CN116751568B - Flexible phase change cold accumulation material, preparation method thereof, cold accumulation agent and flexible cold accumulation bag - Google Patents
Flexible phase change cold accumulation material, preparation method thereof, cold accumulation agent and flexible cold accumulation bag Download PDFInfo
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- CN116751568B CN116751568B CN202311035373.8A CN202311035373A CN116751568B CN 116751568 B CN116751568 B CN 116751568B CN 202311035373 A CN202311035373 A CN 202311035373A CN 116751568 B CN116751568 B CN 116751568B
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- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003860 storage Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 45
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- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
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- 239000000243 solution Substances 0.000 claims description 38
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- 238000010438 heat treatment Methods 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001459 lithography Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
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- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
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- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
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- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 3
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- 239000001257 hydrogen Substances 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 238000010257 thawing Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 238000005054 agglomeration Methods 0.000 description 3
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 3
- 235000010234 sodium benzoate Nutrition 0.000 description 3
- 239000004299 sodium benzoate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
-
- 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)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of heat energy storage, in particular to a flexible phase change cold storage material, a preparation method thereof, a cold storage agent and a flexible cold storage bag. The flexible phase change cold storage material of the application comprises: the aqueous inorganic salt solution, the hydrophilic polymer and the crosslinking degree enhancer, and optionally other additives; the hydrophilic polymer is formed by copolymerizing a mixed monomer, a modified nucleating agent and a crosslinking agent; the crosslinking degree reinforcing agent is nano silicon dioxide with the particle size of 10 nm-80 nm. The flexible phase change cold storage material of the application overcomes the problems of low phase change latent heat, easy release of free water, high packaging design requirement and the like of the existing inorganic salt flexible phase change cold storage material by dispersing and modifying the granular modified nucleating agent in the hydrophilic polymer structure and using the crosslinking degree reinforcing agent to form a dual-network interpenetrating conformation with the hydrophilic polymer, and has the advantages of high phase change latent heat and high recycling stability, and can ensure that the photoetching material can obtain a specific and durable low-temperature environment in the storage and transportation process.
Description
Technical Field
The application relates to the technical field of heat energy storage, in particular to a flexible phase change cold storage material and a preparation method thereof, a cold storage agent and a flexible cold storage bag, and especially relates to a flexible phase change cold storage material and a preparation method thereof, a freezing type cold storage agent, a cold storage agent for storing a photoetching material and a flexible cold storage bag, wherein the photoetching material comprises photoresist, an anti-reflection coating, a spin-on hard mask and a spin-on glass hard mask used in the photoetching process.
Background
The basic storage modes of heat energy can be divided into sensible heat energy storage, latent heat energy storage and thermochemical energy storage, wherein the latent heat energy storage has the advantages of low cost, high energy storage density, stable output temperature, energy and the like compared with the other two modes, and is an important research object in the current energy storage technology field. The implementation of latent heat energy storage is based on the phase change process (melting, evaporating, solidifying, liquefying and the like) of substances, so that the phase change energy storage is also called phase change energy storage, the phase change energy storage can be divided into heat storage and cold storage from the point of energy storage and release utilization, the application of cold storage is exemplified by air conditioner cold storage, building cold storage, cold chain logistics, food preservation and the like, and the development of phase change cold storage materials is also an indispensable part of the phase change cold storage field.
The main energy storage agent of the conventional freezing type phase-change cold storage material (the phase-change temperature is below 0 ℃) is generally inorganic salt water solution, the phase-change cold storage density is high, the phase-change temperature adjusting space is large, the preparation process is simple, the cost is low, the application is wide in cold chain transportation of foods, medicines, biological agents and the like, however, the volume change of the inorganic salt water solution in the phase-change process is large, and the requirement on the packaging material is severe in order to avoid leakage.
Compared with the solution from the aspect of packaging container design, the preparation of the phase-change gel not only has the advantages of simple process, convenience in large-scale application, high reliability and the like, but also has the advantage that the use of the hydrophilic polymer can increase the viscosity of the inorganic salt water solution system so as to solve the phase separation problem of the system. Although inorganic salt phase-change gel based on hydrophilic polymer has many advantages, most of the hydrophilic polymers at present are characterized by low internal crosslinking degree and less rigid structure, so that the phase-change gel prepared based on hydrophilic polymer is loose in form, irreversible free water precipitation phenomenon is easy to occur after multiple temperature rise and reduction phase transitions or under the action of lower external force, and the recycling stability of the cold storage gel is poor. In addition, the hydrophilic polymer mainly absorbs water molecules by ionizing the polymer chains to stretch and further lock the water. However, this process breaks down the hydrogen bonds formed between some of the water molecules, thereby reducing the latent heat of phase change of the aqueous inorganic salt solution. Furthermore, since the hydrophilic polymer forms a gel after being combined with the inorganic salt aqueous solution, when the granular inorganic nucleating agent is used to reduce the supercooling degree of the inorganic salt aqueous solution phase-change cold-storage liquid, the nucleating agent having poor water solubility is difficult to disperse in the gel, resulting in failure to exert the nucleating effect.
Based on the above, it is necessary to develop a cold storage gel having a better cold storage effect, a longer service life and a better risk resistance.
Disclosure of Invention
In order to solve the problems, the application fully researches the swelling behavior of the composite cold storage material on inorganic salt aqueous solution, the free water precipitation condition after cyclic temperature rise and reduction, the flexible change condition thereof and the like, and aims to provide the flexible phase change cold storage material with more stable cold storage performance, stronger cold storage capacity and lower leakage risk.
The application aims to provide a flexible phase change cold storage material which has high phase change latent heat, lasting stability, flexible shaping effect and lower phase change temperature, and is suitable for low-temperature storage and transportation of photoetching materials; the application further aims to provide a preparation method of the flexible phase change cold storage material, which is simple to operate, and can be used for preparing the flexible phase change cold storage material with high phase change latent heat, lasting stability, flexible shaping effect and lower phase change temperature; it is still another object of the present application to provide a frozen type coolant having a relatively stable phase transition temperature; it is still another object of the present application to provide a cold storage agent for storing a photolithography material; the reaction of the chemical active groups of the photoetching material in the storage and transportation process can be avoided; the application further aims to provide a flexible cold accumulation bag which has high cold accumulation density, good circulation stability and flexible deformation, and can be flexibly filled around an object to be stored and transported at a low temperature according to specific requirements.
In a first aspect of the present application, there is provided a flexible phase change cold storage material comprising, in weight percent:
80-99.5% of inorganic salt water solution,
0.5-10% of hydrophilic polymer,
0.1% -5% of crosslinking degree reinforcing agent and
0-1% of other additives;
the inorganic salt aqueous solution comprises inorganic salt and water, wherein the weight of the inorganic salt accounts for 3% -40% of the total weight of the inorganic salt aqueous solution;
the hydrophilic polymer is formed by copolymerizing a mixed monomer, a modified nucleating agent and a crosslinking agent; the mixed monomer comprises the following components in a molar ratio of 1: (3-8): (0.05-0.5) acrylic compound, acrylic acid salt compound and acrylamide compound; the modified nucleating agent is a product obtained by carrying out functional group surface modification treatment on the nucleating agent by adopting a silane coupling agent, wherein the modified nucleating agent contains 0.5% -5% of modified groups by weight of the total weight of the modified nucleating agent;
the crosslinking degree reinforcing agent is nano silicon dioxide with the particle size of 10 nm-80 nm;
the other additives include corrosion inhibitors.
In some of these embodiments, the modified nucleating agent is chemically bonded in the structural backbone or branch of the hydrophilic polymer.
In some embodiments, the weight of the modified nucleating agent is 0.05% -0.5% of the total weight of the mixed monomers;
the molar addition amount of the crosslinking agent relative to the acrylic compound is 0.05% -0.5%.
In some embodiments, the flexible phase change cold storage material has at least one of the following technical features:
(1) The acrylic compound is at least one selected from acrylic acid and methacrylic acid;
(2) The acrylic acid salt compound is at least one selected from sodium acrylate, potassium acrylate, sodium methacrylate and potassium methacrylate;
(3) The acrylamide compound is at least one selected from acrylamide and methacrylamide;
(4) The cross-linking agent is at least one selected from ethylene glycol diglycidyl ether, N' -methylene dipropionamide, N-vinyl-2-pyrrolidone and ethylene glycol diacrylate;
(5) The nucleating agent is at least one selected from nano zinc oxide, nano aluminum oxide, nano silicon carbide and carbon nano tubes;
(6) The corrosion inhibitor is at least one selected from nitrite, chromate, phosphate, silicate and benzoate.
In a second aspect of the present application, a method for preparing a flexible phase change cold storage material is provided, comprising the steps of:
Preparing raw materials according to the formula of the flexible phase change cold storage material provided by the first aspect of the application;
taking the inorganic salt aqueous solution, optionally adding the other additives, and mixing to prepare a first solution;
adding the hydrophilic polymer into the first solution under a first dispersion condition, and mixing to prepare a first gel;
the crosslinking degree enhancer is added to the first gel under a second dispersion condition.
In some of these embodiments, the hydrophilic polymer is prepared by an emulsion polymerization process;
and adding the modified nucleating agent in the emulsion polymerization process for copolymerization.
In some of these embodiments, the modified nucleating agent is prepared by steps comprising the following preparation method:
dispersing the nucleating agent in an organic solvent, adding a silane coupling agent, mixing, carrying out ultrasonic treatment, and heating to 80-90 ℃ for reaction.
In some embodiments, the preparation method has at least one of the following preparation conditions:
(1) The first dispersion condition includes: stirring at 30 r/min-100 r/min;
(2) The second dispersion condition includes: stirring at 30 r/min-100 r/min;
(3) The first dispersing time is 0.5-2 hours;
(4) The second dispersing time is 0.5 h-3.5 h.
In a third aspect, the present application provides a frozen type cold storage agent, which contains the flexible phase change cold storage material provided in the first aspect of the present application or the flexible phase change cold storage material prepared by the preparation method provided in the second aspect of the present application.
According to a fourth aspect of the present application, there is provided a cool storage agent for storing a lithography material, comprising the flexible phase change cool storage material according to the first aspect of the present application, or the flexible phase change cool storage material prepared by the preparation method according to the second aspect of the present application.
In some embodiments, the photoresist comprises photoresist, an anti-reflection coating, a spin-on carbon hard mask and a spin-on glass hard mask.
In a fifth aspect of the present application, there is provided a flexible cold storage pack comprising a sealed package and a cold storage agent filled in the sealed package;
the cold accumulation agent contains the flexible phase change cold accumulation material provided by the first aspect of the application or the flexible phase change cold accumulation material prepared by the preparation method provided by the second aspect of the application.
The flexible phase change cold storage material provided by the application has the advantages that the particle-shaped modified nucleating agent is dispersed in the hydrophilic polymer structure, and the crosslinking degree reinforcing agent and the hydrophilic polymer form a dual-network interpenetrating conformation, so that the problems of low phase change latent heat, easy release of free water, difficult dispersion of the particle-shaped nucleating agent, high packaging design requirement and the like of the conventional inorganic salt phase change cold storage gel are solved, the high phase change latent heat and high recycling stability are shown, and the specific and durable low-temperature environment of the photoetching material can be ensured in the storage and transportation process.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a comparison result of the flexible setting effect of the phase change regenerator gel of example 1 and comparative example 1 according to the present application, a of fig. 1 is the phase change regenerator gel prepared in example 1, and B of fig. 1 is the phase change regenerator gel prepared in comparative example 1.
Detailed Description
The application is further illustrated below in conjunction with the embodiments, examples and figures. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of the application, and such equivalents are intended to fall within the scope of the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
herein, "preferred", "better", etc. are merely embodiments or examples that describe better results, and it should be understood that they do not limit the scope of the application.
In the present application, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the application.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. When a numerical range merely points to integers within the numerical range, both end integers of the numerical range are included, as well as each integer between the two ends, unless expressly stated otherwise. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations in a range such as + -5 deg.C, + -4 deg.C, + -3 deg.C, + -2 deg.C, + -1 deg.C.
In the present application, the weight may be a weight unit known in the chemical industry such as mu g, mg, g, kg.
In the present application, the dimensions, particle diameter and diameter are generally average values, unless otherwise specified.
In the present application, the terms "first", "second", "third", "fourth", "fifth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of the indicated technical features. Also, "first," "second," "third," "fourth," "fifth," etc. are for non-exhaustive list of descriptive purposes only and are not to be construed as limiting the number of closed forms.
In a first aspect of the present application, there is provided a flexible phase change cold storage material comprising suitable amounts of an aqueous inorganic salt solution, a hydrophilic polymer and a crosslinking degree enhancer, optionally together with other additives, the components interacting to provide the material with high latent heat of phase change properties, long lasting stability and flexible styling effect.
In some embodiments, the flexible phase change cold storage material has at least one of the following characteristics:
(1) The phase-change potential heat value is 230 kJ/kg-300 kJ/kg;
(2) The phase transition temperature is-15 ℃ to-5 ℃;
(3) The absolute value of the supercooling degree is 0.5-1.5 ℃;
(4) The sum of the contents of the non-latent heat functional components can be 0.5% -20%.
The flexible phase change cold storage material has a phase change latent heat value of more than 230kJ/kg, further 230 kJ/kg-300 kJ/kg, further 250 kJ/kg-300 kJ/kg and good cold storage effect. In one embodiment, the phase change latent heat value of the flexible phase change cold storage material is selected from 230 kJ/kg-300 kJ/kg, 230 kJ/kg-240 kJ/kg, 232 kJ/kg-252 kJ/kg, 250 kJ/kg-260 kJ/kg, 255 kJ/kg-275 kJ/kg, 270 kJ/kg-290 kJ/kg, 280 kJ/kg-300 kJ/kg and the like, and the phase change latent heat value is exemplified by 251.35kJ/kg, 251.28kJ/kg, 258.02kJ/kg, 270.19kJ/kg, 236.44kJ/kg and the like.
The phase transition temperature of the flexible phase transition cold storage material is below 0 ℃, and further can be-15 ℃ to-5 ℃, and the flexible phase transition cold storage material can be applied to storage and transportation of substances with high chemical activity, such as photoetching materials and the like.
In one embodiment, the phase transition temperature of the flexible phase change cold storage material is selected from the group consisting of-15 to-5 ℃, -15 to-10 ℃, -13 to-10 ℃, -12 to-8 ℃, -10 to-5 ℃, and the like, and the phase transition temperature is exemplified by-11.81 ℃, -11.64 ℃, -10.81 ℃, -13.11 ℃, -9.86 ℃ and the like.
The flexible phase change cold storage material has low supercooling degree, the absolute value of the supercooling degree can be less than 1.5 ℃, and further can be 0.5-1.5 ℃. Supercooling means that liquid substances are not crystallized when cooled to a theoretical freezing point, but are required to be cooled to be below the theoretical freezing point to start crystallization, and the existence of supercooling ensures that the phase change material needs lower cold source temperature and more energy consumption when being charged for cooling. The supercooling degree is the difference between the theoretical solidification temperature and the actual solidification temperature.
In one embodiment, the absolute value of the supercooling degree of the flexible phase change cold storage material is selected from 0.5 ℃ to 1.5 ℃, 0.5 ℃ to 0.8 ℃, 0.6 ℃ to 0.9 ℃, 0.8 ℃ to 1.2 ℃, 0.9 ℃ to 1.5 ℃, 1.2 ℃ to 1.5 ℃, etc., and the absolute value of the supercooling degree is exemplified as 0.53 ℃, 1.02 ℃, 0.83 ℃, 0.78 ℃, 0.69 ℃, etc.
The flexible phase change cold storage material has higher cold storage density, can contain inorganic salt water solution (latent heat functional components) with higher content according to weight percentage, can contain the sum of the contents of the rest non-latent heat functional components to be 0.5% -20%, can further contain 2% -10%, can not cause deterioration of water absorption effect due to the excessively high content of the inorganic salt water solution, well maintains the flexibility of the material in freezing and thawing, and has excellent cycle stability.
The cycling stability of the flexible phase change cold storage material can be embodied according to the cycle times of freezing and thawing and the water retention state and the phase change latent heat change value of the material after the cycle of freezing and thawing.
In one embodiment, after 100 cycle tests, the change rate of the phase change latent heat of the flexible phase change cold storage material is less than 3%, and further can be 1% -3%.
In one embodiment, after 100 times of cycle test, the flexible phase change cold storage material has no free water exudation and good water retention.
In some more preferred embodiments, the flexible phase change cold storage material has a phase change latent heat value of 250kJ/kg to 300kJ/kg, a phase change temperature of-15 ℃ to-10 ℃, and an absolute value of supercooling degree of 0.5 ℃ to 1.1 ℃; further, after 100 cooling/thawing cycle tests, the phase change latent heat change rate of the phase change cold storage gel is less than 3%, and the problems of cold storage failure and free water exudation are avoided, so that the phase change cold storage gel has high phase change latent heat and high cycle stability. The flexible phase change cold storage material comprises the following components in percentage by weight:
80-99.5% of inorganic salt water solution,
0.5-10% of hydrophilic polymer,
0.1% -5% of crosslinking degree reinforcing agent and
0-1% of other additives;
further, the inorganic salt aqueous solution comprises inorganic salt and water, wherein the weight of the inorganic salt accounts for 3% -40% of the total weight of the inorganic salt aqueous solution;
the hydrophilic polymer is formed by copolymerizing a mixed monomer, a modified nucleating agent and a crosslinking agent; the mixed monomer comprises the following components in a molar ratio of 1: (3-8): (0.05-0.5) an acrylic compound, an acrylic salt single compound and an acrylamide monomer; the modified nucleating agent is a product obtained by carrying out functional group surface modification treatment on the nucleating agent by adopting a silane coupling agent, wherein the modified nucleating agent contains 0.5% -5% of modified groups by weight of the total weight of the modified nucleating agent;
the crosslinking degree reinforcing agent is nano silicon dioxide with the particle size of 10 nm-80 nm;
other additives include corrosion inhibitors.
Inorganic salt water solution
In one embodiment, the inorganic salt in the aqueous inorganic salt solution may be selected from one or a combination of two or more of chlorides; the inorganic salt aqueous solution formed by the chloride has high phase transition latent heat, and the phase transition temperature accords with the low-temperature storage and transportation temperature range (-15 ℃ to-5 ℃) of the photoetching material containing high chemical active groups.
Preferably, the inorganic salt may be selected from one or a combination of two or more of sodium chloride, potassium chloride, ammonium chloride, and barium chloride. In some embodiments, the weight of the inorganic salt is 3% -40% of the total weight of the inorganic salt aqueous solution; further, the weight of the inorganic salt accounts for 5% -35% of the total weight of the inorganic salt aqueous solution; still further, the weight of the inorganic salt is 8% -25% of the total weight of the inorganic salt aqueous solution.
In some embodiments, the weight of the inorganic salt aqueous solution is 80% -99.5% of the total weight of the flexible phase change cold storage material; further, the weight of the inorganic salt aqueous solution is 82.7% -99.2% of the total weight of the flexible phase change cold storage material, and further, the weight of the inorganic salt aqueous solution is 86.6% -98.5% of the total weight of the flexible phase change cold storage material.
In some embodiments, the weight of the inorganic salt aqueous solution is 90% -95% of the total weight of the flexible phase change cold storage material, further may be 92% -94%, and preferably the inorganic salt is potassium chloride.
Hydrophilic polymers
Hydrophilic polymers play an important role in the absorption of water in the composite. Before the inorganic salt water solution is absorbed, the macromolecular chains in the polymer are mutually close to each other, and the whole fastening state is presented; when the hydrophilic polymer is contacted with the inorganic salt water solution, the high molecular chains in the polymer stretch, water molecules enter the polymer network structure, and the polymer volume expands to form hydrogel.
In the application, the hydrophilic polymer is formed by copolymerizing a mixed monomer, a modified nucleating agent and a crosslinking agent. Propionic acid compounds and acrylamide compounds can provide active sites for the hydrophilic polymer to form hydrogen bonds with water; the acrylate compound can provide active sites for ionization of the hydrophilic polymer in water; the cross-linking agent can provide cross-linking sites for the linearly polymerized acrylic polymer segments to form a polymer three-dimensional cross-linked network; the nucleating agent has the functions of reducing supercooling degree of inorganic salt water solution in the cooling process, and the modified nucleating agent also has the comprehensive functions of improving stability, flexible deformation and latent heat of phase change.
In some embodiments, the molar ratio of acrylic, acrylate, and acrylamide is 1: (3-8): (0.05 to 0.5).
In some embodiments, the molar amount of the crosslinker is 0.05% -0.5% of the molar amount of the acrylic compound.
Alternatively, the acrylic compound is selected from one or a combination of two or more of acrylic acid and methacrylic acid.
Optionally, the acrylate compound is selected from one or more than two of sodium acrylate, potassium acrylate, sodium methacrylate and potassium methacrylate.
Optionally, the acrylamide compound is selected from one or more than two of acrylamide and methacrylamide.
Optionally, the cross-linking agent is selected from one or more than two of ethylene glycol diglycidyl ether, N' -methylene dipropionamide, N-vinyl-2-pyrrolidone and ethylene glycol diacrylate.
Further, the chemical bond linking of the modified nucleating agent in the structural backbone or branch of the hydrophilic polymer has two roles in linking the modified nucleating agent to the structure of the hydrophilic polymer: firstly, the pre-dispersion of the granular nucleating agent in the hydrophilic polymer structure is realized, so that the nucleating agent obtains more uniform dispersion effect in the low-temperature cold storage gel; and secondly, the tight connection between the hydrophilic resin and the nucleating agent is realized, so that the sedimentation of the nucleating agent in a gel system and the agglomeration among nucleating agent particles caused by repeated freezing of the gel are avoided.
In some embodiments, the weight of the modified nucleating agent is 0.05% to 0.5% of the total weight of the mixed monomers.
In some embodiments, the modified nucleating agent is the product of a functional group surface modification treatment of the nucleating agent with a silane coupling agent.
In some embodiments, the weight of the grafting group in the modified nucleating agent is 0.5% -5% of the weight of the modified nucleating agent.
In some embodiments, the silane coupling agent is selected from one of KH560 and KH 570.
In some embodiments, the nucleating agent is selected from one or a combination of two or more of nano zinc oxide, nano aluminum oxide, nano silicon carbide, carbon nanotubes.
In some embodiments, the weight of the hydrophilic polymer is 0.5% -10% of the total weight of the flexible phase change cold storage material; further, the weight of the hydrophilic polymer is 1% -9% of the total weight of the flexible phase change cold storage material; still further, the weight of the hydrophilic polymer is 2% -8% of the total weight of the flexible phase change cold storage material.
Crosslinking degree enhancer
The application adopts nano silicon dioxide with proper particle size as crosslinking degree reinforcing agent. The silicon hydroxyl structure on the surface of the nano silicon dioxide can form a large number of hydrogen bonds with water molecules in inorganic salt water solution, and can be combined with partial group structures (such as carboxyl groups) in the hydrophilic polymer in a hydrogen bond mode, so that a hydrogen bond network with certain structural rigidity is constructed, the hydrogen bond network is interpenetrated with the hydrophilic polymer cross-linked network, and the water molecules are further fixed in a gel system, so that the possibility of water molecule exudation in the phase-change gel is reduced. The phase change cold accumulation gel can maintain stable phase change thermal performance in the long-term cyclic use process, and the cyclic use times of the phase change cold accumulation gel are increased.
The three-dimensional network conformation formed by the nano silicon dioxide and the water molecules and based on hydrogen bonds can enhance the binding force between the water molecules, further repair the damage of the hydrophilic polymer added to the binding capacity between partial water molecules in the inorganic salt water solution, and improve the phase change latent heat of the phase change gel.
The nano silicon dioxide can be interpenetrated with a hydrophilic polymer network through forming a silicon hydroxyl-water molecule network with certain structural rigidity based on hydrogen bonds, so that the binding force between phase change cold accumulation gel particles can be improved, the loose binding state between the phase change cold accumulation gels is avoided, and the effect of improving the flexible solid phase shaping effect of the phase change cold accumulation gels is achieved.
When the particle size of the nano silicon dioxide is smaller than 10nm, the difficulty is high from the viewpoint of the preparation technology, and the economic cost is high; when the particle diameter of the nano silica is larger than 80nm, the nano silica particles have a large size and a relatively small specific surface area, and it is difficult to achieve an ideal uniform dispersion effect.
In some embodiments, the nano-silica has a particle size of 10nm to 80nm; further, the particle size of the nano silicon dioxide is 20 nm-50 nm.
In some embodiments, the weight of the nano silicon dioxide is 0.1% -5% of the flexible phase change cold storage material; further, the weight of the nano silicon dioxide is 0.3% -3% of that of the flexible phase change cold storage material; still further, the weight of the nano silicon dioxide is 0.5% -3% of that of the flexible phase change cold storage material.
Other additives
The flexible phase change cold storage material of the application can optionally contain a corrosion inhibitor or not.
Alternatively, the corrosion inhibitor may be selected from any one or a combination of two or more of nitrite, chromate, phosphate, silicate, benzoate. When the flexible phase change cold storage material is contacted with common metals (such as copper, aluminum and steel), the corrosion inhibitor contained in the flexible phase change cold storage material can slow down the corrosion process of inorganic salt medium on the metals. For example, if sodium benzoate is selected as a corrosion inhibitor, the corrosion process of the phase change cold storage gel to metals such as brass, red copper and the like can be slowed down; if sodium chromate is used as corrosion inhibitor, the corrosion process of the phase change cold accumulation gel to steel metal can be slowed down.
In some embodiments, the weight of the corrosion inhibitor is 0.1% -1% of the weight of the inorganic salt aqueous solution in the flexible phase change cold storage material.
In some embodiments, the flexible phase change cold storage material is comprised of the following components in weight percent: 80% -99.5% of inorganic salt water solution, 0.5% -10% of hydrophilic polymer, 0.1% -5% of crosslinking degree enhancer and 0% -1% of other additives;
further, as long as the sum of the weight percentages of the components is 100%, the weight percentage of the inorganic salt aqueous solution in the flexible cold storage material may be independently selected from 80% -99.5%, further may be selected from 92% -94%, for example, 80%, 92%, 92.54%, 93%, 93.53%, 94%, 99.5%, etc.; the weight percentage of the hydrophilic polymer in the flexible cold accumulation material can be independently selected from 0.5% -10%, further can be selected from 2% -8%, for example, 0.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10% and the like; the weight percentage of the crosslinking degree enhancer in the flexible cold storage material can be independently selected from 0.1% -5%, further can be selected from 0.5% -3%, for example, 0.1%, 0.5%, 1%, 2%, 3%, 5% and the like; the weight percentage of other additives in the flexible cold accumulation material can be independently selected from 0-1%, further can be selected from 0.4% -0.5%, for example, 0, 0.4%, 0.46%, 0.47%, 0.5%, 1% and the like;
Still further, the inorganic salt aqueous solution is selected from at least one of potassium chloride and barium chloride solution; the crosslinking degree enhancer is at least one selected from nano silicon dioxide with the particle size of 30nm, nano silicon dioxide with the particle size of 80nm and carboxymethyl cellulose; in the technical scheme that the slow release agent exists, the slow release agent is selected from sodium benzoate; the hydrophilic polymer is selected from the hydrophilic polymers described in any of the above embodiments.
In one embodiment, the flexible phase change cold storage material is composed of the following components in percentage by weight:
18.7% of the inorganic salt, 74.83% of the water, 5% of the hydrophilic polymer, 1% of the crosslinking degree enhancer, and 0.47% of the corrosion inhibitor; or alternatively, the first and second heat exchangers may be,
18.51% of the inorganic salt, 74.03% of the water, 5% of the hydrophilic polymer, 2% of the crosslinking degree enhancer, and 0.46% of the corrosion inhibitor; or alternatively, the first and second heat exchangers may be,
18.7% of the inorganic salt, 74.83% of the water, 4% of the hydrophilic polymer, 2% of the crosslinking degree enhancer, and 0.47% of the corrosion inhibitor; or alternatively, the first and second heat exchangers may be,
9.35% of the inorganic salt, 84.18% of the water, 5% of the hydrophilic polymer, 1% of the crosslinking degree enhancer, and 0.47% of the corrosion inhibitor; or alternatively, the first and second heat exchangers may be,
20.58% of the inorganic salt, 72.95% of the water, 5% of the hydrophilic polymer, 1% of the crosslinking degree enhancer, and 0.47% of the corrosion inhibitor.
In a second aspect of the present application, a method for preparing a flexible phase change cold storage gel is provided, which can be used to prepare the flexible phase change cold storage material provided in the first aspect of the present application, wherein the flexible phase change cold storage material has high phase change latent heat and has durable stability and flexible shaping effect.
In some embodiments, a method of preparing a flexible phase change cold storage material includes the steps of:
s100: preparing raw materials according to the formula of the flexible phase change cold storage material provided by the first aspect of the application;
s200: taking an inorganic salt aqueous solution, optionally adding other additives, and mixing to prepare a first solution;
s300: adding a hydrophilic polymer into the first solution under a first dispersion condition, and mixing to prepare a first gel;
s400: under second dispersion conditions, a crosslinking degree enhancer is added to the first gel.
S100, raw material preparation:
the features of each raw material are as stated in the first aspect of the present application, and are not described in detail herein.
In some embodiments, the modified nucleating agent is prepared by steps comprising the following preparation method: dispersing a nucleating agent in an organic solvent, adding a silane coupling agent, mixing, carrying out ultrasonic treatment, and heating to 80-90 ℃ for reaction.
In some embodiments, the hydrophilic polymer is prepared by an emulsion polymerization process; and adding a modified nucleating agent in the emulsion polymerization process for copolymerization. The nucleation agent is connected in the main chain or branched chain of the hydrophilic polymer structure in a chemical bond mode, so that the nucleation agent can be dispersed in the inside of the hydrophilic polymer structure in advance, and the nucleation agent and the hydrophilic polymer can be connected in a chemical bond mode, thereby avoiding sedimentation and agglomeration of the nucleation agent in gel due to repeated freeze thawing.
In some embodiments, the conditions of the first dispersion include: stirring at 30 r/min-100 r/min, further 30 r/min-80 r/min, for example, stirring speeds such as 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, etc.
In some embodiments, the first dispersing time is 0.5h to 2h, for example, the first dispersing time is 0.5h, 1h, 1.5h, 2h, etc.
In some embodiments, the conditions of the second dispersion include: stirring at 30 r/min-100 r/min, further 30 r/min-80 r/min, for example, stirring speeds such as 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, etc.
In some embodiments, the second dispersing time is 0.5h to 3.5h, for example, the second dispersing time is 0.5h, 1.5h, 2.5h, 3.5h, etc.
In some embodiments, the hydrophilic polymer is prepared by the steps comprising:
the aqueous acrylic acid solution was placed in a reaction vessel, and an alkali solution was added dropwise to the reaction vessel while cooling the reaction vessel with ice from the outside under mechanical stirring, whereby a molar ratio of acrylic acid to acrylic acid salt of 1 was obtained: the mixed solution of (3-8) is added with an aqueous solution of acrylamide and an initiator to prepare an acrylic compound, an acrylic salt single compound and an acrylamide monomer, wherein the molar ratio of the acrylic compound to the acrylic salt single compound to the acrylamide monomer is 1: (3-8): (0.05-0.5) a mixed monomer solution;
dispersing modified nano alumina in n-heptane at high speed to form modified nano alumina suspension;
mixing n-heptane and ethyl cellulose, heating to 70 ℃ in a water bath under the protection of nitrogen and reflux, and simultaneously dropwise adding a mixed monomer solution and a modified nano alumina suspension to react for 1-2 h; then heating to 120-130 ℃, and extracting water from the reaction system while refluxing the n-heptane by azeotropy of the n-heptane and the water; and then cooling to 70-80 ℃, adding an N, N' -methylene dipropionamide aqueous solution, and continuing to keep the temperature for 1-3 hours.
In a third aspect of the present application, there is provided a frozen type regenerator comprising the flexible phase change regenerator material provided in the first aspect of the present application or the flexible phase change regenerator material produced by the production method provided in the second aspect of the present application.
In one embodiment, the chilled coolant is suitable for freezing requirements at-15 ℃ to-5 ℃.
According to a fourth aspect of the present application, there is provided a cool storage agent for storing a lithography material, comprising the flexible phase change cool storage material according to the first aspect of the present application, or the flexible phase change cool storage material prepared by the preparation method according to the second aspect of the present application.
The photoetching material is an upstream key material of a printed circuit board, a liquid crystal display screen and a semiconductor industry chain, the components of the photoetching material often contain a large number of active group structures, and the groups are easy to crosslink or fall off so as to influence the use effect of the material, so that the storage and transportation conditions and the use period of the photoetching material product need to be strictly limited, and the storage and transportation temperature of the photoetching material product containing the high-chemical active group structure needs to be controlled within the range of-15 ℃ to 0 ℃ or even lower. Exemplary lithographic materials include Photoresist (PR), anti-reflective coating (ARC), spin-on carbon (SOC) hard masks, spin-on Glass (SOG) hard masks, and the like, used during the lithographic process.
The cold storage agent for storing and transporting the lithography material contains the flexible phase-change cold storage material according to any one of the technical schemes or the flexible phase-change cold storage material prepared by the preparation method according to any one of the technical schemes, has stable phase-change temperature, has the phase-change temperature of-15 ℃ to-5 ℃, and can prevent the lithography material from deteriorating during storage and transportation.
In a fifth aspect of the present application, there is provided a flexible cold storage pack comprising a sealed package and a cold storage agent filled in the sealed package; the cold accumulation agent contains the flexible phase change cold accumulation material provided by the first aspect of the application or the flexible phase change cold accumulation material prepared by the preparation method provided by the second aspect of the application. The cold storage agent has high cold storage density and high recycling stability, has the characteristic of variable shape under normal temperature, and can be flexibly filled in the space around the package of active materials such as photoetching materials according to actual needs.
In one embodiment, the sealing packaging material may be selected from polyethylene, polyester, polycarbonate or polypropylene, which has certain flexibility and elasticity, and can enable the flexible phase change cold storage material to be in close contact with the sealing bag, so that heat exchange between the cold storage bag and the object to be stored and transported is facilitated.
The following are some specific examples.
The starting materials and reagents referred to in the following specific examples may be obtained commercially or may be prepared by known means by those skilled in the art.
The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the present document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.
1. Raw material for providing flexible phase change cold storage material
1.1. Preparation of modified nucleating agents
0.5g of nano alumina is weighed, 30mL of ethyl acetate is added, the mixture is mechanically stirred and mixed, and then the mixture is placed in an ultrasonic cleaner at normal temperature for ultrasonic dispersion for 30min, so as to obtain nano alumina suspension. 10g of aqueous solution of a silane coupling agent KH570 with the mass fraction of 0.5% is added into the nano alumina suspension, and the ultrasonic treatment is continued for 5min. The reaction solution was transferred to a flask equipped with a reflux condenser, reacted at 80℃for 5 hours, cooled to room temperature, and filtered to obtain a precipitate. The precipitate was washed with ethyl acetate to form a dispersion, the dispersion was transferred to a centrifuge tube, centrifuged at room temperature at 12000r/min, and the resulting precipitate was washed with deionized water and centrifuged. And (3) placing the obtained product in a vacuum drying oven and drying at 40 ℃ for 24 hours to obtain the product, namely the modified nano alumina.
The weight percentage of the grafting group in the modified nano alumina is measured by adopting a thermogravimetric analysis method, and the testing conditions are as follows: the temperature rising rate is 10 ℃/min, and the test temperature is 25-800 ℃. The measurement result is that the group accounts for 1.562% of the weight of the modified nano alumina.
1.2. Preparation of hydrophilic polymers
1.2.1. Preparation of hydrophilic Polymer HP-01
94g (1.044 mol) of an aqueous solution of acrylic acid having a weight fraction of 80% was placed in a 500mL flask, and 127g (0.794 mol) of an aqueous solution of sodium hydroxide having a weight fraction of 25% was added dropwise to the flask while ice-cooling the flask from the outside under mechanical stirring, whereby a molar ratio of acrylic acid to sodium acrylate of 1:3.17, and then 0.9g (0.0025 mol) of an aqueous acrylamide solution having a mass fraction of 20wt% and 0.15g of potassium persulfate were added to the flask to prepare an aqueous monomer solution. 0.1g of modified nano-alumina was taken and placed in 50g of n-heptane to be dispersed at high speed to form a suspension.
Into a 1L flask, 448g of n-heptane and 3.0g of ethylcellulose were added, and the mixture was stirred and stirred, and the temperature was raised to 70℃in a water bath under nitrogen protection and reflux.
The monomer solution was slowly added dropwise to the flask over a period of 1h. In this procedure, a suspension of modified nano alumina was simultaneously added dropwise to the flask for 10min.
After all reactants were added dropwise, the reaction was continued for 1.5 hours. The reaction flask was placed in an oil bath at 125℃and water was withdrawn from the reaction system while refluxing n-heptane by azeotropy of n-heptane and water. The reaction temperature was then reduced to 75℃and 5.775g (0.75X10 g) -3 mol) N, N' -methylene dipropionamide aqueous solution with the weight content of 2 percent, and the temperature is kept for 2 hours and is cooled.
The obtained product is placed in a vacuum oven at 80 ℃ for drying, and the large particles are crushed, and the obtained product is the hydrophilic polymer which is marked as HP-01.
1.2.2. Preparation of hydrophilic Polymer HP-02
The preparation procedure refers to the preparation method of HP-01, except that modified nano alumina is not synthesized, 0.1g of nano alumina is used for replacing 0.1g of modified nano alumina in the synthesis process of the hydrophilic polymer, and the obtained hydrophilic polymer is named HP-02.
1.2.3. Preparation of hydrophilic Polymer HP-03
The preparation steps refer to the preparation method of HP-01, and the difference is that nano alumina and modified nano alumina are not added in the synthesis process of the hydrophilic polymer. The hydrophilic polymer obtained was designated HP-03. The weight average molecular weight of the hydrophilic polymer HP-03 was 15000 as determined by gel permeation chromatography. (HP-01 and HP-02 polymer structures contain inorganic nanoparticles, and cannot be used for determining molecular weight by gel chromatography)
1.2.4. Preparation of hydrophilic Polymer HP-04
Preparation procedure referring to the preparation method of HP-01, the difference is that 0.05g of modified nano alumina was added to the reaction system instead of 0.1g of nano modified alumina during the synthesis of the hydrophilic polymer, and the obtained hydrophilic polymer was designated HP-04.
2. Preparation of flexible phase change cold storage material
2.1. Preparing raw materials
The raw materials for preparing each component are weighed according to the proportion in tables 1 and 2, and the total weight of the raw materials is 1kg, wherein:
the inorganic salt is selected from potassium chloride and barium chloride.
The hydrophilic polymer is selected from hydrophilic resin HP-01, HP-02, HP-03 and HP-04, wherein the hydrophilic resin HP-01 contains a modified nucleating agent, the hydrophilic resin HP-02 contains a nucleating agent, the hydrophilic resin HP-03 does not contain a modified nucleating agent and a nucleating agent, and the HP-04 contains a small amount of modified nucleating agent; the nucleating agent is nano alumina; the modified nucleating agent is nano alumina grafted by a silane coupling agent KH 570.
The crosslinking degree enhancer is selected from nanosilica (CS-01) with average particle diameter of 30nm, nanosilica (CS-02) with average particle diameter of 80nm, and carboxymethyl cellulose (CS-03).
The corrosion inhibitor is sodium benzoate.
The preparation process of the phase-change gel is carried out at normal temperature.
The rotating speed of mechanical stirring is controlled to be 30 r/min-100 r/min.
The mechanical stirring time for forming the first solution was 1.5h, the mechanical stirring time for forming the first gel was 1h, and the mechanical stirring time for forming the second gel was 1.5h.
Table 1. Raw material ratios of preparation examples of flexible phase change cold storage materials.
Table 2. Raw material ratios of comparative examples were prepared from flexible phase change cold storage materials.
2.2. Preparation of flexible phase change cold storage material
The preparation process of the flexible phase change cold storage material is carried out at normal temperature, and specifically comprises the following steps:
(1) Dissolving inorganic salt in deionized water, stirring for 1.5h at 80r/min to obtain inorganic salt water solution, adding corrosion inhibitor, mixing, and stirring for 1.5h at 80r/min to obtain a first solution;
(2) Mixing the first solution with the hydrophilic polymer, and stirring for 1h at 40r/min to prepare a first gel;
(3) The first gel and the crosslinking enhancer were mixed and stirred at 40r/min for 1.5h.
3. Performance testing
The phase-change thermal properties and the cycle stability of the flexible phase-change cold storage materials prepared in examples and comparative examples were tested and evaluated by the following methods. The specific method comprises the following steps:
3.1. and testing the phase change thermal performance of the flexible phase change cold storage material.
The phase change thermal properties of the flexible phase change cold storage material mainly comprise the phase change temperature, the phase change latent heat and the supercooling degree of the flexible phase change cold storage material.
The phase change latent heat of the flexible phase change cold storage material is measured by adopting a differential calorimetric scanning method. The method comprises the following steps: the flexible phase change cold storage materials prepared in the examples and the comparative examples are respectively taken as samples, the mass of the samples can be 3 mg-8 mg, each sample is placed in a sealed aluminum crucible, and then the samples are respectively tested by using a differential calorimeter scanner (model T25, manufactured by TA company). The temperature range of the test is-50-40 ℃, the temperature rising rate of the test is 10 ℃/min, nitrogen is used as the protective gas, and the flow rate of the nitrogen is 50mL/min. The test shows that the heat flux density vs. temperature curve and the heat flux density vs. time curve of the obtained sample can be obtained. And integrating the area of the phase-change endothermic peak in the heat flow density vs. time curve to obtain the peak area of the phase-change endothermic peak, namely the phase-change latent heat of the sample.
Considering that the heat flow density vs. temperature curve obtained in the differential scanning calorimetric test process of the flexible phase change cold storage materials prepared in the embodiment and the comparative example of the application shows a relatively large peak width of the phase change peak, and the temperature rising rate in the test process is too fast, the phase change temperature of the flexible phase change cold storage material is not accurate by adopting the traditional test method to select the initial temperature point of the phase change peak as the phase change temperature of the flexible phase change cold storage material, so the phase change temperature of the flexible phase change cold storage material in the embodiment and the comparative example of the application is measured through the step-by-step thermal curve of the flexible phase change cold storage material. The supercooling degree of the flexible phase change cold storage material is measured through the step cooling curve of the flexible phase change cold storage material.
The testing steps of the step heating and step cooling curve of the flexible phase change cold storage material are as follows: the flexible phase change cold storage materials prepared in the examples and comparative examples with a weight of 40g were placed in a 100mL polyethylene test tube at room temperature, sealed and placed on a test tube rack. The temperature of the gel is measured by extending a T-shaped thermocouple probe with the diameter of 0.5mm into a flexible phase change cold storage material in a measuring test tube. The test tube rack with the test sample placed therein was placed in a refrigerator having a refrigerating temperature of-30 ℃. In the test tube filled with the flexible phase change cold storage material, the other end of the T-shaped thermocouple probe for measuring the temperature is connected with a thermocouple wire, the thermocouple wire penetrates out of the refrigerator door and is connected with a data acquisition instrument to record the temperature value acquired by the probe. The interval time of the data recording is 10s. The temperature-time curve (namely the step cooling curve of the flexible phase change cold storage material) of the flexible phase change cold storage material in the process of reducing the room temperature to the refrigerating temperature of the refrigerator can be obtained by the method. And taking the test tube which is provided with the flexible phase-change cold storage material and is connected with the thermocouple out of the refrigerator and placing the test tube under the room temperature condition, so that the flexible phase-change cold storage material naturally heats up, and the recorded temperature-time curve of the flexible phase-change cold storage material in the process is the step-by-step heating curve of the flexible phase-change cold storage material. And (3) carrying out data processing on the step-by-step heat curve of the obtained flexible phase-change cold storage material sample, wherein the temperature corresponding to the intersection point of the tangent line of the sharp temperature rising curve and the tangent line of the phase-change constant temperature (or near constant temperature) section curve before the phase-change constant temperature (or near constant temperature) section is reached in the step-by-step heat curve is recorded as T1, and the phase-change temperature of the flexible phase-change cold storage material is obtained. And processing a step cooling curve of the flexible phase change cold storage material sample. The starting point temperature of the phase change platform in the step-by-step cooling curve is recorded as T2, and the supercooling degree of the flexible phase change cold storage material sample can be obtained through calculation according to a formula 1:
Equation 1:
；
3.2. testing and evaluating the cycle stability of flexible phase change cold storage materials
The quality of the cycle stability of the flexible phase change cold storage material is mainly evaluated by testing whether the flexible phase change cold storage material has the change of the phase change latent heat value, the cold storage failure and the liquid water exudation after a plurality of cooling/heating cycle tests.
The cold and hot circulation test method of the flexible phase change cold storage material sample comprises the steps of firstly, respectively placing the flexible phase change cold storage materials prepared in the examples and the comparative examples in a 100mL polyethylene test tube at room temperature, placing a thermocouple probe in the test tube, and then sealing the test tube. Transferring the test tube into a refrigerator with the refrigeration temperature of minus 30 ℃ for 7 hours, freezing until the flexible phase change cold storage material is completely changed into white solid, and then taking out the test tube, placing the test tube into normal temperature for thawing for 6 hours until the flexible phase change cold storage material is completely changed into semitransparent gel. The repeated freezing/thawing operation of the test tube makes the flexible phase change cold storage material perform repeated cooling/heating cycles with the repetition number of 100 times.
Taking a 100-cycle flexible phase change cold storage material sample, measuring the phase change latent heat value of the sample by adopting a differential scanning calorimetry method, and recording as H2, test is not passedThe phase change potential heat value of the flexible phase change cold storage material sample subjected to the phase change cycle test is recorded asH1, the change rate of the phase change latent heat value of the flexible phase change cold storage material before and after the cyclic test can be obtained through calculation of a formula 2:
equation 2:
；
determination of phase change latent heat variation evaluation of flexible phase change cold storage material in cyclic test process:
comparing the temperature-time curve of the flexible phase change cold storage material in the cooling process of each test cycle, and judging that the flexible phase change cold storage material stores cold successfully in the cycle if a constant temperature platform appears in the temperature-time curve of the flexible phase change cold storage material in the cooling process of any cycle; if the constant temperature platform does not appear in the temperature-time curve of the cooling process of the flexible phase change cold storage material in any cycle, judging that the flexible phase change cold storage material fails to store cold in the cycle.
Whether the flexible phase change cold storage material subjected to 100 times of cycle tests has free water exudation can be judged by naked eye observation.
The test results of the flexible phase change cold storage materials prepared in the above examples and comparative examples are shown in table 3.
Table 3. Performance test results data for flexible phase change cold storage materials.
As can be seen from Table 3, the phase change cold storage gel obtained in each of examples (examples 1 to 5) has a latent heat value of phase change of more than 230kJ/kg, a phase change temperature controlled within a range of-15 ℃ to-5 ℃, a supercooling degree of less than 1.1 ℃, a change rate of latent heat of phase change of the phase change cold storage gel after 100 cooling/thawing cycle tests of less than 3%, and has no problems of cold storage failure and free water exudation, and exhibits high latent heat of phase change and high cycle stability.
In comparison with any one of examples 1 to 5, the phase change cold storage gel prepared in the comparative example had a problem of bleeding of free water after thermal cycling in the absence of a crosslinking degree enhancer (comparative example 1), or in the use of CS-02 as a crosslinking degree enhancer (comparative example 2), or in the presence of only the crosslinking degree enhancer CS-01 without the addition of a hydrophilic polymer (comparative example 3).
When the common thickener CS-03 is used as a crosslinking degree enhancer (comparative example 4), a large amount of free water is precipitated in the phase-change gel, the phase separation of the phase-change gel is serious, and the phase-change performance and the cycle stability performance cannot be tested, probably because the CS-03 structure contains a large amount of hydroxyl groups which can form a hydrogen bond network with water molecules, but the network lacks solid particles to ensure the structural rigidity, and the severe shrinkage causes a large amount of water molecules to be precipitated. In addition, the phase change cold storage gel (comparative example 1) using only the hydrophilic polymer as the flexible setting medium has a smaller phase change latent heat, and the phase change gel (comparative example 3) added with the crosslinking degree enhancer CS-01 of the same dosage can obtain a larger phase change latent heat. The supercooling degree of the phase change cold storage gels of comparative example 5, comparative example 6 and comparative example 8 is higher because the phase change gel of comparative example 5 has partial agglomeration of the nucleating agent inside, the hydrophilic polymer used in comparative example 6 does not contain the nucleating agent, the amount of the modified nucleating agent participating in copolymerization in the hydrophilic polymer in comparative example 8 is smaller, and the prepared phase change cold storage gel contains less nucleating agent. In comparative example 7, the amount of hydrophilic polymer used was large, and the prepared phase change cold storage gel had low latent heat of phase change.
Fig. 1 is a comparison result of the flexible setting effect of the phase change cold storage gel of the examples and comparative examples of the present application, and a in fig. 1 and B in fig. 1 show the flexible setting effect of the phase change cold storage gel prepared in example 1 and comparative example 1, respectively. As can be seen from FIG. 1, the cold storage gel without using the crosslinking degree enhancer CS-01 is in a loose state (B in FIG. 1), the granular gel is adhered to the wall of the container, and after using the crosslinking degree enhancer CS-01, the loose bonding degree of the gel is reduced (A in FIG. 1), and the flexible setting effect is remarkably improved.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Unless otherwise indicated to the contrary by the intent and/or technical scheme of the present application, all references to which this application pertains are incorporated by reference in their entirety for all purposes. When reference is made to a cited document in the present application, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the cited document are also incorporated. In the case of the cited documents, examples and preferred modes of the cited relevant technical features are also incorporated into the present application by reference, but are not limited to being able to implement the present application. It should be understood that when a reference is made to the description of the application in conflict with the description, the application is modified in light of or adaptive to the description of the application.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely represent a few embodiments of the present application and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Further, it is understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above teachings, and equivalents thereof are intended to fall within the scope of the present application. It should also be understood that, based on the technical solutions provided by the present application, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (10)
1. The flexible phase change cold storage material is characterized by comprising the following components in percentage by weight:
80-99.5% of inorganic salt water solution,
0.5-10% of hydrophilic polymer,
0.1% -5% of crosslinking degree reinforcing agent and
0-1% of other additives;
the inorganic salt aqueous solution comprises inorganic salt and water, wherein the weight of the inorganic salt accounts for 3% -40% of the total weight of the inorganic salt aqueous solution;
the hydrophilic polymer is formed by copolymerizing a mixed monomer, a modified nucleating agent and a cross-linking agent, the modified nucleating agent is connected in a main chain or a branched chain of the structure of the hydrophilic polymer in a chemical bond mode,
wherein the mixed monomers comprise the following components in a molar ratio of 1: (3-8): 0.01 of acrylic compound, acrylic salt single compound and acrylamide monomer, wherein the molar addition amount of the cross-linking agent relative to the acrylic compound is 0.05% -0.5%,
the weight of the modified nucleating agent is 0.1-0.5% of the total weight of the mixed monomers,
the modified nucleating agent is a product obtained by adopting a silane coupling agent to carry out functional group surface modification treatment on the nucleating agent, wherein the modified nucleating agent contains 0.5% -5% of a modifying group accounting for the total weight of the modified nucleating agent, and the nucleating agent is at least one selected from nano zinc oxide, nano aluminum oxide, nano silicon carbide and carbon nano tubes;
The crosslinking degree reinforcing agent is nano silicon dioxide with the particle size of 20-50 nm;
the other additives include corrosion inhibitors.
2. The flexible phase change cold storage material of claim 1, having at least one of the following technical characteristics:
(1) The acrylic compound is at least one selected from acrylic acid and methacrylic acid;
(2) The acrylic acid salt compound is at least one selected from sodium acrylate, potassium acrylate, sodium methacrylate and potassium methacrylate;
(3) The acrylamide compound is at least one selected from acrylamide and methacrylamide;
(4) The cross-linking agent is at least one selected from ethylene glycol diglycidyl ether, N' -methylene dipropionamide, N-vinyl-2-pyrrolidone and ethylene glycol diacrylate;
(5) The corrosion inhibitor is at least one selected from nitrite, chromate, phosphate, silicate and benzoate.
3. The preparation method of the flexible phase change cold storage material is characterized by comprising the following steps of:
preparing raw materials according to the formula of the flexible phase change cold storage material as claimed in claim 1 or 2;
taking the inorganic salt aqueous solution, optionally adding the other additives, and mixing to prepare a first solution;
Adding the hydrophilic polymer into the first solution under a first dispersion condition, and mixing to prepare a first gel;
the crosslinking degree enhancer is added to the first gel under a second dispersion condition.
4. The method according to claim 3, wherein the hydrophilic polymer is prepared by emulsion polymerization;
and adding the modified nucleating agent in the emulsion polymerization process for copolymerization.
5. A method of preparation according to claim 3, wherein the modified nucleating agent is prepared by steps comprising the following preparation method:
dispersing the nucleating agent in an organic solvent, adding a silane coupling agent, mixing, carrying out ultrasonic treatment, and heating to 80-90 ℃ for reaction.
6. The production method according to any one of claims 3 to 5, characterized by comprising at least one of the following production conditions:
(1) The first dispersion condition includes: stirring for 0.5-2 h at 30-100 r/min;
(2) The second dispersion condition includes: stirring for 0.5-3.5 h at 30-100 r/min.
7. A frozen type cold storage agent characterized by comprising the flexible phase change cold storage material according to claim 1 or 2 or the flexible phase change cold storage material produced by the production method according to any one of claims 3 to 5.
8. A cold storage agent for storing a lithography material, comprising the flexible phase change cold storage material according to claim 1 or 2, or the flexible phase change cold storage material produced by the production method according to any one of claims 3 to 5.
9. The cold storage agent for storage and transportation of a lithography material according to claim 8, wherein the lithography material comprises a photoresist, an anti-reflection coating, a spin-on carbon hard mask, and a spin-on glass hard mask.
10. A flexible cold accumulation bag, which is characterized by comprising a sealed package and a cold accumulation agent filled in the sealed package;
the cold accumulation agent contains the flexible phase change cold accumulation material according to claim 1 or 2 or the flexible phase change cold accumulation material prepared by the preparation method according to any one of claims 3-5.
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