CN105289436A - Preparation method of inorganic hybrid nanometer phase change energy storage capsule - Google Patents
Preparation method of inorganic hybrid nanometer phase change energy storage capsule Download PDFInfo
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Abstract
The invention relates to a preparation method of an inorganic hybrid nanometer phase change energy storage capsule. The preparation method is characterized by comprising the following steps that 1 to 10 parts of amphipathic ternary molecular brush polymers are dissolved in 1 to 40 parts of methylene dichloride and 1 to 40 parts of organic phase change materials; the mixture is dripped into 100 to 400 parts of water; the stirring is performed at 28 DEG C to 32 DEG C to obtain mixed liquid; the mixed liquid is heated and stirred; the heating temperature is 48 DEG C to 52 DEG C; the stirring time is 28 to 32 minutes; then, after heat-insulation stirring is performed for 28 to 32 minutes, the mixture is cooled to the normal temperature to obtain oil-in-water nanometer phase change material emulsion; 1 to 5 parts of metal ions are added into the oil-in-water nanometer phase change material emulsion; after the reaction is performed for 28 to 32 minutes, 1 to 5 parts of metal ion precipitating agents are added; inorganic hybrid cross-linking reaction is performed for 1 to 2 hours at the normal temperature to obtain the inorganic hybrid nanometer phase change energy storage capsule with a stable structure. The preparation method has the advantages that inorganic nanoparticles are introduced into the surface layer of the phase change energy storage capsule, and the thermal conductivity and the stability of the phase change energy storage capsule are improved.
Description
Technical field
The invention belongs to phase-changing energy storage material and self assembly polymeric material field, be specifically related to the preparation method of inorganic hybrid nano phase-change energy storage capsule.
Background technology
The world today, energy shortage problem has become one of major issue that the whole world faces.Due to the continuous consumption of non-renewable energy resources and exhaustion more and more outstanding, improve energy utilization rate and exploitation regenerative resource and become important topic faced by the current mankind.In order to improve energy utilization rate, the mankind propose the concept of green building.Green building refers in the life cycle management of building, economizes on resources to greatest extent, provides healthy and is suitable for, effective use and the building with natural harmony symbiosis.Green building one of them the most key problem be the regulation and control problem to indoor temperature, reducing air-conditioning system can maintain indoor temperature as far as possible.In order to better realize the regulation and control of indoor temperature, phase-changing energy-storing building materials obtains unprecedented development.Phase-changing energy-storing building materials is a kind of hot functional composite material, energy can be stored with the form of latent heat of phase change, realizes the conversion of energy between different time and locus.Such as, the heat energy transfer higher daytime was discharged to night, human settlement is improved, and absorb and release heat process in, own temperature changes hardly, thus formation indoor temperature relative equilibrium.The normal phase-changing energy-storing building materials used has inorganic phase-changing material and organic phase change material at present.Though inorganic phase-changing material has the advantage that thermal conductivity factor is high and phase transformation heat content is large, it there is surfusion and the strong defect of corrosivity limits its application.Organic phase change material, as a kind of desirable low temperature solid-liquid phase change material, is applicable to the application of air conditioning system for building, has energy storage density large, cheap, little to container corrosion, and preparation is simple, large area can be used for energy storage.Normal alkane C
nh
2ncarbochain when rising to 24 from 14, the melting temperature of normal alkane is increased to 50.6 DEG C from 5.5 DEG C, and such normal alkane melting temperature is very suitable for building temperature adjusting.
Organic phase change material phase transition process occurs to become solid-state phase in version from solid state into liquid state or liquid state, easily causes liquid seepage, is separated, the problem such as volumetric expansion and poor heat stability during use.In order to address these problems, current mainstream development direction utilizes microcapsules technology at the film of the coated one deck stable performance of normal alkane microparticle surfaces, can effectively address these problems.But microcapsules are due to size comparatively large (1 ~ 2000 μm), and density is comparatively light, not easily reaches homogeneous with standard aqueous coating on market and mixes, poor storage stability, easily floating transport phenomena occurs.Large-sized microcapsules are added into the combination property that standard aqueous coating also can affect coating simultaneously, and as the adhesive force of film, fineness, the performances such as viscosity all can be influenced.Therefore, need the phase-change energy storage capsule preparing Nano grade to improve its performance.Usually, Nano capsule is of a size of 1 ~ 1000nm, several order of magnitude less of the size (1 ~ 2000 μm) of microcapsules.Nano capsule has higher specific area relative to microcapsules, shows special nano effect.Nano phase change energy storage capsule has more violent Brownian movement relative to micron phase-change energy storage capsule, is enough to the impact overcoming gravitational field, not easily occurs layering and sedimentation, and keep dispersity, anti-freezing cumulative power is strong.In order to improve stability and the thermal conductivity of nanometer organic phase-change energy storage capsule further, inorganic hybrid nano particle can be introduced on nanometer organic phase-change energy storage capsule top layer, and then promote stability and the thermal conductivity of nanometer organic phase-change energy storage capsule.But there be limited evidence currently of report is about the technology of preparing of inorganic hybrid nano organic phase-change energy storage capsule.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and the preparation method that a kind of inorganic hybrid nano organic phase-change energy storage capsule is provided; owing to adopting inorganic hybrid nano particle parcel organic phase change material; not only protect organic phase change material in the anti-phenomenon that leaks outside of phase transition process; inorganic nano-particle has higher thermal conductivity factor simultaneously, improves the heat exchanger effectiveness of organic phase change material.
In order to achieve the above object, technical scheme of the present invention is achieved in that it is a kind of preparation method of inorganic hybrid nano phase-change energy storage capsule, it is characterized in that comprising the steps:
Step one
The amphipathic ternary molecular brush polymer of 1 ~ 10 part is dissolved in the organic phase change material of the carrene of 1 ~ 40 part and 1 ~ 40 part, in the water of instillation 100 ~ 400,28
oc ~ 32
ostir under C and obtain mixed liquor, then heat mixed liquor and stir, heating-up temperature is 48
oc ~ 52
oc, mixing time is 28 ~ 32 minutes, and then insulated and stirred is after 28 ~ 32 minutes, under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The metal ion of 1 ~ 5 part is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 28 ~ 32 minutes, frame enters 1 ~ 5 part of precipitation by metallic ion agent again, carries out down inorganic hybrid cross-linked reaction 1 ~ 2 hour at normal temperatures, obtains constitutionally stable inorganic hybrid nano phase-change energy storage capsule;
More than be mass fraction.
Described organic phase change material can be the one in normal alkane, paraffin, Tissuemat E, and melting range is 0
oc ~ 120
oc, organic phase change material and water quality are than being 1:3 ~ 10.
The particle diameter of described inorganic hybrid nano phase-change energy storage capsule is 20 ~ 500nm.
The general formula of described amphipathic ternary molecular brush polymer: A-g-(B-r-C-r-D), wherein, g represents grafting, r represents random distribution, A representation polymer main chain, B represents lipophile side chain and compatible with organic phase change material, C representative can with the polymer side chain of metal ion generation chelating, D represents hydrophilic high mol side chain, and side chain B, C and D are grafted on main chain A randomly;
The polymer of described main chain A is the one in poly (glycidyl methacrylate) (PGMA), polyglycidyl acrylate (PGA);
Described lipophile side chain B is the one in octadecane, eicosane, pentacosane and melissane, and lipophile side chain must be completely compatible with organic phase change material;
Described can be polyacrylamide (PAM) with the polymer of the polymer side chain C of metal ion generation chelating;
The polymer of described hydrophilic high mol side chain D is polyethylene glycol (PEG);
Described metal ion is calcium ion (Ca
2+), copper ion (Cu
2+), lead ion (Pb
2+), zinc ion (Zn
2+), ferrous ion (Fe
2+) in one.
Described precipitation by metallic ion agent is sodium carbonate, the one in sodium sulfide.
The degree of polymerization of described main chain A is 5 ~ 100, and the degree of polymerization of described side chain B, C, D is 10 ~ 200, and the percent grafting of side chain B, C, D is 10 ~ 100%.
The step of the synthesis of described amphipathic ternary molecular brush polymer is as follows:
Step one synthesizes main chain A
Adopt atom transition free radical polymerization reaction to carry out initiated polymerization synthesis main chain to monomer, then azide functionalization is carried out to main chain, obtain main polymer chain;
Step 2 synthesis side chain B, C, D
Transfer Radical Polymerization is adopted to carry out initiated polymerization to monomer or directly carry out chemical modification synthesis side chain B, C, D to side chain, introduce in building-up process simultaneously alkynyl functional group or to synthesis after side chain carry out alkynyl functionalization, obtain hydrophilic, oleophylic or can with the side chain polymer of metal ion generation chelating;
Step 3 synthesizing amphipathic ternary molecular brush polymer
The side chain D of the main chain A of 5 ~ 20, the side chain B of 1 ~ 40 part, 1 ~ 40 part side chain C and 1 ~ 40 part is dissolved in the dimethyl formamide (DMF) of 100 ~ 500 parts, carry out the reaction of a step " nitrine-alkynyl " click chemistry in the presence of a catalyst, obtain final products and amphipathic ternary molecular brush polymer.
In the technical program, the A of main chain described in step one adopts controllable free radical polymerization process; Functionalization described in step one introduces azido group on each unit of main chain; The A of main chain described in step one is P (GMA-N
3) or P (GA-N
3); Side chain described in step 2 adopts controllable free radical polymerization process and end-functionalization modification and obtains; Introducing functional group described in step 2 introduces alkynyl group in the end of side chain; The side chain of hydrophilic high mol described in step 2 D is PEG-CoCH; The side chain of lipophile described in step 2 B is C
17h
35-CO-O-CH
2-CoCH, C
19h
39-CO-O-CH
2-CoCH, C
24h
49-CO-O-CH
2-CoCH or C
29h
59-CO-O-CH
2-CoCH; Can be PAM-CoCH with the side chain C of metal ion generation chelating described in step 2.
In the technical program, catalyst described in step 3 is the one in following combination: copper sulphate and ascorbic acid, or cuprous bromide and pentamethyl-diethylenetriamine, or cuprous bromide and 2,2'-bipyridyl.
The present invention compared with prior art, has following advantage and effect:
(1) the present invention's phase-change energy storage capsule of adopting inorganic hybrid cross-linked construction structure stable, solves organic phase change material problem of leakage in phase transition process;
(2) the present invention has prepared inorganic hybrid nano phase-change energy storage capsule, and the shell of nano phase change energy storage capsule is constructed by inorganic nano-particle, improves the heat transfer efficiency of phase-change energy storage capsule.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.It should be noted that at this, the explanation for these embodiments understands the present invention for helping, but does not form limitation of the invention.Number involved in following examples is all mass fractions.
embodiment one
First synthesizing amphipathic ternary molecular brush polymer, is prepared by following steps:
Step one P (GMA-N
3) synthesis of main chain A
Get the 2-isobutyl ethyl bromide initator of 2 parts, 200 parts GMA (GMA), part diphenyl ether of 200,3 parts CuBr and 2 part N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), under nitrogen protection, temperature controls at 30 DEG C; carry out ATRP and react 1 hour, obtains the poly (glycidyl methacrylate) (PGMA) that the degree of polymerization (DP) is 30;
Get poly (glycidyl methacrylate) (PGMA) (DP=30) of 100 parts, the NaN of 50 parts
3and the dimethyl formamide of 300 parts (DMF), temperature controls at 50 DEG C, reacts 24 hours, obtains P (GMA-N
3) main chain;
The synthesis of step 2 three kinds of side chains
The synthesis of hydrophilic high mol side chain D: the carrene getting the mono methoxy polyethylene glycol (Mn=5000) of 100 parts, the 2-propynyl acetic acid of 40 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) of 40 parts and 400 parts, temperature controls at 30 DEG C, react 24 hours, obtain hydrophilic high mol side chain D and PEG-CoCH(DP=114 that the degree of polymerization (DP) is 120);
The synthesis of lipophile side chain B: the carrene getting the eicosyl acid of 30 parts, the 2-propynyl ethanol of 30 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl) of 40 parts and 300 parts, normal-temperature reaction 30 hours, obtain lipophile side chain B and C that the degree of polymerization (DP) is 120
19h
39-CO-O-CH
2-CoCH;
Can with the synthesis of the side chain C of metal ion generation chelating: get the bromo acid propynyl ester initator of 2 parts, the acrylamide (AM) of 100 parts, the dimethyl formamide (DMF) of 200 parts, 2 parts of frerrous chloride (FeCl
2) and the triphenyl phosphorus (PPh of 2 parts
3), under nitrogen protection, temperature controls at 80 DEG C, carries out ATRP and reacts 8 hours, obtain the degree of polymerization (DP) be 120 can with side chain C and PAM-CoCH of metal ion generation chelating;
The amphipathic ternary molecular brush polymer of step 3 and PGMA-g-(C
19h
39-r-PAM-r-PEG) synthesis
Get the P (GMA-N of 8 parts
3), the PEG-CoCH of 20 parts, the C of 5 parts
19h
39-CO-O-CH
2the PAM-CoCH of-CoCH and 5 part is dissolved in the dimethyl formamide (DMF) of 300 parts, then adds the CuSO of 1 part
4and 5 parts of sodium ascorbates, temperature controls at 30 DEG C, reacts 24 hours, obtains amphipathic ternary molecular brush polymer PGMA-g-(C
19h
39-r-PAM-r-PEG), PEG, PAM, C
19h
39the percent grafting of side chain is respectively 20%, 5%, 30%.
Inorganic hybrid nano phase-change energy storage capsule of the present invention, adopt emulsion self-assembly method to obtain, its preparation method comprises the following steps:
Step one
Get the amphipathic ternary molecular brush PGMA-g-(C of 1 part
19h
39-r-PAM-r-PEG) be dissolved in the paraffin (fusing point is 70 DEG C) of the carrene of 5 parts and 10 parts, temperature controls at 30 DEG C, and mechanical agitation 1000rpm is mixed to get mixed liquor, will be dissolved with PGMA-g-(C
19h
39-r-PAM-r-PEG) mixed liquor to instill in the water of 100 parts and to stir 30 minutes, heat while stirring, heating-up temperature is 50 DEG C, then is incubated 30 minutes, under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The calcium chloride of 2 parts is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 30 minutes, add the calcium carbonate of 4 parts, carry out inorganic hybrid cross-linked reaction 2 hours at normal temperatures, obtain the inorganic hybrid nano phase-change energy storage capsule of rock-steady structure, its particle diameter of Dynamic Light Scattering Determination (D
h) be 300nm.
embodiment two
First synthesizing amphipathic ternary molecular brush polymer, is prepared by following steps:
Step one P (GA-N
3) synthesis of main chain A
Get the 2-isobutyl ethyl bromide initator of 2 parts, 200 parts glycidyl acrylate (GA), part diphenyl ether of 200,3 parts CuBr and 2 part N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), under nitrogen protection, temperature controls 30 DEG C time; carry out ATRP and react 2 hours, obtains the poly (glycidyl methacrylate) (PGA) that the degree of polymerization (DP) is 60;
Get the PGA(DP=60 of 100 parts), the NaN of 50 parts
3and the dimethyl formamide of 300 parts (DMF), temperature controls at 50 DEG C, reacts 24 hours, obtains P (GMA-N
3) main chain;
The synthesis of step 2 three kinds of side chains
The synthesis of hydrophilic high mol side chain D: the carrene getting the mono methoxy polyethylene glycol (Mn=2000) of 100 parts, the 2-propynyl acetic acid of 40 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) of 40 parts and 400 parts, temperature controls at 30 DEG C, react 24 hours, obtain hydrophilic high mol side chain D and PEG-CoCH that the degree of polymerization (DP) is 80;
The synthesis of lipophile side chain B: get the melissyl acid of 30 parts, the 2-propynyl ethanol of 30 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl) of 40 parts and the carrene of 300 parts, normal-temperature reaction 30 hours, obtains lipophile side chain B and C that the degree of polymerization (DP) is 80
29h
59-CO-O-CH
2-CoCH;
Can with the synthesis of the side chain C of metal ion generation chelating: get the bromo acid propynyl ester initator of 2 parts, the acrylamide (AM) of 200 parts, the dimethyl formamide (DMF) of 200 parts, 2 parts of frerrous chloride (FeCl
2) and the triphenyl phosphorus (PPh of 2 parts
3), under nitrogen protection, temperature controls at 80 DEG C, carries out ATRP and reacts 8 hours, obtain the degree of polymerization (DP) be 100 can with side chain C and PAM-CoCH of metal ion generation chelating;
The amphipathic ternary molecular brush PGA-g-of step 3 (C
24h
49-r-PAM-r-PEG) synthesis
Get the P (GA-N of 10 parts
3), the PEG-CoCH of 10 parts, the C of 8 parts
24h
49-CO-O-CH
2the PAM-CoCH of-CoCH and 10 part is dissolved in the dimethyl formamide (DMF) of 400 parts, then adds the CuSO of 1 part
4and 5 parts of sodium ascorbates, temperature controls at 30 DEG C, reacts 30 hours, obtains amphipathic ternary molecular brush polymer PGA-g-(C
24h
49-r-PAM-r-PEG), PEG, PAM, C
24h
49the percent grafting of side chain is respectively 30%, 8%, 10%.
Inorganic hybrid nano phase-change energy storage capsule of the present invention, adopt emulsion self-assembly method to obtain, its preparation method comprises the following steps:
Step one
Get the amphipathic ternary molecular brush PGA-g-(C of 5 parts
24h
49-r-PAM-r-PEG) be dissolved in the NSC 77136 of the carrene of 5 parts and 30 parts, temperature controls at 32 DEG C, under mechanical agitation 1000rpm, will be dissolved with PGA-g-(C
24h
49-r-PAM-r-PEG) mixed solution to instill in the water of 400 parts and to stir 28 minutes, heat when stirring, heating-up temperature is 52 DEG C, is then incubated 28 minutes, then under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The plumbi nitras of 2 parts is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 28 minutes, add the vulcanized sodium of 3 parts, carry out inorganic hybrid cross-linked reaction 1.5 hours at normal temperatures, obtain the inorganic hybrid nano phase-change energy storage capsule of rock-steady structure, its particle diameter of Dynamic Light Scattering Determination (D
h) be 400nm.
embodiment three
First synthesizing amphipathic ternary molecular brush polymer, is prepared by following steps:
Step one P (GA-N
3) synthesis of main chain A
Get the 2-isobutyl ethyl bromide initator of 2 parts, 200 parts glycidyl acrylate (GA), part diphenyl ether of 300,3 parts CuBr and 2 part N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), under nitrogen protection, temperature controls at 30 DEG C; carry out ATRP and react 3 hours, obtains the poly (glycidyl methacrylate) (PGA) that the degree of polymerization (DP) is 90;
Get the PGA(DP=90 of 100 parts), the NaN of 50 parts
3and the dimethyl formamide of 300 parts (DMF), 50 DEG C of reactions 24 hours, obtain P (GMA-N
3) main chain.
The synthesis of step 2 three kinds of side chains
The synthesis of hydrophilic high mol side chain D: the carrene getting the mono methoxy polyethylene glycol (Mn=2000) of 100 parts, the 2-propynyl acetic acid of 40 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) of 40 parts and 400 parts, temperature controls at 30 DEG C, react 24 hours, obtain the PEG-CoCH that the degree of polymerization (DP) is 46 hydrophilic high mol side chain D;
The synthesis of oleophylic side chain B: get the pentacosyl acid of 30 parts, the 2-propynyl ethanol of 30 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl) of 40 parts and the carrene of 300 parts, normal-temperature reaction 30 hours, obtains oleophylic side chain B and C that the degree of polymerization is 70
29h
59-CO-O-CH
2-CoCH;
Can with the synthesis of the side chain C of metal ion generation chelating: get the bromo acid propynyl ester initator of 2 parts, the acrylamide (AM) of 120 parts, the dimethyl formamide (DMF) of 200 parts, 2 parts of frerrous chloride (FeCl
2) and the triphenyl phosphorus (PPh of 2 parts
3), under nitrogen protection, temperature controls at 80 DEG C, carries out ATRP and reacts 4 hours, obtain the degree of polymerization (DP) be 60 can with side chain C and PAM-CoCH of metal ion generation chelating;
The amphipathic ternary molecular brush PGA-g-of step 3 (C
29h
59-r-PAM-r-PEG) synthesis
Get the P (GA-N of 15 parts
3), the PEG-CoCH of 15 parts, the C of 5 parts
29h
59-CO-O-CH
2the PAM-CoCH of-CoCH and 15 part is dissolved in the dimethyl formamide (DMF) of 450 parts, then adds the CuSO of 1 part
4and 5 parts of sodium ascorbates, temperature controls at 30 DEG C, reacts 30 hours, obtains amphipathic ternary molecular brush polymer PGA-g-(C
29h
59-r-PAM-r-PEG), PEG, PAM, C
29h
59the percent grafting of side chain is respectively 15%, 5%, 15%.
Inorganic hybrid nano phase-change energy storage capsule of the present invention, adopt emulsion self-assembly method to obtain, its preparation method comprises the following steps:
Step one
Get the amphipathic ternary molecular brush PGA-g-(C of 7 parts
29h
59-r-PAM-r-PEG) be dissolved in the Tissuemat E (fusing point: 80 DEG C) of the carrene of 10 parts and 30 parts, temperature controls at 28 DEG C, under mechanical agitation 1000rpm, will be dissolved with PGA-g-(C
29h
59-r-PAM-r-PEG) mixed solution to instill in the water of 200 parts and to stir 28 minutes, heat when stirring, heating-up temperature is 48 DEG C, is then incubated 28 minutes, under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The zinc sulfate of 4 parts is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 32 minutes, add the vulcanized sodium of 4 parts, carry out inorganic hybrid cross-linked reaction 1 hour at normal temperatures, obtain the inorganic hybrid nano phase-change energy storage capsule of rock-steady structure, its particle diameter of Dynamic Light Scattering Determination (D
h) be 200nm.
embodiment four
First synthesizing amphipathic ternary molecular brush polymer, is prepared by following steps:
Step one P (GMA-N
3) synthesis of main chain A
Get the 2-isobutyl ethyl bromide initator of 2 parts, 400 parts GMA (GMA), part diphenyl ether of 200,3 parts CuBr and 2 part N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), under nitrogen protection, temperature controls at 30 DEG C; carry out ATRP and react 4 hours, obtains the poly (glycidyl methacrylate) (PGMA) that the degree of polymerization (DP) is 100;
Get the PGMA(DP=80 of 100 parts), the NaN of 50 parts
3and the dimethyl formamide of 300 parts (DMF), temperature controls at 50 DEG C, reacts 24 hours, obtains P (GMA-N
3), as main chain;
The synthesis of step 2 three kinds of side chains
The synthesis of hydrophilic high mol side chain D: the carrene getting the mono methoxy polyethylene glycol (Mn=5000) of 100 parts, the 2-propynyl acetic acid of 40 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) of 40 parts and 400 parts, temperature controls at 30 DEG C, react 24 hours, obtain the hydrophilic high mol side chain DPEG-CoCH that the degree of polymerization (DP) is 114;
The synthesis of lipophile side chain B: get the pentacosyl acid of 30 parts, the 2-propynyl ethanol of 30 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl) of 40 parts and the carrene of 300 parts, normal-temperature reaction 30 hours, obtains lipophile side chain B and C that the degree of polymerization (DP) is 110
24h
49-CO-O-CH
2-CoCH;
Can with the synthesis of the side chain C of metal ion generation chelating: get the bromo acid propynyl ester initator of 2 parts, the acrylamide (AM) of 100 parts, the dimethyl formamide (DMF) of 200 parts, 2 parts of frerrous chloride (FeCl
2) and the triphenyl phosphorus (PPh of 2 parts
3), under nitrogen protection, temperature controls at 80 DEG C, carries out ATRP and reacts 4 hours, obtain the degree of polymerization (DP) be 30 can with side chain C and PAM-CoCH of metal ion generation chelating;
The amphipathic ternary molecular brush PGMA-g-of step 3 (C
24h
49-r-PAM-r-PEG) synthesis
Get the P (GMA-N of 20 parts
3), the PEG-CoCH of 25 parts, the C of 9 parts
24h
49-CO-O-CH
2the PAM-CoCH of-CoCH and 15 part is dissolved in the dimethyl formamide (DMF) of 500 parts, then adds the CuSO of 1 part
4and 5 parts of sodium ascorbates, temperature controls at 30 DEG C, reacts 24 hours, obtains amphipathic ternary molecular brush polymer PGMA-g-(C
24h
49-r-PAM-r-PEG), PEG, PAM, C
24h
49the percent grafting of side chain is respectively 25%, 15%, 14%.
Inorganic hybrid nano phase-change energy storage capsule of the present invention, adopt emulsion self-assembly method to obtain, its preparation method comprises the following steps:
Step one
Get the amphipathic ternary molecular brush PGMA-g-(C of 7 parts
24h
49-r-PAM-r-PEG) be dissolved in the NSC 77136 of the carrene of 20 parts and 40 parts, temperature controls at 30 DEG C, under mechanical agitation 1000rpm, will be dissolved with PGMA-g-(C
24h
49-r-PAM-r-PEG) mixed solution to instill in the water of 200 parts and to stir 30 minutes, heat when stirring, heating-up temperature is 52 DEG C, is then incubated 30 minutes, under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The copper sulphate of 2 parts is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 30 minutes, add the vulcanized sodium of 2 parts, carry out inorganic hybrid cross-linked reaction 2 hours at normal temperatures, obtain the inorganic hybrid nano phase-change energy storage capsule of rock-steady structure, its particle diameter of Dynamic Light Scattering Determination (D
h) be 100nm.
embodiment five
First synthesizing amphipathic ternary molecular brush polymer, is prepared by following steps:
Step one P (GMA-N
3) synthesis of main chain A
Get the 2-isobutyl ethyl bromide initator of 2 parts, 400 parts GMA (GMA), part diphenyl ether of 200,3 parts CuBr and 2 part N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), under nitrogen protection, temperature controls at 30 DEG C; carry out ATRP and react 1 hour, obtains the poly (glycidyl methacrylate) (PGMA) that the degree of polymerization (DP) is 50;
Get the PGMA(DP=50 of 100 parts), the NaN of 50 parts
3and the dimethyl formamide of 300 parts (DMF), temperature controls at 50 DEG C, reacts 24 hours, obtains P (GMA-N
3), as main chain;
The synthesis of step 2 three kinds of side chains
The synthesis of hydrophilic high mol side chain D: the carrene getting the mono methoxy polyethylene glycol (Mn=5000) of 100 parts, the 2-propynyl acetic acid of 40 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) of 40 parts and 400 parts, temperature controls at 30 DEG C, react 24 hours, obtain hydrophilic high mol side chain D and PEG-CoCH that the degree of polymerization (DP) is 120;
The synthesis of lipophile side chain B: get the melissyl acid of 30 parts, the 2-propynyl ethanol of 30 parts, the DMAP (DMAP) of 40 parts, 1-(3-the dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl) of 40 parts and the carrene of 300 parts, normal-temperature reaction 30 hours, obtain the degree of polymerization for (DP) be 130 lipophile side chain B and C
29h
59-CO-O-CH
2-CoCH;
Can with the synthesis of the side chain C of metal ion generation chelating: get the bromo acid propynyl ester initator of 2 parts, the acrylamide (AM) of 100 parts, the dimethyl formamide (DMF) of 200 parts, 2 parts of frerrous chloride (FeCl
2) and the triphenyl phosphorus (PPh of 2 parts
3), under nitrogen protection, temperature controls at 80 DEG C, carries out ATRP and reacts 10 hours, obtain the degree of polymerization (DP) be 90 can with side chain C and PAM-CoCH of metal ion generation chelating;
The amphipathic ternary molecular brush PGMA-g-of step 3 (C
29h
59-r-PAM-r-PEG) synthesis
Get the P (GMA-N of 5 parts
3), the PEG-CoCH of 30 parts, the C of 7 parts
29h
59-CO-O-CH
2the PAM-CoCH of-CoCH and 10 part is dissolved in the dimethyl formamide (DMF) of 200 parts, then adds the CuSO of 1 part
4and 5 parts of sodium ascorbates, temperature controls at 30 DEG C, reacts 24 hours, obtains amphipathic ternary molecular brush polymer PGMA-g-(C
29h
59-r-PAM-r-PEG), PEG, PAM, C
29h
59the percent grafting of side chain is respectively 27%, 6%, 10%.
Inorganic hybrid nano phase-change energy storage capsule of the present invention, adopt emulsion self-assembly method to obtain, its preparation method comprises the following steps:
Step one
Get the amphipathic ternary molecular brush PGMA-g-(C of 3 parts
29h
59-r-PAM-r-PEG) be dissolved in the paraffin (fusing point: 90 DEG C) of the carrene of 20 parts and 40 parts, temperature controls at 30 DEG C, under mechanical agitation 1000rpm, will be dissolved with PGMA-g-(C
29h
59-r-PAM-r-PEG) mixed solution to instill in the water of 150 parts and to stir 30 minutes, heat while stirring, heating-up temperature is 50 DEG C, is then incubated 30 minutes, under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The frerrous chloride of 2 parts is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 30 minutes, add the vulcanized sodium of 2 parts, carry out inorganic hybrid cross-linked reaction 1 hour at normal temperatures, obtain the inorganic hybrid nano phase-change energy storage capsule of rock-steady structure, its particle diameter of Dynamic Light Scattering Determination (D
h) be 150nm.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for inorganic hybrid nano phase-change energy storage capsule, is characterized in that comprising the steps:
Step one
The amphipathic ternary molecular brush polymer of 1 ~ 10 part is dissolved in the organic phase change material of the carrene of 1 ~ 40 part and 1 ~ 40 part, in the water of instillation 100 ~ 400,28
oc ~ 32
ostir under C and obtain mixed liquor, then heat mixed liquor and stir, heating-up temperature is 48
oc ~ 52
oc, mixing time is 28 ~ 32 minutes, and then insulated and stirred is after 28 ~ 32 minutes, under being cooled to normal temperature, obtains " oil-in-water " nano phase change material emulsion;
Step 2
The metal ion of 1 ~ 5 part is added in above-mentioned " oil-in-water " nano phase change material emulsion, react after 28 ~ 32 minutes, add 1 ~ 5 part of precipitation by metallic ion agent again, carry out down inorganic hybrid cross-linked reaction 1 ~ 2 hour at normal temperatures, obtain constitutionally stable inorganic hybrid nano phase-change energy storage capsule;
More than be mass fraction.
2. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 1, is characterized in that described organic phase change material can be the one in normal alkane, paraffin, Tissuemat E, and melting range is 0
oc ~ 120
oC, organic phase change material and water quality are than being 1:3 ~ 10.
3. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 1, is characterized in that the particle diameter of described inorganic hybrid nano phase-change energy storage capsule is 20 ~ 500nm.
4. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 1, it is characterized in that the general formula of described amphipathic ternary molecular brush polymer: A-g-(B-r-C-r-D), wherein, g represents grafting, and r represents random distribution, A representation polymer main chain, B represents lipophile side chain and compatible with organic phase change material, C representative can with the polymer side chain of metal ion generation chelating, D represents hydrophilic high mol side chain, and side chain B, C and D are grafted on main chain A randomly;
The polymer of described main chain A is the one in poly (glycidyl methacrylate) (PGMA), polyglycidyl acrylate (PGA);
Described lipophile side chain B is the one in octadecane, eicosane, pentacosane and melissane, and lipophile side chain must be completely compatible with organic phase change material;
Described can be polyacrylamide (PAM) with the polymer of the polymer side chain C of metal ion generation chelating;
The polymer of described hydrophilic high mol side chain D is polyethylene glycol (PEG).
5. the preparation method of the inorganic hybrid nano phase-change energy storage capsule according to claim 1 or 4, is characterized in that described metal ion is calcium ion (Ca
2+), copper ion (Cu
2+), lead ion (Pb
2+), zinc ion (Zn
2+), ferrous ion (Fe
2+) in one.
6. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 1, is characterized in that described precipitation by metallic ion agent is sodium carbonate, the one in sodium sulfide.
7. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 4, it is characterized in that the degree of polymerization of described main chain A is 5 ~ 100, the degree of polymerization of described side chain B, C, D is 10 ~ 200, and the percent grafting of side chain B, C, D is 10 ~ 100%.
8. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 4, is characterized in that the step of the synthesis of described amphipathic ternary molecular brush polymer is as follows:
Step one synthesizes main chain A
Adopt atom transition free radical polymerization reaction to carry out initiated polymerization synthesis main chain to monomer, then azide functionalization is carried out to main chain, obtain main polymer chain;
Step 2 synthesis side chain B, C, D
Transfer Radical Polymerization is adopted to carry out initiated polymerization to monomer or directly carry out chemical modification synthesis side chain B, C, D to side chain, introduce in building-up process simultaneously alkynyl functional group or to synthesis after side chain carry out alkynyl functionalization, obtain hydrophilic, oleophylic or can with the side chain polymer of metal ion generation chelating;
Step 3 synthesizing amphipathic ternary molecular brush polymer
The side chain D of the main chain A of 5 ~ 20, the side chain B of 1 ~ 40 part, 1 ~ 40 part side chain C and 1 ~ 40 part is dissolved in the dimethyl formamide (DMF) of 100 ~ 500 parts, carry out the reaction of a step " nitrine-alkynyl " click chemistry in the presence of a catalyst, obtain final products and amphipathic ternary molecular brush polymer.
9. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 7, is characterized in that the A of main chain described in step one adopts controllable free radical polymerization process; Functionalization described in step one introduces azido group on each unit of main chain; The A of main chain described in step one is P (GMA-N
3) or P (GA-N
3); Side chain described in step 2 adopts controllable free radical polymerization process and end-functionalization modification and obtains; Introducing functional group described in step 2 introduces alkynyl group in the end of side chain; The side chain of hydrophilic high mol described in step 2 D is PEG-CoCH; The side chain of lipophile described in step 2 B is C
17h
35-CO-O-CH
2-CoCH, C
19h
39-CO-O-CH
2-CoCH, C
24h
49-CO-O-CH
2-CoCH or C
29h
59-CO-O-CH
2-CoCH; Can be PAM-CoCH with the side chain C of metal ion generation chelating described in step 2.
10. the preparation method of inorganic hybrid nano phase-change energy storage capsule according to claim 7, it is characterized in that catalyst described in step 3 is the one in following combination: copper sulphate and ascorbic acid, or cuprous bromide and pentamethyl-diethylenetriamine, or cuprous bromide and 2,2'-bipyridyl.
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| CN104645907A (en) * | 2015-02-06 | 2015-05-27 | 顺德职业技术学院 | Preparation method of hot cross-linking type nano paraffin phase-change energy-storage capsule |
| CN104826564A (en) * | 2015-02-06 | 2015-08-12 | 顺德职业技术学院 | Negative-charged nano-paraffin phase-change energy-storing capsule preparing method |
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| CN104826564A (en) * | 2015-02-06 | 2015-08-12 | 顺德职业技术学院 | Negative-charged nano-paraffin phase-change energy-storing capsule preparing method |
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| WO2019104987A1 (en) * | 2017-11-28 | 2019-06-06 | 大连理工大学 | Thermal conduction enhanced organic composite shaping phase change material and preparation method therefor |
| US11479701B2 (en) | 2017-11-28 | 2022-10-25 | Dalian University Of Technology | Thermal conduction enhanced organic composite shape-stabilized phase change material and preparation method thereof |
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