CN110819308A - Phase change energy storage microcapsule and preparation method and application thereof - Google Patents
Phase change energy storage microcapsule and preparation method and application thereof Download PDFInfo
- Publication number
- CN110819308A CN110819308A CN201810907817.5A CN201810907817A CN110819308A CN 110819308 A CN110819308 A CN 110819308A CN 201810907817 A CN201810907817 A CN 201810907817A CN 110819308 A CN110819308 A CN 110819308A
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- Prior art keywords
- phase change
- change energy
- energy storage
- urea
- phenol
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- 230000008859 change Effects 0.000 title claims abstract description 103
- 238000004146 energy storage Methods 0.000 title claims abstract description 93
- 239000003094 microcapsule Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 83
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000004202 carbamide Substances 0.000 claims abstract description 43
- 239000011232 storage material Substances 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011162 core material Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229920001897 terpolymer Polymers 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims description 93
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 150000001299 aldehydes Chemical class 0.000 claims description 34
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000012188 paraffin wax Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 12
- 239000012874 anionic emulsifier Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 6
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 150000004676 glycans Chemical class 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 229920001282 polysaccharide Polymers 0.000 claims description 5
- 239000005017 polysaccharide Substances 0.000 claims description 5
- 108090000623 proteins and genes Proteins 0.000 claims description 5
- 102000004169 proteins and genes Human genes 0.000 claims description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- FNAZRRHPUDJQCJ-UHFFFAOYSA-N henicosane Chemical compound CCCCCCCCCCCCCCCCCCCCC FNAZRRHPUDJQCJ-UHFFFAOYSA-N 0.000 claims description 4
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 4
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 claims description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 240000007472 Leucaena leucocephala Species 0.000 claims description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
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- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
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- 238000000879 optical micrograph Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ZQZJKHIIQFPZCS-UHFFFAOYSA-N propylurea Chemical compound CCCNC(N)=O ZQZJKHIIQFPZCS-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 description 1
- AUIXNZFZSGLHKP-UHFFFAOYSA-M sodium;2,3-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=CC(S([O-])(=O)=O)=C1C AUIXNZFZSGLHKP-UHFFFAOYSA-M 0.000 description 1
- KQSJSRIUULBTSE-UHFFFAOYSA-M sodium;3-(3-ethylcyclopentyl)propanoate Chemical compound [Na+].CCC1CCC(CCC([O-])=O)C1 KQSJSRIUULBTSE-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 1
- JUAHWAGHDQJOLT-UHFFFAOYSA-M sodium;propane-2-sulfonate Chemical compound [Na+].CC(C)S([O-])(=O)=O JUAHWAGHDQJOLT-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- JLEHSYHLHLHPAL-UHFFFAOYSA-N tert-butylurea Chemical compound CC(C)(C)NC(N)=O JLEHSYHLHLHPAL-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- 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
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Thermal Sciences (AREA)
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a phase change energy storage microcapsule, which comprises a wall material and a core material, wherein the wall material is a phenol/urea/aldehyde terpolymer, the core material is a phase change energy storage material, and the content of nitrogen element in the wall material is less than or equal to 12 wt%. The invention also relates to a preparation method and application of the phase change microcapsule.
Description
Technical Field
The invention relates to a phase change energy storage microcapsule, a preparation method and application thereof, in particular to a microcapsule of a phenol/urea/aldehyde terpolymer coated phase change energy storage material, a preparation method and application thereof.
Background
The problem of energy utilization is more and more emphasized nowadays, and the phase change energy storage material can store or release a large amount of heat at a certain temperature through a phase change behavior, so that energy waste is reduced, and the phase change energy storage material is emphasized by scientific workers and is widely applied. Because the phase-change energy storage material is in a liquid state and flows at a high temperature, the phase-change energy storage material can be contacted and mixed with other materials in the using process to influence the performance, and the phase-change energy storage material is generally required to be packaged by utilizing a microcapsule technology in practical application.
The Chinese patent application publication CN102191018A synthesizes resorcinol modified urea-formaldehyde resin coated low-melting-point paraffin microcapsules by a one-step method. Chinese patent application publication CN 104357019a adds a heat conductive filler in a urea-formaldehyde resin wall material, coats paraffin by a two-step method, and improves the heat conductivity of urea-formaldehyde resin by only triggering paraffin solid-solid phase change to store energy. The Chinese patent application publication CN104861935A prepares the microcapsules of the solid-liquid phase change energy storage material by a two-step method. Chinese patent application publication CN105838334A discloses a resorcinol-modified urea-formaldehyde resin phase-change energy-storage microcapsule.
From the above published chinese patent application, it can be seen that the microcapsule product in which the phase change energy storage material is coated with urea formaldehyde and its modified resin still has some problems, which makes it hindered in practical popularization and application. The main points are as follows: 1. the latent heat retention is not preferable. 2. The phase change energy storage material is easy to seep out. 3. The influence on an application system is large, and the system generates serious thixotropy. 4. The surface of the wall material is rough, so that the viscosity of the system is obviously increased, and the addition amount is low.
Disclosure of Invention
In view of the prior art, the inventor of the present application has conducted extensive research in the field of modified urea-formaldehyde resin coated phase-change energy storage materials, so as to obtain a phase-change energy storage microcapsule with high latent heat, no leakage and little influence on an application system. As a result, it was found that the above object can be achieved by copolymerizing phenol as a third monomer with urea formaldehyde to reduce the content of nitrogen in the wall material. The present invention has been completed based on the above findings.
The invention aims to provide a microcapsule of a phase change energy storage material coated by a phenol/urea/aldehyde terpolymer.
Another object of the present invention is to provide a method for preparing the phase change energy storage microcapsule.
The invention further aims to provide application of the phase change energy storage microcapsule in the field of adhesives.
In one aspect of the invention, a phase change energy storage microcapsule is provided, which comprises a wall material and a core material, wherein the wall material is a phenol/urea/aldehyde terpolymer, and the core material is a phase change energy storage material, and is characterized in that the content of nitrogen element in the wall material is less than or equal to 15%.
In another aspect of the present invention, there is also provided a method for preparing a microcapsule of a phase change energy storage material coated with a phenol/urea/aldehyde terpolymer, comprising the steps of:
① emulsifying water, urea, phenol, inorganic electrolyte salt, emulsifier and phase-change energy-storage material at pH of 1.0-2.5;
② aqueous aldehyde solution was added to the emulsion of step ① at a constant rate.
In another aspect of the invention, the invention provides an application of the phase change energy storage microcapsule in the field of adhesives.
The invention utilizes a one-step method, adjusts acid once, and prepares the microcapsule of the phase change energy storage material coated by the phenol/urea/aldehyde terpolymer by a method of adding aldehyde at a constant speed. The method has the advantages of cheap and easily obtained raw materials, simple process, insensitivity to pH, large operation window, high reproducibility and easy amplification production.
The invention has the following characteristics:
1. the latent heat retention rate of the microcapsules is about 85-95%, and the phenomena of overheating and supercooling are avoided.
2. The wall material is thin, the content of the wall material is small, and the heat shielding effect is negligible.
3. The wall material has good toughness and is not easy to break, and the problem of core material seepage of the phase change energy storage microcapsule of the phenol modified urea-formaldehyde resin is solved.
4. Compared with the traditional resorcinol modified urea-formaldehyde resin phase change energy storage microcapsule, the phase change energy storage microcapsule has the advantages of single-particle dispersion of the microcapsule, smooth surface, fine powder, no agglomeration, easy dispersion in application, low content of amido bond (low content of nitrogen element) of wall materials, high steric hindrance, strong inertia, no action with other substances, small influence on an application system and unobvious viscosity rise.
5. Compared with other types of phase change energy storage microcapsules, the phase change energy storage microcapsules have lower cost on the basis of achieving higher performance.
Drawings
FIG. 1: DSC cycle curve for semi-refined paraffin # 58;
FIG. 2: DSC cycle curve for paraffin # 44;
FIG. 3: DSC cycle curve for n-octadecane;
FIG. 4: DSC cycle curves for the phase change energy storage microcapsule products of example 1;
FIG. 5: DSC cycle curves for the phase change energy storage microcapsule products of example 2;
FIG. 6: DSC cycle curves for the phase change energy storage microcapsule products of example 3;
FIG. 7: DSC cycle curves for the phase change energy storage microcapsule products of example 10;
FIG. 8: DSC cycle curves for the phase change energy storage microcapsule products of comparative example 1;
FIG. 9: DSC cycle curves for the phase change energy storage microcapsule products of comparative example 2;
FIG. 10: scanning electron micrographs of the phase change energy storage microcapsule product of comparative example 1;
FIG. 11: scanning electron micrographs of the phase change energy storage microcapsule product of comparative example 2;
FIGS. 12-16: optical micrographs of the phase change energy storage microcapsule product of example 10 at various time points during cooling.
Figure 17 scanning electron micrograph of phase change energy storage microcapsule product of example 10.
Detailed Description
The phase change energy storage microcapsule comprises a wall material and a core material, wherein the wall material is a phenol/urea/aldehyde terpolymer, the core material is a phase change energy storage material, and the content of nitrogen in the wall material is less than or equal to 15 wt%. In the phase change energy storage microcapsule, the surface of the wall material is smooth and has no obvious bulge.
In the phase change energy storage microcapsule of the present invention, the wall material may be polymerized from urea, aldehyde and phenol, wherein the mass ratio of urea to phenol is less than or equal to 1:1.75, preferably less than or equal to 1:2, and the mass ratio of phenol to aldehyde is 3:1 to 1:3, preferably 2:1 to 1:2, wherein the ratio ranges to any value between the endpoints, such as 2.5:1, 1: 1.5. The phenol is entirely involved in the overall urea/aldehyde reaction, and the upper limit of the amount of phenol is such that the content of nitrogen in the wall material is 15% or less, preferably 8% or less, and more preferably 5% or less. The thickness of the wall material can be 200-500nm, preferably 350-400 nm. The wall thickness may be any value between 200 and 500nm, such as 260, 320, 330, 345, 380, 420, 480nm, etc.
In the phase change energy storage microcapsule, the mass ratio of the core material to the wall material can be 2-7.5: 1, preferably 4-7: 1. The core material is a phase change energy storage material, the phase change energy storage material can be one or more of an inorganic phase change energy storage material or an organic phase change energy storage material, and preferably, the phase change temperature of the phase change energy storage material is less than 100 ℃, and more preferably, the phase change temperature is less than or equal to 85 ℃. The inorganic phase-change energy storage material can be calcium chloride containing CaCl2·6H2O、BaS、CaHPO4、CaSO4、Ca(OH)2And acetate of alkaline earth metal. The organic phase change energy storage material can be one or more of n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracosane, capric acid, myristic acid, lauric acid, stearic acid, palmitic acid, hexadecanol or 18-58 # paraffin, wherein the paraffin is low in price and stable in property, free of supercooling and precipitation phenomena, non-toxic, corrosion-free, environment-friendly, and about 18-30 in carbon atom number, the phase change temperature is in the range of 28-80 ℃, the latent heat of phase change is in the range of 180-250J/g, and the organic phase change energy storage material is a phase change energy storage material with extremely high cost performance.
Compared with the traditional resorcinol modified urea-formaldehyde resin, the microcapsule of the invention has regular appearance, smooth wall material surface and no obvious protrusion, and the capsule is dispersed in single particles and has no obvious accumulation. The proportion of phenol and urea is increased, the content of amido bond (nitrogen element) in the wall material is reduced, meanwhile, due to the fact that a large number of benzene rings exist in the wall material structure, the nitrogen element lone electron pair is delocalized through a hyperconjugation effect, the benzene ring structure increases a steric hindrance effect, the risks of thixotropy generation, viscosity increase and catalyst activity reduction in an application system are reduced, and due to the fact that the wall material is thin and does not generate a thermal barrier effect, the phase change latent heat retention rate of the phase change energy storage capsule is greater than or equal to 85%, and preferably 85-95%.
The method for preparing the phase change energy storage microcapsule realizes primary acid adjustment, simplifies the process, reduces the sensitivity of the system to pH, has large operation window and high repeatability, and improves the toughness and the smoothness of the wall material. The preparation steps of the phase change energy storage microcapsule are as follows:
① emulsifying water, urea, phenol, inorganic electrolyte salt, emulsifier and phase-change energy-storage material at pH of 1.0-2.5;
② aqueous aldehyde solution was added to the emulsion of step ① at a constant rate.
The emulsification process of step ① can be performed in a manner common in the art, such as conventional emulsification or so-called reverse emulsification, where the pH can be adjusted to 1.0-2.5 using a pH adjusting agent, either before or after the system is formed into an emulsion.
In steps ① and ②, the mass ratio of urea to phenol may be less than or equal to 1:1.75, preferably less than or equal to 1:2, the mass ratio of phenol to aldehyde may be 3:1 to 1:3, preferably 2:1 to 1:2, the total amount of urea, phenol and aldehyde and the amount of phase change energy storage material are such that the mass ratio of core material to wall material is 2 to 7.5:1, preferably 4 to 7:1, the amount of inorganic electrolyte salt may be 1 to 5%, preferably 1.5 to 4.0% of the total weight of urea, phenol and aldehyde, and the amount of emulsifier may be 20 to 60%, preferably 25 to 50% of the total weight of urea, phenol and aldehyde, wherein each ratio range relates to any value between the two endpoints.
The inorganic electrolyte salt can be any inorganic substance which is soluble in water and can be ionized into anion and cation, and is preferably one or more of ammonium salt, sodium salt and potassium salt; the ammonium salt is further preferably one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium hypochlorite, ammonium sulfite and ammonium chlorate; the sodium salt is further preferably one or more of sodium sulfite, sodium chlorate, sodium chloride, sodium sulfate, sodium nitrate and sodium hypochlorite; the potassium salt is further preferably one or more of potassium chloride, potassium sulfate, potassium nitrate, potassium hypochlorite, potassium sulfite, and potassium chlorate.
The emulsifier can be one or more of polysaccharide emulsifier, protein emulsifier or water-soluble anionic emulsifier, preferably mixture of water-soluble anionic emulsifier and polysaccharide emulsifier or protein emulsifier; the polysaccharide or protein emulsifier is one or more of acacia, gelatin, guar gum and methyl cellulose; the water-soluble anionic emulsifier is preferably a carboxylate type anionic emulsifier or a sulfonate type anionic emulsifier, and is further preferably sodium oleate, sodium abietate, sodium laurate, sodium naphthenate, sodium stearate, sodium dodecylbenzenesulfonate, sodium didodecylphenyl ether disulfonate, sodium benzenesulfonate, sodium methylsulfate, sodium dimethylbenzenesulfonate, and sodium isopropylsulfonate.
The urea may be one or more of urea and water-soluble substituted derivatives thereof, preferably urea, methyl urea, ethyl urea, diethyl urea, hydroxyethyl urea, ethylene urea, dihydroxy ethylene urea, n-propyl urea, isopropyl urea, 1, 3-dipropyl urea, n-butyl urea, isobutyl urea, tert-butyl urea, phenyl urea or mixtures thereof; further, urea or hydroxyethylurea is preferably used as the urea. The aldehyde may be one or more of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, and phenylpropylaldehyde. The phenol may be a water soluble phenol, preferably resorcinol or phenol. The pH adjuster may be a strong proton donor which is easily soluble in water or a mixture thereof, and more preferably one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and hypochlorous acid. The amount of water used may be 30 to 80%, preferably 40 to 70%, based on the total weight of the reaction system.
In step ②, the aqueous solution of aldehyde is added into the emulsion of step ① at a constant speed within 1 to 4 hours, preferably within 2.5 to 3.5 hours, the urea/aldehyde ratio in the reaction system is continuously decreased with time as the aldehyde is added at a constant speed, linear urea/aldehyde molecules dissolved in the continuous phase at the initial stage of the reaction are separated out through semi-crystallization under the influence of the reaction system to generate a dense and soft inner wall material, the urea/aldehyde molecular crosslinking degree is continuously increased due to continuous change of the urea-formaldehyde ratio at the middle and later stages of the reaction, the wall material is gradually transited from semi-crystallization to crosslinking polymerization and separation, the generated wall material is uniformly transited from an inner semi-crystalline dense and soft wall material to an outer high crosslinking rigid wall material, the whole has high flexibility, the stress concentration phenomenon is not easy to generate when the volume of the core material is changed, the core material is broken, the high compactness of the inner wall material enables the core material not easy to seep out, and the seepage problem of the core material of the single-layer urea-formaldehyde phase change energy storage microcapsule is solved, the concentration of the aqueous solution of the core material of the aldehyde is preferably 20 to 45.
The steps ① and ② can be performed in a reactor with heating function, such as a three-neck flask with a heating jacket, an electromagnetic heating stirring device, a reaction kettle with a heating function, etc., the heating temperature is controlled at 30-95 ℃, preferably 45-85 ℃, in order to complete the reaction, the reaction can be continuously maintained for 1-3 hours after the aqueous solution of the aldehyde is added, the specific reaction time can be adjusted according to the needs, the device for adding the aqueous solution of the aldehyde at a constant speed can be a dropping funnel or a constant flow pump, and a constant flow pump is preferably used.
Further preferably, the method of the present invention may comprise a step ③ of cooling the temperature of the reaction solution obtained in the step ② to ambient temperature or below, and then taking the upper layer slurry, washing with water, drying, and sieving to obtain the phase change energy storage microcapsule.
In step ③, to improve the yield, the reaction solution is allowed to stand for a period of time after it is cooled to ambient temperature, the standing time is determined by the amount of the reactants, usually at least 2 hours, if the amount of the reactants is large, the standing time is prolonged, if the amount of the reactants is large, the longer the standing time is, the better the standing time is, the adjustment can be made according to the actual production and yield requirements, in this step, the reaction solution is washed at least twice with water and then dried at 50-60 ℃ for at least 2 hours, however, the number of washing times and the drying temperature and time can be adjusted according to the amount of the reaction product, and 60-100 mesh sieve, preferably 70-80 mesh sieve, is used.
The raw materials used in the method of the invention are commercially available, and can be both industrially pure and analytically pure.
For the purposes of the present invention, the expression "smooth wall material surface without significant protrusions" means that there is no significant excess of particulate material on the outer surface of the wall material and "regular shape" means that the particles are substantially similar in shape. Throughout the specification, all percentages are percentages by weight unless otherwise indicated, and the phase change process refers to a process in which the phase change material in the phase change microcapsule undergoes a solid-liquid-solid transition.
The present invention is further illustrated by the following specific examples, but the present invention is not limited thereto.
Examples
Example 1
Into a 250ml flask were charged 125g of deionized water, 1.5g of urea, 3g of resorcinol, 1.8g of gum arabic, 0.3g of sodium dodecylbenzenesulfonate, 0.3g of ammonium chloride, pH adjusted to 1.2-1.3 with 38% hydrochloric acid, and 50g of paraffin # 58 was added. Heating to 65 deg.C and stirring for emulsification.
The temperature was maintained at 65 ℃ and 8.9g of 37% aqueous formaldehyde solution was added at 0.1ml/min using a constant flow pump, and the reaction was maintained for 2 hours after the addition.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 2
Into a 250ml flask were added 100g of deionized water, 0.5g of urea, 2.5g of phenol, 1.8g of gum arabic, 0.3g of sodium dodecylbenzenesulfonate, 0.3g of ammonium chloride, pH adjusted to 1.2-1.3 with 38% hydrochloric acid, and 40g of paraffin wax # 44 was added. Heating to 55 deg.C, stirring and emulsifying.
The temperature was maintained at 55 ℃ and 8.9g of 37% aqueous formaldehyde solution was added at 0.1ml/min using a constant flow pump, and the reaction was maintained for 2 hours after the addition.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 3
Into a 250ml flask were charged 125g of deionized water, 1.0g of urea, 2.5g of resorcinol, 2.3g of gum arabic, 0.3g of sodium dodecylbenzenesulfonate, 0.3g of ammonium chloride, adjusted to pH 1.2-1.4 with 98% sulfuric acid, and 50g of n-octadecane was added. Heating to 45 deg.C, stirring and emulsifying.
Keeping the temperature at 45 ℃, adding 18.9g of 37% formaldehyde aqueous solution by a constant flow pump at 0.1ml/min, and heating to 55 ℃ after the addition to maintain the reaction for 2 hours.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 4
Into a 250ml flask were charged 125g of deionized water, 1.5g of urea, 4.5g of resorcinol, 1.6g of gum arabic, 0.5g of sodium dodecylbenzenesulfonate, 0.4g of sodium chloride, adjusted to pH 1.4-1.5 with 98% sulfuric acid, and 60g of n-octadecane was added. The temperature was raised to 45 ℃ and emulsified.
Keeping the temperature at 45 ℃, adding 7.5g of 37% formaldehyde aqueous solution by a constant flow pump at 0.08ml/min, and heating to 55 ℃ after the addition to maintain the reaction for 1.5 hours.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 5
Into a 250ml flask was charged 140g of deionized water, 0.5g of urea, 2g of resorcinol, 1.2g of gum arabic, 1.0g of sodium dodecylbenzenesulfonate, 0.35g of potassium chloride, pH adjusted to 1.4-1.5 with 38% hydrochloric acid, and 45g of n-octadecane was added. The temperature was raised to 45 ℃ and emulsified.
Keeping the temperature at 45 ℃, adding 12.5g of 37% formaldehyde water solution by a constant flow pump at 0.12ml/min, and heating to 55 ℃ after the addition to maintain the reaction for 2 hours.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 6
Into a 250ml flask were charged 120g of deionized water, 1.0g of urea, 3.0g of resorcinol, 2.2g of gum arabic, 0.5g of sodium stearate, 0.35g of potassium chloride, adjusted to pH 1.4-1.5 with 68% nitric acid, and 55g of paraffin # 58 was added. The temperature is raised to 60 ℃ and emulsified.
The temperature was maintained at 60 ℃ and 12.5g of 37% aqueous formaldehyde solution was added at 0.12ml/min using a constant flow pump, and the reaction was maintained for 2 hours after the addition.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 7
Into a 250ml flask were charged 120g of deionized water, 1.0g of urea, 3.0g of resorcinol, 2.2g of gum arabic, 0.5g of sodium stearate, 0.35g of potassium chloride, pH adjusted to 1.4-1.5 with 38% hydrochloric acid, and 55g of paraffin # 58 was added. The temperature is raised to 60 ℃ and emulsified.
The temperature was maintained at 60 ℃ and 12.5g of 40% aqueous acetaldehyde solution was added at 0.12ml/min using a constant flow pump, and the reaction was maintained for 2 hours after the addition.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 8
Into a 250ml flask were charged 120g of deionized water, 1.0g of hydroxyethyl urea, 3.0g of resorcinol, 2.2g of gum arabic, 0.5g of sodium stearate, 0.35g of potassium chloride, pH adjusted to 1.4-1.5 with 38% hydrochloric acid, and 55g of paraffin # 58 was added. The temperature is raised to 60 ℃ and emulsified.
The temperature was maintained at 60 ℃ and 12.5g of 40% aqueous acetaldehyde solution was added at 0.12ml/min using a constant flow pump, and the reaction was maintained for 2 hours after the addition.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 9
Into a 250ml flask were charged 120g of deionized water, 1.0g of ethyl urea, 3.0g of resorcinol, 2.2g of gum arabic, 0.5g of sodium stearate, 0.35g of potassium chloride, pH adjusted to 1.4-1.5 with 38% hydrochloric acid, and 55g of # 58 paraffin wax was added. The temperature is raised to 60 ℃ and emulsified.
The temperature was maintained at 60 ℃ and 12.5g of 40% aqueous acetaldehyde solution was added at 0.12ml/min using a constant flow pump, and the reaction was maintained for 2 hours after the addition.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Example 10: microcapsule for preparing resorcinol modified urea-formaldehyde resin coated 58# paraffin by amplification one-step method
50Kg of deionized water, 0.6Kg of urea, 1.2Kg of resorcinol, 600g of gum arabic, 20g of sodium dodecylbenzenesulfonate and 120g of ammonium chloride were placed in a 100L jacketed kettle equipped with a high shear homogenizer and a lower discharge port, the pH was adjusted to 1.2-1.3 with 38% hydrochloric acid, and 20Kg of paraffin wax 58 was added. The temperature is raised to 65 ℃, after the paraffin is melted, a high-shear homogenizing machine is started to emulsify for 10 minutes at 10000 rpm.
The temperature is kept at 65 ℃, 3.56Kg of 37 percent formaldehyde aqueous solution is added by a constant flow pump at 40ml/min, and the reaction is maintained for 2 hours after the addition.
And cooling the reaction mother liquor to room temperature, standing for 6 hours, discharging lower-layer turbid liquid through a lower discharge port, washing upper-layer sludge-like substances for 4 times by deionized water, drying for 5 hours at 50 ℃, and sieving by a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
The microcapsules were wetted with water and prepared into a sample, and the phase transition of the resulting product was observed by analysis with an optical microscope XSP-12CA (Shanghai optical instruments, Inc.). Heating a sample wafer by using an electric blower, stopping heating after complete phase change (no solid paraffin exists by visual observation), naturally cooling the sample wafer, repeating the process for 3 times, recording the change process in a workstation to generate a video file, selecting any one of the complete phase change processes, and recording the screenshot every 30 seconds, wherein the result is shown in figures 12-16.
Comparative example 1: microcapsule for preparing resorcinol modified urea-formaldehyde resin coated 58# paraffin by traditional acid-regulating one-step method
Into a 250ml flask were added 90g of deionized water, 4.4g of urea, 0.44g of resorcinol, 35g of a 5% aqueous solution of polyvinyl alcohol, 0.3g of sodium dodecylbenzenesulfonate and 0.5g of sodium chloride, and 50g of paraffin wax # 58 was added after adjusting the pH to 1.2 to 1.5 with 38% hydrochloric acid. The temperature is raised to 65 ℃, and the paraffin is emulsified for 10 minutes after being melted.
After the temperature was maintained at 65 ℃, 8.9g of 37% aqueous formaldehyde solution was added, the mixture was maintained at pH 5.0 with 38% hydrochloric acid for 0.5 hour, at pH 4.2 with 38% hydrochloric acid for 0.5 hour, at pH 3.8 with 38% hydrochloric acid for 0.5 hour, at pH 3.5 with 38% hydrochloric acid for 0.5 hour, at pH 3.2 with 38% hydrochloric acid for 0.5 hour, and at pH 3.2 with 38% hydrochloric acid for 0.5 hour, the reaction was slowly decreased to 2.0 by a decrease in pH per minute of 0.02, the reaction was maintained for 1 hour, and the reaction was maintained at 72 ℃ for 0.5 hour.
And (3) cooling the reaction mother liquor to room temperature, standing for 2 hours, removing the suspension on the lower layer, washing the slurry-like substance on the upper layer for 2 times by using deionized water, drying for 2 hours at 50 ℃, and sieving by using a 80-mesh sieve to obtain a powdery product, namely the phase change energy storage microcapsule.
Comparative example 2
The procedure of example 1 was repeated except that the amount of resorcinol used was changed to 0.5 g.
The phase transition behavior of the microcapsules prepared in the above examples and comparative examples was analyzed by differential scanning calorimetry, and the specific test conditions were: a single cycle test was performed using a DSC instrument (TA Instruments-waters. llt) model TAQ200, with a temperature ramp of: the initial temperature is 0 ℃, the end point temperature is 100 ℃, the temperature is 120 ℃, the temperature is 150 ℃, the speed is 20 ℃/min, and the cooling process is as follows: the initial temperature is 100 ℃, 120 ℃, 150 ℃, the end temperature is 0 ℃, and the speed is 20 ℃/min. The wall material thickness was measured at 200 times magnification by microscope XSP-12CA (Shanghai optical instruments, Inc.). 10g of the microcapsules prepared in the above examples and comparative examples were added to 15g of silicone oil having a viscosity of 300cps, mixed by a speedmixer, the viscosity of the microcapsules after the addition was measured by a rotor viscometer, and thixotropy was measured using rotors different ten times in type, for example, the ratio of the viscosity measured by the 50# rotor to the viscosity measured by the 5# rotor was defined as the thixotropic index. And (3) putting 50g of sample into a 100L open container, stirring by using a glass rod, picking up some samples to be about 20cm away from the container opening, automatically flowing the samples into the container from the glass rod, and judging whether the samples can rapidly self-level to judge whether the samples have flowability. Taking a small amount of sample to prepare a sample piece on a glass slide, repeatedly heating the sample piece by using a hot air gun to enable the microcapsules to carry out phase change circulation, and simultaneously observing the damage or exudation condition of the microcapsules in the process under an optical microscope. The content of nitrogen element was measured by SEM scanning electron microscope in combination with an energy spectrometer (analysis center of Qinghua university, probe spacing 15mm, voltage 15KV), and the surface roughness and regularity of the capsules were observed. The results are now summarized in the following table:
comparative example 1 uses the traditional one-step method, controls the reaction rate by adjusting the pH value, has high requirement on the acid exchange process, has narrow process window and is not easy to control in the amplification process. The pH value of 3.5-2.8 is a key area, the surface of the microcapsule is rough and is adhered or agglomerated too fast, and the reaction rate is insufficient too slow. The formed wall material has high brittleness and is easy to be damaged by stress.
Comparative example 2 substantially the same conditions as in example 1 were employed, but the amount of resorcinol used was significantly reduced, resulting in a significant increase in viscosity in the silicone oil.
Example 1 is the preferred condition, the phenol-urea ratio is increased, and the appearance of the microcapsule is improved. The silicone oil detection sample has good fluidity.
Example 10 is a pilot scale test of the preferred conditions of example 1, and it can be seen that the process of the present invention is simple, the operating window is large, and the product quality is consistent with that of the pilot scale test.
From the heat release curve of DSC, it can be seen that the phase change latent heat retention rate of the phase change energy storage microcapsule prepared by adding aldehyde at a constant speed can reach more than 85%, while the phase change latent heat retention rate of the traditional method is only 68%.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. The phase change energy storage microcapsule comprises a wall material and a core material, wherein the wall material is a phenol/urea/aldehyde terpolymer, and the core material is a phase change energy storage material, and is characterized in that the content of nitrogen element in the wall material is less than or equal to 15 wt%.
2. Phase change energy storage microcapsule according to claim 1, characterized in that the thickness of the wall material is 200-500nm, preferably 350-400 nm.
3. Phase change energy storing microcapsules according to claim 1 or 2, characterized in that the content of nitrogen element in the wall material is less than or equal to 8 wt. -%, preferably less than or equal to 5 wt. -%.
4. The phase change energy storage microcapsule according to any one of claims 1 to 3, wherein the mass ratio of the core material to the wall material is 2 to 7.5:1, preferably 4 to 7: 1.
5. A phase change energy storage microcapsule according to any one of claims 1 to 4, characterized in that said phase change energy storage material is one or more of an inorganic phase change energy storage material or an organic phase change energy storage material, preferably said phase change energy storage material has a phase change temperature < 100 ℃.
6. The phase-change energy-storage microcapsule according to claim 5, wherein said inorganic phase-change energy-storage material is CaCl, an aqueous salt of calcium chloride2·6H2O、BaS、CaHPO4、CaSO4、Ca(OH)2The organic phase change energy storage material can be one or more of n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, alkali earth metal acetate, and the like,One or more of n-tricosane, n-tetracosane, capric acid, myristic acid, lauric acid, stearic acid, palmitic acid, cetyl alcohol or 18-58 # paraffin.
7. A phase change energy storage microcapsule according to any one of claims 1 to 6, characterized in that said wall material has a smooth outer surface.
8. A phase change energy storage microcapsule according to any one of claims 1 to 7, characterized in that the wall material has a smooth outer surface and the latent heat retention of the microcapsule is > 85%.
9. A phase change energy storage microcapsule according to any one of claims 1 to 8, characterized in that said microcapsule is made flowable in an application system.
10. A phase change energy storing microcapsule according to any of claims 1 to 9, wherein said microcapsule does not leak during repeated phase change cycles.
11. A process for the preparation of a phase change energy storage microcapsule according to any of claims 1 to 10 comprising the steps of:
① water, urea, phenol, inorganic electrolyte salt, emulsifier and phase change energy storage material are emulsified at pH 1.0-2.5.
② aqueous aldehyde solution was added to the emulsion of step ① at a constant rate.
12. The method of claim 11, wherein said steps ① and ② are performed at 45-85 ℃.
13. The method of claim 12, wherein said step ② is continued for 1-3 hours after the addition of the aqueous aldehyde solution is completed.
14. The method of claims 11-13, further comprising a step ③ of cooling the reaction solution obtained in step ② to ambient temperature or below, and then collecting the upper slurry, washing with water, drying, and sieving.
15. The method according to claims 11-14, characterized in that the pH of step ① is controlled to 1.0-2.5 by using a pH adjusting agent.
16. The process according to any one of claims 11 to 15, characterized in that the urea to phenol mass ratio is less than or equal to 1:1.75, preferably less than or equal to 1: 2; the mass ratio of the phenol to the aldehyde is 3:1-1: 3; the total dosage of the urea, the phenol and the aldehyde and the dosage of the phase change energy storage material are such that the mass ratio of the core material to the wall material is 2-7.5: 1, preferably 4-7: 1; the amount of the inorganic electrolyte salt is 1 to 5 percent, preferably 1.5 to 4 percent of the total weight of the urea, the phenol and the aldehyde; the amount of the emulsifier is 20-60%, preferably 25-50% of the total weight of urea, phenol and aldehyde; the inorganic electrolyte salt can be one or more of ammonium salt, sodium salt and potassium salt; the emulsifier can be one or more of polysaccharide, protein emulsifier or water-soluble anionic emulsifier; the urea may be one or more of urea and water-soluble substituted derivatives thereof; the aldehyde can be one or more of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde and phenylpropyl aldehyde; the phenol is water-soluble phenol, preferably resorcinol or phenol, and the pH regulator is a strong proton donor which is easily soluble in water.
17. The method according to claim 16, characterized in that the ammonium salt can be one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium hypochlorite, ammonium sulfite, ammonium chlorate; the sodium salt can be one or more of sodium sulfite, sodium chlorate, sodium chloride, sodium sulfate, sodium nitrate and sodium hypochlorite; the potassium salt can be one or more of potassium chloride, potassium sulfate, potassium nitrate, potassium hypochlorite, potassium sulfite and potassium chlorate; the polysaccharide or protein emulsifier can be one or more of acacia, gelatin, guar gum and methylcellulose; the water-soluble anionic emulsifier can be a carboxylate type anionic emulsifier or a sulfonate type anionic emulsifier; the strong proton donor easily soluble in water can be one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and hypochlorous acid.
18. Use of the phase change energy storage microcapsules of claims 1-10 in the field of adhesives.
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| CN113355045A (en) * | 2020-03-06 | 2021-09-07 | 苏州天山新材料技术有限公司 | Adhesive with energy storage function and application thereof |
| CN116218216A (en) * | 2023-03-21 | 2023-06-06 | 电子科技大学 | Polyimide-based composite material with high energy storage density and preparation method thereof |
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| CN113861942B (en) * | 2021-09-14 | 2024-05-03 | 中北大学 | Organic-microcapsule phase change material, preparation method thereof and application thereof in battery thermal management system |
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