CN104531081A - Phase change cold accumulation composite material based on polyethylene glycol - Google Patents
Phase change cold accumulation composite material based on polyethylene glycol Download PDFInfo
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- CN104531081A CN104531081A CN201510021194.8A CN201510021194A CN104531081A CN 104531081 A CN104531081 A CN 104531081A CN 201510021194 A CN201510021194 A CN 201510021194A CN 104531081 A CN104531081 A CN 104531081A
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- phase change
- polyoxyethylene glycol
- change cold
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- storage matrix
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- 230000008859 change Effects 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 title abstract description 5
- 229920001223 polyethylene glycol Polymers 0.000 title abstract description 5
- 238000009825 accumulation Methods 0.000 title abstract 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002904 solvent Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 296
- -1 polyoxyethylene Polymers 0.000 claims description 138
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 133
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 133
- 238000003860 storage Methods 0.000 claims description 105
- 239000011159 matrix material Substances 0.000 claims description 89
- 239000000463 material Substances 0.000 claims description 52
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920002401 polyacrylamide Polymers 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 100
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 77
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 39
- 235000011187 glycerol Nutrition 0.000 description 38
- 230000009466 transformation Effects 0.000 description 28
- 238000005119 centrifugation Methods 0.000 description 21
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 description 19
- 229950009789 cetomacrogol 1000 Drugs 0.000 description 19
- 230000008569 process Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000012782 phase change material Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 5
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229940093430 polyethylene glycol 1500 Drugs 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- 230000001953 sensory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010019345 Heat stroke Diseases 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Medicinal Preparation (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a phase change cold accumulation composite material based on polyethylene glycol. The phase change cold accumulation composite material comprises 8-10 parts of polyethylene glycol and 0.3-5 parts of solvent, wherein the solvent is water and one or more of organic solvent soluble with water. The phase change cold accumulation composite material further comprises 0.05-2 parts of nucleating agents. The phase change cold accumulation composite material has high phase change heat and low phase change temperature and can be circularly used, and the cold accumulation capacity of the phase change cold accumulation composite material keeps good. Meanwhile, a preparing method of the phase change cold accumulation composite material is simple, practicable and low in cost.
Description
Technical field
The present invention relates to matrix material, particularly, relate to a kind of phase change cold-storage matrix material, more particularly, relate to a kind of phase change cold-storage matrix material based on polyoxyethylene glycol.
Background technology
Material storage heat energy has two kinds of modes usually: sensible heat and latent heat (latent heat and heat of phase transformation).It is utilize the temperature variation of the specific heat capacity of material and material to carry out that sensible heat stores; Latent heat stores and utilizes material to carry out along with energy absorption and release in transformation process, wherein latent heat stores usually to store than sensible heat and has much higher energy storage density, therefore utilizes the latent heat of material to carry out energy storage cold-storage and has more wide prospect.
As described in non-patent literature " phase change material and phase change energy storage technology ", current phase-changing energy storage material has become the hot topic of Materials science research, the novel material developed in laboratory emerges in an endless stream, but realize the few in number of industrial large-scale production, these novel material ubiquities the defects such as raw materials cost is high, complicated process of preparation, use is inconvenient, product life is short.
The phase-change material for cold storage sold in the market mainly comprises following a few class:
(1) inorganic crystal hydration salt compound, as: nitrate, phosphoric acid salt, vitriol and their composition etc., wherein with Na
2sO
410H
2o is the most conventional, utilizes the change of its desorption crystal water and crystallization-dissolving to reach cold-storage object.
Although inorganic crystal hydration salt compound cost is low, good heat conductivity, energy storage density are large, but its easily occurred in process of cool cold, be separated, the phenomenon such as harden, often need to add anti-cryogen and anti-phase separation agent excessively to reduce the generation of above-mentioned phenomenon, because this increasing inorganic crystal hydration salt compound cost in use in actual application; In addition, due to these inorganic crystal hydration salt compounds along with temperature rising can lose crystal water, thus individual difference is obvious, cold-storage effect poor repeatability to cause material to show as, and occurs the adverse consequencess such as irreversible performance reduction after repeatedly using.
In addition, the density of these inorganic materials is usually all larger, thus under causing the condition of same volume, inorganic materials can weigh a lot, and therefore it has difficulties when extensive use.With the exception of this, the transformation temperature of inorganic materials is all higher, even up to a few Baidu, greatly differs from each other with human body sensory optimum temps, and therefore, the application in clothes exists very large obstruction.
(2) organic phase-change cool storage material: conventional organic phase-change cool storage material comprises higher aliphatic hydrocarbon, aromatic hydrocarbon, polyvalent alcohol, carboxylic acid and lipid acid etc., wherein, extensive with materials application such as paraffin, capric acid, lauric acid, palmitinic acids.
Polyvalent alcohol is mainly used in middle high temperature energy-storage field, and such as neopentyl glycol transformation temperature is 44.1 DEG C, and heat of phase transformation is 116.5J/g; 2-amino-2-methyl 1,3 propylene glycol heat of phase transformation is 57.0 DEG C, heat of phase transformation 114.1J/g; Trimethylolethane transformation temperature is 81.8 DEG C, and heat of phase transformation is 172.6J/g.
Along with the continuous increase of greenhouse gas emission, Global Temperature raises year by year, especially there is heat island phenomenon in city, summer maximum temperature can up to more than 40 DEG C, but under this hot environment, the staff of some industry but keeps away unavoidable at outdoor work, in such hot environment, operation very easily causes the consequence such as heatstroke, hot spoke disease, light then there is dizziness, the uncomfortable symptom such as to feel sick, heavy then can death be caused, in only summer in 2013, at Chinese Yin Gaowen, the number of death is greater than 5 people.Therefore, the problems demand developing a kind of phase-change material for cold storage be applicable in the common daily necessities such as clothes, cushion solves.
Chinese patent CN 102732228 B discloses the phase-change material for cold storage based on lauryl alcohol and paraffin, it uses lauryl alcohol and paraffin as the main body of phase change material, although the current research to lauryl alcohol security is also insufficient, but our known lauryl alcohol is a kind of liquid with irritating smell, long-time suction can cause the headache of people, feel sick, and lauryl alcohol is oil-soluble substance, will extremely bother if packaging leaks cleaning.Therefore, a kind of safety non-toxic, matter phase-change material for cold storage that is soft, comfort level when can ensure to use is needed to develop.
Summary of the invention
In order to overcome the problems referred to above, present inventor has performed and study with keen determination, found that, in polyoxyethylene glycol, add water or one or more in the organic solvent that dissolves each other with water, prepare the good and phase change cold-storage matrix material that comfort level is good of a kind of capacity of heat transmission, thus complete the present invention.
The object of the present invention is to provide a kind of phase change cold-storage matrix material based on polyoxyethylene glycol, this phase change cold-storage matrix material comprises the composition of following parts by weight:
Polyoxyethylene glycol 8 ~ 10 parts,
Solvent 0.3 ~ 5 part.
The object of the present invention is to provide a kind of phase change cold-storage matrix material based on polyoxyethylene glycol, this phase change cold-storage matrix material comprises the composition of following parts by weight:
Polyoxyethylene glycol 8 ~ 10 parts,
Solvent 0.3 ~ 5 part,
Nucleator 0.05 ~ 2 part.
Wherein, described solvent is one or more in water and the organic solvent that dissolves each other with water.
Another object of the present invention is to the preparation method providing a kind of phase change cold-storage matrix material, the method comprises the following steps:
(1) join in container by material I or material II, wherein, material I comprises the polyoxyethylene glycol of 8 ~ 10 parts and the solvent of 0.3 ~ 5 part, and material II comprises the nucleator of the polyoxyethylene glycol of 8 ~ 10 parts, the solvent of 0.3 ~ 5 part and optional 0.05 ~ 2 part;
(2) by the material I that joins in container or material II mixing, the phase change cold-storage matrix material based on polyoxyethylene glycol is obtained.
Another object of the present invention is to provide a kind of phase change cold-storage matrix material for air conditioner clothing field or the purposes in cold pad field.
Phase change cold-storage matrix material provided by the invention has higher heat of phase transformation and lower transformation temperature, and can repeatedly recycle and its cold-storage ability keeps good.
Accompanying drawing explanation
Fig. 1 illustrates the mass spectrum of the polyoxyethylene glycol of the gained after treatment in embodiment 1;
Fig. 2 illustrates the mass spectrum without the polyoxyethylene glycol after any process in comparative example 1;
Fig. 3 illustrates the DSC figure of gained phase change cold-storage matrix material in embodiment 2;
Fig. 4 illustrates the DSC figure of gained phase change cold-storage matrix material in embodiment 3;
Fig. 5 illustrates the DSC figure of gained phase change cold-storage matrix material in embodiment 4;
Fig. 6 illustrates the DSC figure of gained phase change cold-storage matrix material in embodiment 5;
Fig. 7 illustrates the DSC figure of gained phase change cold-storage matrix material in comparative example 1;
Fig. 8 illustrates the infrared spectrum of gained phase change cold-storage matrix material in embodiment 2;
Fig. 9 illustrates the infrared spectrum of gained phase change cold-storage matrix material in embodiment 3;
Figure 10 illustrates the infrared spectrum of gained phase change cold-storage matrix material in embodiment 4;
Figure 11 illustrates the infrared spectrum of gained phase change cold-storage matrix material in embodiment 5;
The embodiment 2 that illustrates Figure 12 circulates 50 gained latent heat of phase change variation diagrams.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will illustrate along with these and become more clear, clear and definite.
According to an aspect of the present invention, provide a kind of phase change cold-storage matrix material based on polyoxyethylene glycol, this phase change cold-storage matrix material comprises the composition of following parts by weight:
Polyoxyethylene glycol 8 ~ 10 parts,
Solvent 0.3 ~ 5 part.
In above-mentioned phase change cold-storage matrix material, described solvent is one or more in water and the organic solvent that dissolves each other with water.
Especially, the organic solvent dissolved each other with water is alcoholic solvent.
As the example of above-mentioned alcoholic solvent, specifically mention: methyl alcohol, ethanol, BDO, Virahol, ethylene glycol, propylene glycol, glycol ether and glycerine.
In above-mentioned phase change cold-storage matrix material, described solvent is one or more in following solvents: water, methyl alcohol, ethanol, BDO, Virahol, ethylene glycol, propylene glycol, glycol ether and glycerine.
In a preferred embodiment, described solvent is one or more in following solvents: water, BDO, Virahol, ethylene glycol and glycerine.
Further, described solvent is one or more in water, BDO, ethylene glycol and glycerine.
Further, described solvent is one or more in water, ethylene glycol and glycerine.
In above-mentioned phase change cold-storage matrix material, described solvent most preferably be in water and glycerine one or more.
Especially, described solvent is the mixture of water and glycerine, and wherein, when the mixture of water and glycerine elected as by solvent, the adding proportion of water and glycerine does not limit especially, according to the actual requirements, can select the adding proportion of water and glycerine.
Need especially it is mentioned that, in the mixture of above-mentioned water and glycerine, water: with the weight ratio of glycerine for making water: glycerine=(1 ~ 10): (1 ~ 4), especially, the weight ratio of water and glycerine is for making water: glycerine=(1 ~ 5): (1 ~ 2).
In above-mentioned phase change cold-storage matrix material, described polyoxyethylene glycol, has another name called α-hydrogen-ω-hydroxyl (oxygen-1,2-second two base) polymkeric substance, be white solid or colourless oil liquid at normal temperatures and pressures, its transformation temperature is 17.9 ~ 50 DEG C, and heat of phase transformation is 121 ~ 178J/g; Surfusion is less than most of inorganic salt, can be stable realize phase change cold-storage effect; Meanwhile, its stable chemical nature, under normal temperature and pressure not with other material generation chemical reaction, therefore not perishable storage receptacle; After dsc (DSC) detects, show that polyoxyethylene glycol self is a kind of desirable low temperature phase change cold storage material.
In above-mentioned phase change cold-storage matrix material, the molecular weight of described polyoxyethylene glycol is 400 ~ 2000, and further, the molecular weight of described polyoxyethylene glycol is 500 ~ 1800, and further, the molecular weight of described polyoxyethylene glycol is 600 ~ 1500.
In a preferred embodiment, one or more in the polyoxyethylene glycol with following molecular weight selected by described polyoxyethylene glycol: Polyethylene Glycol-600, polyethylene glycol-800, cetomacrogol 1000, polyoxyethylene glycol 1200 and polyethylene glycol 1500.
In further preferred embodiment, described polyoxyethylene glycol select in the polyoxyethylene glycol with following molecular weight one or more: polyethylene glycol-800 and cetomacrogol 1000.
In above-mentioned phase change cold-storage matrix material, because water and glycerine can dissolve each other, add in polyoxyethylene glycol with water and glycerol mixture, both effectively can reduce the hardness of the phase change cold-storage matrix material finally obtained, the phase-change material for cold storage finally obtained can be made again to keep satisfactory stability.
Find through experimental study, mixture that water and glycerine formed jointly is added as solvent in polyoxyethylene glycol, under making the phase transformation heat content of the phase change cold-storage matrix material finally obtained substantially not have lossy prerequisite, the phase change cold-storage matrix material finally obtained is more soft.
In above-mentioned phase change cold-storage matrix material, based on the polyoxyethylene glycol of 8 ~ 10 weight parts, with the addition of the solvent of 0.3 ~ 5 weight part, when ensureing that the heat of phase transformation of phase change cold-storage matrix material does not obviously reduce, and significantly can reduce production cost.
Study discovery through the present inventor, when the parts by weight of added solvent are greater than 5, the heat of phase transformation of the phase change cold-storage matrix material finally obtained starts to decline; When the parts by weight of added solvent are less than 0.3, the phase change cold-storage matrix material finally obtained hardness is after the phase change still comparatively large, and its transformation temperature is not the optimal temperature of human body, is therefore not easy to the use in reality.
In addition, due to polyoxyethylene glycol, to solidify rear quality hard, and its to solidify formed shape wayward, be therefore subject to many restrictions in actual use, more cannot make air conditioner clothing.Therefore, in polyethylene glycol system, introduce solvent, the concentration of polyoxyethylene glycol can not only be reduced, and can regulate and control transformation temperature, thus present gel state after making phase change cold-storage composite material solidification, instead of hard solidify state.
Discovery is studied through the present inventor, in above-mentioned phase change cold-storage matrix material, due to the characteristic that the zero pour of polyoxyethylene glycol is higher than the zero pour of solvent, after polyoxyethylene glycol solidifies, solvent does not solidify, thus make solid-state polyoxyethylene glycol fragmentation, thus effectively reduce the hardness of the phase change cold-storage matrix material finally obtained, meanwhile, by regulating and controlling the transformation temperature of the phase change cold-storage matrix material finally obtained the addition of solvent.
In addition, because the heat conductivility of polyoxyethylene glycol is poor, its thermal conductivity is only 0.3W/mK, therefore, in polyoxyethylene glycol, add solvent, on the one hand, improve the heat conductivility of the phase change cold-storage matrix material finally obtained, on the other hand, the phase change cold-storage matrix material making finally to obtain become a kind of stable homogeneous system.
Wherein, it should be noted that especially when water selected by solvent, not only increase the heat conductivility of the phase change cold-storage matrix material finally obtained, and polyoxyethylene glycol and water can form homodisperse stabilising system.
In a preferred embodiment, based on the polyoxyethylene glycol of 8 ~ 10 parts by weight, the parts by weight of described solvent are 0.5 ~ 4.5 part, and further, the addition of described solvent is 0.6 ~ 4 part, and further, the addition of described solvent is 0.8 ~ 3.5 part.
In above-mentioned phase change cold-storage matrix material, selected polyoxyethylene glycol can directly use, and also can use after treatment.
In a preferred embodiment, selected polyoxyethylene glycol prepares after carrying out centrifugal treating, and this centrifugal treating comprises following two steps:
Step one, the polyoxyethylene glycol selected heated and makes it melt;
Step 2, by fusing after polyoxyethylene glycol carry out centrifugal.
In above-mentioned steps one, the temperature of polyoxyethylene glycol heating is not limited, especially as long as polyoxyethylene glycol can be melted completely.
Especially, the temperature of heating is below the fusing point of selected polyoxyethylene glycol.
In a preferred embodiment, the polyoxyethylene glycol selected heated and after making it melt completely, saltout.
Described concrete steps of saltouing are as described below: add in inorganic salt in polyoxyethylene glycol after being melted down one or more.
As the example of inorganic salt, specifically mention: sodium sulfate, potassium sulfate, sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus.
In a preferred embodiment, described inorganic salt are one or more in sodium sulfate, sodium carbonate and sodium bicarbonate.
The addition of described inorganic salt does not limit especially, can add according to the actual requirements.
Especially, based on the polyoxyethylene glycol of 8 ~ 10 parts by weight, the addition of described inorganic salt is 1.5 ~ 10 parts, is preferably 2 ~ 8 parts, is further more preferably 2.5 ~ 7 parts, most preferably is 3 ~ 6 parts.
Study discovery through the present inventor, the mode that inorganic salt add does not limit especially, directly adds or inorganic salt is mixed with aqueous solution interpolation.
In a preferred embodiment, inorganic salt are mixed with the aqueous solution, wherein, the concentration of the aqueous solution does not limit especially, as long as inorganic salt can be mixed with the solution of stable homogeneous.
In a preferred embodiment, the aqueous solution be mixed with by inorganic salt joins after in the polyoxyethylene glycol after fusing completely, system is stirred, then carries out the centrifugal treating described in step 2.
Find after deliberation, after polyoxyethylene glycol melts completely, add inorganic salt, can make in centrifugation step, be conducive to making being separated of small molecules polyoxyethylene glycol and macromole polyoxyethylene glycol.
In above-mentioned steps two, temperature time centrifugal is 15 ~ 30 DEG C, and especially, temperature time centrifugal is preferably 16 ~ 28 DEG C.
In above-mentioned steps two, centrifugation rate time centrifugal does not limit especially, can arrange according to the actual requirements.
Especially, centrifugation rate is set to 10000 ~ 20000rpm/min, and centrifugation rate is preferably 15000 ~ 18000rpm/min.
In above-mentioned steps two, centrifugation time does not limit especially, can set according to the actual requirements.
Especially, centrifugation time is 5 ~ 30 minutes, and centrifugation time is preferably 8 ~ 25 minutes, and further, centrifugation time is preferably 10 ~ 20 minutes.
In a preferred embodiment, by fusing after polyoxyethylene glycol join in centrifuge tube, be then positioned over carry out in whizzer centrifugal, wherein, temperature time centrifugal is 15 ~ 30 DEG C, and speed time centrifugal is 10000 ~ 20000rpm/min, and centrifugation time is 5 ~ 30 minutes.
Polyoxyethylene glycol after fusing is joined in centrifuge tube, is placed in whizzer centrifugal, centrifugal 10 minutes, small molecules can be separated with macromole polyoxyethylene glycol.
Study discovery through the present inventor, existing commercially available polyoxyethylene glycol is owing to being subject to the restriction of preparation method, and the molecular weight product prepared is normal distribution.Therefore utilize the principle that the molecular weight of polyoxyethylene glycol and zero pour are proportionate, after first making it melt completely polyoxyethylene glycol heating, carry out low-temperature centrifugation, then micromolecular polyoxyethylene glycol is still liquid, and macromolecular polyoxyethylene glycol solidifies, thus completes separation.
According to a further aspect in the invention, provide a kind of preparation method of the phase change cold-storage matrix material based on polyoxyethylene glycol, the method comprises following two steps:
Step one, polyoxyethylene glycol and solvent to be joined in container.
In above-mentioned steps one, the parts by weight of described polyoxyethylene glycol are 8 ~ 10 parts, and the parts by weight of solvent are 0.3 ~ 5 part, wherein,
The molecular weight of described polyoxyethylene glycol is 400 ~ 2000, and described solvent is one or more in water and the organic solvent that dissolves each other with water.
Especially, the organic solvent dissolved each other with water is alcoholic solvent.
A kind of in above-mentioned steps, the addition manner of polyoxyethylene glycol and solvent does not limit especially, according to the actual requirements, carries out selecting and arranging.
In a preferred embodiment, joined by polyoxyethylene glycol in container, then join in polyoxyethylene glycol by solvent, especially, solvent is selected to add in batches or drip and is added.
Step 2, will the mixing of materials in container be joined, obtain the phase change cold-storage matrix material based on polyoxyethylene glycol.
In above-mentioned steps two, temperature during mixing of materials does not limit especially, room temperature or be heated to certain temperature.
Especially, at ambient temperature, mixing of materials is even.
In above-mentioned steps two, the uniform mode of mixing of materials does not limit especially, as long as can by mixing of materials evenly.
In a preferred embodiment, select the mode of ultra-sonic oscillation that mixing of materials is even.
According to a further aspect of the invention, additionally provide a kind of phase change cold-storage matrix material based on polyoxyethylene glycol, this phase change cold-storage matrix material comprises the composition of following parts by weight:
Polyoxyethylene glycol 8 ~ 10 parts,
Solvent 0.3 ~ 5 part,
Nucleator 0.05 ~ 2 part.
In above-mentioned phase change cold-storage matrix material, the molecular weight of described polyoxyethylene glycol is 400 ~ 2000, and further, the molecular weight of described polyoxyethylene glycol is 500 ~ 1800, and further, the molecular weight of described polyoxyethylene glycol is 600 ~ 1500.
In a preferred embodiment, one or more in the polyoxyethylene glycol with following molecular weight selected by described polyoxyethylene glycol: Polyethylene Glycol-600, polyethylene glycol-800, cetomacrogol 1000, polyoxyethylene glycol 1200 and polyethylene glycol 1500.
In further preferred embodiment, described polyoxyethylene glycol select in the polyoxyethylene glycol with following molecular weight one or more: polyethylene glycol-800 and cetomacrogol 1000.
In above-mentioned phase change cold-storage matrix material, described nucleator is one or more in polyvinylpyrrolidone, polyacrylamide and polyoxyethylene glycol.
In above-mentioned phase change cold-storage matrix material, described solvent is one or more in water and the organic solvent that dissolves each other with water.
Especially, the organic solvent dissolved each other with water is alcoholic solvent.
As the example of above-mentioned alcoholic solvent, specifically mention: methyl alcohol, ethanol, BDO, Virahol, ethylene glycol, propylene glycol, glycol ether and glycerine.
In above-mentioned phase change cold-storage matrix material, described solvent is one or more in following solvents: water, methyl alcohol, ethanol, BDO, Virahol, ethylene glycol, propylene glycol, glycol ether and glycerine.
In a preferred embodiment, described solvent is one or more in following solvents: water, BDO, Virahol, ethylene glycol and glycerine.
Further, described solvent is one or more in water, BDO, ethylene glycol and glycerine.
Further, described solvent is one or more in water, ethylene glycol and glycerine.
In above-mentioned phase change cold-storage matrix material, described solvent most preferably be in water and glycerine one or more.
Especially, described solvent is the mixture of water and glycerine, and wherein, when the mixture of water and glycerine elected as by solvent, the adding proportion of water and glycerine does not limit especially, according to the actual requirements, can select the adding proportion of water and glycerine.
Need especially it is mentioned that, in the mixture of above-mentioned water and glycerine, water: with the weight ratio of glycerine for making water: glycerine=(1 ~ 10): (1 ~ 4), especially, water: with the weight ratio of glycerine for making water: glycerine=(1 ~ 5): (1 ~ 2).
In above-mentioned nucleator, the molecular weight of described polyvinylpyrrolidone is 8000 ~ 100000, is preferably 10000 ~ 80000, is more preferably 20000 ~ 60000, most preferably is 25000 ~ 50000.
In above-mentioned nucleator, the particular type of described polyvinylpyrrolidone does not limit especially, anionic polyvinylpyrrolidone, cationic polyvinylpyrrolidone and nonionic polyvinyl pyrrolidone.
Especially, select nonionic polyvinyl pyrrolidone as nucleator.
In above-mentioned nucleator, the molecular weight of described polyacrylamide is 300,000 ~ 1,100 ten thousand, is preferably 1,000,000 ~ 8,000,000, is more preferably 2,000,000 ~ 6,000,000, most preferably is 3,500,000 ~ 5,000,000.
In above-mentioned nucleator, the particular type of described polyacrylamide does not limit especially, anion-polyacrylamide, cationic-type polyacrylamide, non-ionic polyacrylamide and amphoteric polyacrylamide.
Especially, select non-ionic polyacrylamide as nucleator.
In above-mentioned nucleator, the molecular weight of described polyoxyethylene glycol I is 8000 ~ 40000, is preferably 8500 ~ 30000, is more preferably 9000 ~ 25000, most preferably is 10000 ~ 20000.
In a preferred embodiment, as the example of polyoxyethylene glycol I used in nucleator, PEG20000, polyethylene glycol 1500 0 and PEG 20000 is specifically mentioned.
In a preferred embodiment, selected polyoxyethylene glycol prepares after carrying out centrifugal treating, and this centrifugal treating comprises following two steps:
Step one, the polyoxyethylene glycol selected heated and makes it melt;
Step 2, by fusing after polyoxyethylene glycol carry out centrifugal.
In above-mentioned steps one, the temperature of polyoxyethylene glycol heating is not limited, especially as long as polyoxyethylene glycol can be melted completely.
Especially, the temperature of heating is below the fusing point of selected polyoxyethylene glycol.
In a preferred embodiment, the polyoxyethylene glycol selected heated and after making it melt completely, saltout.
Described concrete steps of saltouing are as described below: add in inorganic salt in polyoxyethylene glycol after being melted down one or more.
As the example of inorganic salt, specifically mention: sodium sulfate, potassium sulfate, sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus.
In a preferred embodiment, described inorganic salt are one or more in sodium sulfate, sodium carbonate and sodium bicarbonate.
The addition of described inorganic salt does not limit especially, can add according to the actual requirements.
Especially, based on the polyoxyethylene glycol of 8 ~ 10 parts by weight, the addition of described inorganic salt is 1.5 ~ 10 parts, is preferably 2 ~ 8 parts, is further more preferably 2.5 ~ 7 parts, most preferably is 3 ~ 6 parts.
Study discovery through the present inventor, the mode that inorganic salt add does not limit especially, directly adds or inorganic salt is mixed with aqueous solution interpolation.
In a preferred embodiment, inorganic salt are mixed with the aqueous solution, wherein, the concentration of the aqueous solution does not limit especially, as long as inorganic salt can be mixed with the solution of stable homogeneous.
In a preferred embodiment, the aqueous solution be mixed with by inorganic salt joins after in the polyoxyethylene glycol after fusing completely, system is stirred, then carries out the centrifugal treating described in step 2.
Find after deliberation, after polyoxyethylene glycol melts completely, add inorganic salt, can in centrifugation step, be conducive to making being separated of small molecules polyoxyethylene glycol and macromole polyoxyethylene glycol.
In above-mentioned steps two, temperature time centrifugal is 15 ~ 30 DEG C, and especially, temperature time centrifugal is preferably 16 ~ 28 DEG C.
In above-mentioned steps two, centrifugation rate time centrifugal does not limit especially, can arrange according to the actual requirements.
Especially, centrifugation rate is set to 10000 ~ 20000rpm/min, and centrifugation rate is preferably 15000 ~ 18000rpm/min.
In above-mentioned steps two, centrifugation time does not limit especially, can set according to the actual requirements.
Especially, centrifugation time is 5 ~ 30 minutes, and centrifugation time is preferably 8 ~ 25 minutes, and further, centrifugation time is preferably 10 ~ 20 minutes.
In a preferred embodiment, by fusing after polyoxyethylene glycol join in centrifuge tube, be then positioned over carry out in whizzer centrifugal, wherein, temperature time centrifugal is 15 ~ 30 DEG C, and speed time centrifugal is 10000 ~ 20000rpm/min, and centrifugation time is 5 ~ 30 minutes.
Polyoxyethylene glycol after fusing is joined in centrifuge tube, is placed in whizzer centrifugal, centrifugal 10 minutes, small molecules can be separated with macromole polyoxyethylene glycol.
Study discovery through the present inventor, existing commercially available polyoxyethylene glycol is owing to being subject to the restriction of preparation method, and the molecular weight product prepared is normal distribution.Therefore utilize the principle that the molecular weight of polyoxyethylene glycol and zero pour are proportionate, after first making it melt completely polyoxyethylene glycol heating, carry out low-temperature centrifugation, then micromolecular polyoxyethylene glycol is still liquid, and macromolecular polyoxyethylene glycol solidifies, thus completes separation.
Discovery is studied through the present inventor, based on the polyoxyethylene glycol of 8 ~ 10 parts by weight and the solvent of 0.3 ~ 5 parts by weight, add the nucleator mentioned by the present invention of 0.05 ~ 2 parts by weight, on the one hand, the crystallization of the phase change cold-storage matrix material finally prepared can be induced, thus weaken the surfusion of the phase change cold-storage matrix material finally obtained, on the other hand, the phase transition process of the phase change cold-storage matrix material finally obtained is made to become solid-solid phase-change by liquid-solid phase transformation, thus avoid cause after the phase change cold-storage matrix material obtained becomes liquid mutually sagging, more comfortable when then wearing.
In a preferred embodiment, based on the polyoxyethylene glycol of 8 ~ 10 parts, the parts by weight of described nucleator are 0.08 ~ 1.8 part, further, are more preferably 0.1 ~ 1.5 part.
In accordance with a further aspect of the present invention, provide a kind of preparation method of the phase change cold-storage matrix material based on polyoxyethylene glycol, the method comprises following two steps:
Step one, polyoxyethylene glycol, solvent and nucleator are joined in container;
Step 2, will the mixing of materials in container be joined, obtain the phase change cold-storage matrix material based on polyoxyethylene glycol.
In above-mentioned preparation method, the addition manner of described polyoxyethylene glycol, solvent and nucleator is not subject to concrete restriction, as long as by mixing of materials evenly.
In a preferred embodiment, first polyoxyethylene glycol is joined in container, and then successively solvent and nucleator are joined in container.Especially, under the condition of heated and stirred, nucleator is added.Wherein, the temperature of heating and the speed of stirring can be selected according to the actual requirements, are not subject to concrete restriction.
In a preferred embodiment, after polyoxyethylene glycol, solvent and nucleator are mixed, under mixed material being placed on the temperature of-20 DEG C ~ 10 DEG C, especially, preferably at 0 DEG C ~ 4 DEG C, make sample quenching, thus make the whole system of the phase change cold-storage matrix material finally prepared more homogeneous, and the particle formed after crystallization is less, and more homogeneous.
Wherein, the time of placing at low temperatures does not limit especially, can select according to the actual requirements.
Especially, mixed material is joined in frozen water or in refrigerator, make sample quenching.
In this article, term used " excessively cold " refers to, fluent meterial is reduced to zero pour in temperature and does not still solidify or the phenomenon of the phase transformation such as crystallization.
In this article, term used " nucleator " refers to, by changing crystallization behavior, accelerating crystallization rate, increases crystal density and impel fine grain size, reach shorten shaping cycle, heat-drawn wire, etc. the New function auxiliary agent of physical and mechanical properties.
In this article, the not special restriction of described water, especially, is preferably distilled water.
Phase change cold-storage matrix material provided by the invention has the following advantages:
The first, the transformation temperature of phase change cold-storage matrix material provided by the invention is in the low temperature range of 15 ~ 30 DEG C, said temperature scope is the optimum temperature range that human body sensory is comfortable, and the heat of phase transformation of this phase change cold-storage matrix material is up to 111J/g, and the heat of phase transformation of pure polyoxyethylene glycol is 133J/g, therefore, the heat of phase transformation of the phase change cold-storage matrix material prepared accounts for 84.0% of total heat of phase transformation of pure polyoxyethylene glycol, has the application prospect in the field such as air conditioner clothing field and cold pad of manufacture;
The second, phase change cold-storage matrix material provided by the invention is after repeatedly recycling, and its cold-storage ability still keeps good, due to repeatedly using of cold-storage matrix material, makes it have practical value;
Three, phase change cold-storage matrix material stable chemical nature provided by the invention, not perishable storage receptacle;
Four, select solvent cut polyoxyethylene glycol in the present invention, prepare compound system, preparation method is simple, and meanwhile, raw material is conveniently easy to get, and saves great amount of cost.
embodiment
The present invention is further described below by way of specific examples.But these examples are only exemplary, do not form any restriction to protection scope of the present invention.
The AVANTI J-25 type whizzer that in embodiment and comparative example, the whizzer of centrifugal use is produced for U.S. BECKMANCOULTER;
The polyoxyethylene glycol used in embodiment and comparative example, polyvinylpyrrolidone, polyacrylamide are traditional Chinese medicines group and produce, analytical pure;
In embodiment, water is distilled water.
Embodiment 1
the centrifugal treating of polyoxyethylene glycol
(1) take 25.00g cetomacrogol 1000, at 60-80 DEG C, heating makes it melt completely;
(2) by completely fusing after polyoxyethylene glycol pour in centrifuge tube, be placed in whizzer centrifugal, centrifugal 10 minutes, wherein, rotating speed is 20000rpm/min, and centrifuging temperature is 24 DEG C.
Embodiment 2
(1) at ambient temperature, take cetomacrogol 1000 and 0.60g water that 9.40g processes gained in embodiment 1, first 9.4g cetomacrogol 1000 is added in beaker, then drip the water taken;
(2), after cetomacrogol 1000 and water being mixed, phase change cold-storage matrix material I is prepared.
Material I is after infrared test, and infrared signature peak is as follows:
3438cm
-1(OH stretching vibration), 2872cm
-1(CH
3symmetrical stretching vibration), 1648cm
-1(liquid H
2o angle vibrates), 1466cm
-1(CH
2angle vibrates), 1434cm
-1, 1280cm
-1, 1242cm
-1(C-O-C unsymmetrically is stretched), 1090cm
-1(alcohols COH stretches), 947cm
-1(C-O-C symmetry is flexible), 841cm
-1.
Embodiment 3
(1) at ambient temperature, take cetomacrogol 1000 and 1.50g glycerine that 8.50g processes gained in embodiment 1, first the cetomacrogol 1000 taken is added in beaker, under the condition stirred, drip load weighted glycerine;
(2) cetomacrogol 1000 and glycerine are mixed, prepare phase change cold-storage matrix material II.
Material II is after infrared test, and infrared signature peak is as follows:
3377cm
-1(the OH stretching vibration of R-OH), 2882cm
-1(CH
3symmetrical stretching vibration), 1466cm
-1(CH
2angle vibrates), 1359cm
-1, 1341cm
-1, 1279cm
-1, 1240cm
-1(C-O-C unsymmetrically is stretched), 1146cm
-1, 1105cm
-1(alcohols COH stretches), 1060cm
-1(alcohols COH stretches), 947cm
-1(C-O-C symmetry is flexible), 841cm
-1.
Embodiment 4
(1) at ambient temperature, take 0.1g PEG 20000 as nucleator, 8.71g is without the cetomacrogol 1000 of any process and 1.19g water, first load weighted cetomacrogol 1000 is added in beaker, then add load weighted water wherein, finally add the PEG 20000 taken;
(2) by even for the mixing of materials joined in container, be then positioned in frozen water by the material mixed, wherein, the temperature of frozen water remains 0 DEG C, prepares phase change cold-storage matrix material III.
Material III is after infrared test, and infrared signature peak is as follows:
3448cm
-1(OH stretching vibration), 2870cm
-1(CH
3symmetrical stretching vibration), 1647cm
-1(liquid H
2o angle vibrates), 1466cm
-11(CH
2angle vibrates), 1347cm
-1, 1282cm
-1, 1248cm
-1(C-O-C unsymmetrically is stretched), 1089cm
-1(alcohols COH stretches), 947cm
-11(C-O-C symmetry is flexible), 841cm
-1.
Embodiment 5
(1) 0.85g PEG 20000 is taken, 7.17g cetomacrogol 1000,0.98g water and 1.5g glycerine, join in beaker by the load weighted cetomacrogol 1000 without any process and water, then in beaker, add the glycerine taken, finally add the PEG 20000 taken;
(2) by even for the mixing of materials joined in container, be then positioned in frozen water by mixed material, wherein the temperature of frozen water remains 0 DEG C, prepares phase change cold-storage matrix material IV.
Material IV is after infrared test, and infrared signature peak is as follows:
3042cm
-1(OH stretching vibration), 2874cm
-1(CH
3symmetrical stretching vibration), 1647cm
-1(liquid H
2o angle vibrates), 1466cm
-1(CH
2angle vibrates), 1343cm
-1, 1280cm
-1, 1242cm
-1(C-O-C unsymmetrically is stretched), 1093cm
-1(alcohols COH stretches), 947cm
-1(C-O-C symmetry is flexible), 841cm
-1.
Embodiment 6
(1) 0.1g PVPK30 000 is taken, 8.71g cetomacrogol 1000 and 1.19g water, process the cetomacrogol 1000 of gained and water joins in beaker by load weighted through embodiment 1, then add the type PVPK30 000 taken;
(2) by even for the mixing of materials joined in container, be then positioned in frozen water by mixed material, wherein the temperature of frozen water remains 0 DEG C, prepares phase change cold-storage matrix material V.
Embodiment 7
(1) take 0.1g polyacrylamide, molecular weight is 300,000,8.71g cetomacrogol 1000 and 1.19g water, joins in beaker, then add the polyacrylamide taken by the load weighted cetomacrogol 1000 without any process and water;
(2) by even for the mixing of materials joined in container, be then positioned in frozen water by mixed material, wherein the temperature of frozen water remains 0 DEG C, prepares phase change cold-storage matrix material VI.
Comparative example 1
Take the cetomacrogol 1000 that 25.00g is commercially available, it can be used as phase-change material for cold storage VII without any process.
test example
mass spectrometric measurement
Carry out mass spectrometric measurement respectively to the polyoxyethylene glycol after unprocessed in the polyoxyethylene glycol after process in embodiment 1 and comparative example 1, result as depicted in figs. 1 and 2.
Can be learnt by Fig. 1 and Fig. 2, existing commercially available polyoxyethylene glycol is owing to being subject to the restriction of preparation method, and the molecular weight of the product prepared is normal distribution.
Comparison diagram 1 and Fig. 2 find the molecular weight polyethylene glycol after centrifugation 300 ~ 600 part completely separatedly to open.Can learn thus, after being heated by polyoxyethylene glycol, after carrying out centrifugal treating, micromolecular polyoxyethylene glycol is still liquid, and macromolecular polyoxyethylene glycol is for solidifying state, can complete separation.
dsc (DSC)
Respectively DSC test is carried out according to the method comprised the steps to the phase change cold-storage matrix material I ~ VII of gained in embodiment 2 ~ 5 and comparative example 1, wherein, the Q100 differential scanning calorimeter that Thermal Analysis company produces is used in the mensuration of DSC, upwards (exo up), heat absorption peak-to-peak point is downward for test result heat release peak-to-peak point:
(1) 60 DEG C of balances;
(2) 10 DEG C/min is down to 4 DEG C;
(3) at 4 DEG C of stable 5min;
(4) 10 DEG C/min rises to 60 DEG C.
Respectively as shown in figure 3 to figure 7, wherein, the information can learnt by above-mentioned Fig. 3 ~ 7 is as shown in table 1 below for result
Table 1
| Group number | Heat of phase transformation/J/g | Fusing point/DEG C |
| Material I | 111.7 | 32.2 |
| Material II | 116.1 | 34.5 |
| Material III | 96.6 | 24.4 |
| Material IV | 80.7 | 31.1 |
| Material VII | 133.3 | 37.0 |
Can be learnt by upper table, heat of phase transformation and the fusing point of the phase change cold-storage matrix material prepared by the present invention are substantially unchanged relative to polyoxyethylene glycol.
infrared test
Carry out infrared analysis according to ATR method respectively to the phase change cold-storage matrix material I ~ IV preparing gained in embodiment 2 ~ 5, wherein, instrument is the NICOLET 6700 that Thermo Scientific company produces, and resolving power is 4cm
-1, scanning times 32 times.Result is respectively as shown in Fig. 8 ~ 11.
loop test
The phase change cold-storage matrix material of gained in embodiment 2 is carried out loop test by the following method:
(1) 60 DEG C of balances;
(2) 10 DEG C/min is down to 4 DEG C;
(3) at 4 DEG C of stable 5min;
(4) 10 DEG C/min rises to 60 DEG C;
Repeat (2)-(4) step 49 times again.
Can learn to have excellent cycle performance by phase-change material for cold storage provided by the invention thus, circulating after 50 times, there is not obvious reduction in latent heat of phase change.
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. based on a phase change cold-storage matrix material for polyoxyethylene glycol, it is characterized in that, this phase change cold-storage matrix material comprises the composition of following parts by weight:
Polyoxyethylene glycol 8 ~ 10 parts,
Solvent 0.3 ~ 5 part.
2. phase change cold-storage matrix material according to claim 1, this phase change cold-storage matrix material also comprises:
Nucleator 0.05 ~ 2 part,
Wherein, preferred described solvent is one or more in water and the organic solvent that dissolves each other with water.
3. phase change cold-storage matrix material according to claim 2, wherein, described nucleator is one or more in polyoxyethylene glycol I, polyacrylamide and polyvinylpyrrolidone, and the molecular weight of preferred described polyoxyethylene glycol I is 8000 ~ 40000, the molecular weight of preferred described polyacrylamide is 300,000 ~ 1,100 ten thousand, and the molecular weight of preferred described polyvinylpyrrolidone is 8000 ~ 100000.
4. the phase change cold-storage matrix material according to any one of claims 1 to 3, wherein, the molecular weight of described polyoxyethylene glycol is 400 ~ 2000.
5. the phase change cold-storage matrix material according to any one of claim 2 ~ 4, wherein, the described organic solvent dissolved each other with water is alcoholic solvent.
6. the phase change cold-storage matrix material according to any one of Claims 1 to 5, wherein, described polyoxyethylene glycol is prepared by the method comprised the following steps:
(1) polyoxyethylene glycol selected heated and make it melt;
(2) polyoxyethylene glycol after fusing is carried out centrifugal.
7. according to the phase change cold-storage matrix material described in claim 6, wherein, in described step (1), after polyoxyethylene glycol melts completely, add in inorganic salt one or more.
8. prepare a method for the phase change cold-storage matrix material according to any one of claim 1 ~ 7, the method comprises the following steps:
(1) material I or material II are joined in container, wherein, material I comprises the polyoxyethylene glycol of 8 ~ 10 weight parts and the solvent of 0.3 ~ 5 weight part, and material II comprises the nucleator of the polyoxyethylene glycol of 8 ~ 10 weight parts, the solvent of 0.3 ~ 5 weight part and 0.05 ~ 2 optional weight part;
(2) by the material I that joins in container or material II mixing, the phase change cold-storage matrix material based on polyoxyethylene glycol is obtained.
9. according to Claim 8 described in preparation method, wherein, when being joined after in container by material II, in described step (2), mixed material is placed on-20 DEG C ~ 10 DEG C, at the temperature of preferably 0 DEG C ~ 4 DEG C.
10. one kind is used for air conditioner clothing field or the purposes in cold pad field by the phase change cold-storage matrix material described in claim 1 or 2.
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