6 and the example 3, and replacing furfuryl mercaptan with dodecyl mercaptan to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 72 ℃, the enthalpy value is 192J/g, the crystallization temperature is 59 ℃, and the enthalpy value is 187J/g.
Example 14
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) keeping other conditions in the example 6(3) unchanged, replacing furfuryl mercaptan with octadecanethiol to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 84 ℃, the enthalpy value is 226J/g, the crystallization temperature is 66 ℃, and the enthalpy value is 221J/g.
Example 15
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) keeping other conditions unchanged in the embodiment 6 and 3, and replacing furfuryl mercaptan with 3-mercaptopropionic acid to obtain the comb-shaped bio-based polycarbonate phase-change material, wherein the melting temperature is 56 ℃, the enthalpy value is 156J/g, the crystallization temperature is 47 ℃, and the enthalpy value is 154J/g.
Example 16
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) keeping other conditions in the example 6(3) unchanged, and replacing furfurylthiol with thioglycolic acid to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the melting temperature is 43 ℃, the enthalpy value is 137J/g, the crystallization temperature is 37 ℃, and the enthalpy value is 129J/g.
Example 17
(1) Same as example 6 (1);
(2) same as example 6 (2);
(3) and (3) keeping other conditions unchanged in the embodiment 6 and (3), replacing furfuryl mercaptan with methyl thioglycolate to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the melting temperature is 43 ℃, the enthalpy value is 163J/g, the crystallization temperature is 29 ℃, and the enthalpy value is 161J/g.
In embodiments 1 to 8, lauric acid, palmitic acid, cerotic acid, oleic acid, 10-undecylenic acid, 12-tridecenoic acid, linoleic acid and cycloacrylic acid are respectively used as raw materials to prepare the comb-shaped bio-based polycarbonate phase change material, the source of the biological hyaluronic acid raw material is wide, and the production cost is reduced; in embodiments 9 to 17, different thiol functional monomers are grafted by polymer side chain double bonds, the temperature of the prepared phase-change material changes within a range of-6 to 84 ℃, the phase-change enthalpy changes within a range of 105 to 226J/g, the multi-stage heat storage and temperature adjustment functions are realized, a series of different phase-change materials are prepared, and the application in different environments and conditions can be met. The comb-shaped bio-based polycarbonate phase change material prepared by the invention has complete biodegradability, accords with the development of environmental protection and low carbon, and has good application prospect.
The invention is not the best known technology.
Claims (9)
1. The comb-shaped bio-based polycarbonate phase-change material is characterized in that the phase-change material firstly takes biomass epoxy fatty acid ester as a raw material and CO2Gas polymerization to obtain bio-based polycarbonate; the content of carbonate units of the bio-based polycarbonate is 20-100%, the number average molecular weight is 1.0-50.0 kg/mol, and the molecular weight distribution is 1.10-5.60; reacting the bio-based polycarbonate with a thiol functional monomer to obtain the comb-shaped bio-based polycarbonate phase change material, wherein the molar ratio of the double bonds of the side chain of the bio-based polycarbonate to the thiol functional monomer is 1: 0.1-1.0; the phase transition temperature is-20 to 150 ℃, and the phase transition enthalpy is 30 to 320J/g;
the biomass epoxy fatty acid ester is obtained by reacting biological hyaluronic acid and epoxy chloropropane, wherein the molar ratio of the biological hyaluronic acid to the epoxy chloropropane is 1: 0.5-1.5.
2. The comb-shaped bio-based polycarbonate phase change material as claimed in claim 1, wherein the bio-hyaluronic acid is carboxylic acid compound taken from animals and plants, preferably selected from one or more of saturated fatty acid, monoenoic acid, dienoic acid, trienic acid, methyl substituted acid, oxidized acid, ring substituted acid, acetylenic acid and isomerized terminal olefinic acid; further preferably one or more selected from the group consisting of butyric acid, lauric acid, palmitic acid, cerotic acid, oleic acid, erucic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, linoleic acid, linolenic acid, isovaleric acid, keto acid, ricinoleic acid, cyclopropenoic acid, cyclopentenic acid, furan acid, tallic acid and behenic acid.
3. The comb-shaped bio-based polycarbonate phase change material as claimed in claim 1, wherein the thiol-functional monomer has a chemical formula of R (CH)2)nCH2SH and R are methyl, ester group, carboxylic acid, thiophene, furan and the like, wherein n is 0-25, and the compound is preferably one or more selected from methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, ren mercaptan, decyl mercaptan, undecanol mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, hexadecyl mercaptan, heptadecyl mercaptan, octadecyl mercaptan, furfuryl mercaptan, 3-mercaptopropionic acid, thioglycolic acid, 2-mercaptothiophene, methyl thioglycolate, 3-mercaptobenzoic acid, 1, 2-ethanedithiol and 1, 3-propanedithiol.
4. The preparation method of the comb-shaped bio-based polycarbonate phase-change material as claimed in claim 1, characterized by comprising the following steps:
(1) reacting biological hyaluronic acid, a catalyst A and epoxy chloropropane at 50-140 ℃ for 1-6 h, cooling to 20-80 ℃, adding sodium hydroxide to react for 1-12 h, and performing column chromatography to obtain a biological epoxy monomer;
wherein the molar ratio of the biomass acid to the sodium hydroxide to the catalyst A to the epichlorohydrin is 1: 1-2: 0.001-0.01: 3-10; the catalyst A is a phase transfer catalyst and is one of polyethers, quaternary ammonium salts, cyclic crown ethers, tertiary amines and quaternary phosphonium salts; the biological hyaluronic acid is carboxylic acid compounds taken from animals and plants;
(2) putting the catalyst B into a high-pressure autoclave, vacuum drying, adding the bio-based epoxy monomer and filling CO2Reacting at 25-140 ℃ for 1-48 h in methanolWashing to obtain bio-based polycarbonate;
wherein the catalyst B is double metal cyanide, a Salen metal complex catalyst, an organic acid zinc catalyst or a porphyrin metal complex; the molar ratio of the catalyst B to the bio-based epoxy monomer is 1: 60000-100;
(3) stirring the bio-based polycarbonate, the mercapto functional monomer, the photoinitiator and the solvent for 5-60 min in the dark, then placing the mixture in ultraviolet light for irradiating for 5-180 min, and then separating out the mixture in a precipitator to obtain the comb-shaped bio-based polycarbonate phase change material;
wherein the molar ratio of the bio-based polycarbonate to the mercapto functional monomer to the photoinitiator to the solvent is 1: 0.1-5.0: 0.01-0.001: 1-4; the photoinitiator is one or more of benzoin and derivatives, benzil, acyl phosphorus oxide, benzophenone and alkyl benzophenone; the chemical general formula of the mercapto functional monomer is R (CH)2)nCH2SH, R is methyl, ester group, carboxylic acid, thiophene or furan, and n is 0-25;
the biological acid in the step (1) is preferably one or more selected from saturated fatty acid, monoenoic acid, dienoic acid, trienoic acid, methyl substituted acid, oxidized acid, ring substituted acid, acetylenic acid and isomerized terminal olefine acid; further preferably one or more selected from the group consisting of butyric acid, lauric acid, palmitic acid, cerotic acid, oleic acid, erucic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, linoleic acid, linolenic acid, isovaleric acid, keto acid, ricinoleic acid, cyclopropenoic acid, cyclopentenic acid, furan acid, tallic acid and behenic acid;
the mercapto functional monomer in step (3) is preferably one or more selected from the group consisting of methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, ren mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, hexadecyl mercaptan, heptadecyl mercaptan, octadecyl mercaptan, furfuryl mercaptan, 3-mercaptopropionic acid, thioglycolic acid, 2-mercaptothiophene, methyl thioglycolate, 3-mercaptobenzoic acid, 1, 2-ethanedithiol and 1, 3-propanedithiol.
5. The method for preparing comb-shaped bio-based polycarbonate phase change material as claimed in claim 4, wherein the catalyst A in step (1) is preferably one selected from benzyltriethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium chloride, trioctylmethylammonium chloride, cyclodextrin, pyridine, tributylamine and chain polyethylene glycol.
6. The preparation method of the comb-shaped bio-based polycarbonate phase change material as claimed in claim 4, wherein the mobile phase for column chromatography in step (1) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 2-30, preferably 1: 5-20.
7. The preparation method of the comb-shaped bio-based polycarbonate phase change material as claimed in claim 4, wherein the vacuum drying temperature in the step (2) is 60-100 ℃; CO charging in the step (2)2The pressure is 1.0-7.0 MPa.
8. The method for preparing the comb-shaped bio-based polycarbonate phase change material as claimed in claim 5, wherein the photoinitiator in the step (3) is one or more selected from the group consisting of benzoin dimethyl ether, benzoin isopropyl ether, α -hydroxyalkyl benzophenone, α -amine alkyl benzophenone, 2, 4-dihydroxy benzophenone and diphenylethanone;
the solvent in the step (3) is one or more of tetrahydrofuran, dichloromethane, toluene and N, N-dimethylformamide;
and (3) the precipitator in the step (3) is one or more of n-hexane, diethyl ether, methanol, ethanol and water.
9. The method for preparing comb-shaped bio-based polycarbonate phase change material as claimed in claim 4, wherein the catalyst B in step (2) is one or more selected from zinc cobalt cyanide, zinc ferricyanide, zinc nickel cyanide, SalencOx catalyst, SalencRX catalyst, SalenAlX catalyst, porphyrin cobalt catalyst, porphyrin chromium catalyst, porphyrin aluminum catalyst, zinc glutarate catalyst, zinc pimelate catalyst and zinc benzoate catalyst.
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