CN115305063A - 基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 - Google Patents
基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 Download PDFInfo
- Publication number
- CN115305063A CN115305063A CN202211125149.3A CN202211125149A CN115305063A CN 115305063 A CN115305063 A CN 115305063A CN 202211125149 A CN202211125149 A CN 202211125149A CN 115305063 A CN115305063 A CN 115305063A
- Authority
- CN
- China
- Prior art keywords
- solution
- millimeter
- core
- shell
- wet spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002775 capsule Substances 0.000 title claims abstract description 63
- 230000008859 change Effects 0.000 title claims abstract description 25
- 238000002166 wet spinning Methods 0.000 title claims abstract description 16
- 239000011258 core-shell material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 81
- 239000011257 shell material Substances 0.000 claims description 46
- 239000012792 core layer Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000005345 coagulation Methods 0.000 claims description 20
- 229940057995 liquid paraffin Drugs 0.000 claims description 17
- 230000015271 coagulation Effects 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012782 phase change material Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000001112 coagulating effect Effects 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 9
- 238000005538 encapsulation Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 238000005338 heat storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000011162 core material Substances 0.000 description 15
- 239000003094 microcapsule Substances 0.000 description 14
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002088 nanocapsule Substances 0.000 description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 6
- 229940038384 octadecane Drugs 0.000 description 5
- 229920002396 Polyurea Polymers 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010410 calcium alginate Nutrition 0.000 description 2
- 239000000648 calcium alginate Substances 0.000 description 2
- 229960002681 calcium alginate Drugs 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- ZYURHZPYMFLWSH-UHFFFAOYSA-N octacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC ZYURHZPYMFLWSH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229940018038 sodium carbonate decahydrate Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
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
- C09K5/063—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
- B01J13/06—Making microcapsules or microballoons by phase separation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
本发明提供了一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法。本方法以水为凝固浴,通过同轴湿法纺丝技术实现胶囊化。采用上述工艺制备的毫米级相变胶囊,具有典型的储热/蓄冷功能,潜热高,适用温度范围无泄漏、循环稳定性好,相变温度稳定,具备良好的力学性能,无需其它外供能源。本方法加工过程简单、快速、经济,安全,无需使用特殊设备,能够降低成本,提高生产效率。
Description
技术领域
本发明涉及一种具有储热/蓄冷功能毫米级核壳相变胶囊的制备方法。尤其涉及一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法。
本发明提供了一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法。本方法以水为凝固浴,通过同轴湿法纺丝技术实现胶囊化。采用上述工艺制备的毫米级相变胶囊,具有典型的储热/蓄冷功能,潜热高,适用温度范围无泄漏、循环稳定性好,相变温度稳定,具备良好的力学性能,无需其它外供能源。本方法加工过程简单、快速、经济,安全,无需使用特殊设备,能够降低成本,提高生产效率。
背景技术
相变材料能够在其相变点附近吸收和释放能量,具有储热/蓄冷功能。大多数相变材料在发生相变时会出现固液转变,导致泄漏,因此将相变材料胶囊化成为一种防止相变材料泄漏和维持其形状稳定的重要方法。相变胶囊通常以聚合物或无机材料为壳,以相变材料为核,胶囊壳层的存在确保了相变发生时液体的泄漏,维持了整体的形状稳定。
近年来,相变微胶囊由于性能稳定、使用方便、应用前景广阔,因此成为研究热点,相关研究较多。目前研究中相变微胶囊的尺寸一般从不到1μm到300μm以上。原位悬浮聚合、界面聚合或乳液聚合是最常用的微胶囊化方法,其他方法包括凝聚法、喷雾干燥法、溶胶-凝胶法等。J.S.Cho通过界面缩聚以甲苯二异氰酸酯(TDI)和二乙烯三胺(DETA)为单体,以十八烷为相变材料,以壬基酚聚氧乙烯醚NP-10非离子表面活性剂为乳化剂,在乳液体系中制备了直径为1μm左右的聚脲微胶囊,微胶囊的相变温度在29-30℃。A.Sari等以聚甲基丙烯酸甲酯(PMMA)为壳材通过乳液聚合将正二十八烷胶囊化,相变胶囊的熔融和结晶温度分别为50.6和53.2℃,熔融和结晶潜热分别为86.4和-88.5J/g。X.Lan等以正二十烷为核,以DETA和TDI为单体,通过乳液界面聚合制备了聚脲微胶囊。N.Sar1er和E.Onder制备了几种聚脲醛微胶囊,所用的胶囊核材包括正十六烷、正十八烷、正二十烷、PEG600、PEG1000和十水碳酸钠,并探讨了它们在织物领域的应用前景。美国Triangle公司合成了直径15-40μm的微胶囊。这种微胶囊具有吸热作用,将其整理在织物表面,就使织物具有了调节温度的功能。Triangle公司申请了一项关于具有可逆蓄热特点纤维的专利,这种纤维是在直径为1-10μm的微胶囊中封入石蜡类碳氢化合物,然后经过和聚合物溶液一起纺丝而制得的。在某些应用场景下,纳米胶囊比微米胶囊具有更好的结构稳定性,相对而言不容易在通过流体进行输运过程中发生破坏,也有利于降低流体粘度,因此相关研究也很活跃。G.Fang等以正十四烷为核,以十二烷基硫酸钠为乳化剂,以间苯二酚为体系调节剂,制备了直径在100nm左右的纳米聚脲醛胶囊,其潜热可达134.16kJ/kg。Y.Fang等以聚苯乙烯为壳,以十八烷为核,通过超声辅助微乳液原位聚合制备了直径范围在100nm到123nm的相变纳米胶囊。H.Li等以十六醇为核,交联聚苯乙烯为壳,通过一步乳液沉淀聚合制备了相变纳米胶囊,胶囊平均直径约为120nm,熔融潜热达到124.85J/g,具备良好的机械性能和热稳定性。
对于相变胶囊而言,尺寸越小,壳材在胶囊中质量占比越高,为了提高胶囊的储能密度,将胶囊尺寸提升至毫米级是一个显而易见的策略。更关键的是,毫米尺寸相变胶囊在一些特定领域具有重要应用价值。可用于热管理服装,如医用防护服、极端环境服装等;以及建筑热管理领域,如用于地板下或墙体内。W.Li等首先以PMMA为壳,以十八烷为核,通过乳液聚合制备相变微胶囊,再将其分散在海藻酸钠溶液中形成悬浮液,将其滴加进氯化钙水溶液凝固浴中,通过锐孔-凝固浴法获得了以海藻酸钙为毫米胶囊壳材,以相变微胶囊为核的毫米胶囊结构。P.Han等采用类似方法制备了以十四烷为相变材料的毫米相变胶囊,首先通过乳液聚合将十四烷封装在微胶囊中,微胶囊壳材分别选用了聚脲醛和PMMA,再通过锐孔-凝固浴法制备毫米胶囊,其壳材为海藻酸钙,相变焓最高达到194.1J/g。H.Qi等利用乳液锐孔-凝固浴法制备了石蜡/壳聚糖毫米相变胶囊,胶囊尺寸可通过乳化剂用量进行调节,胶囊中石蜡含量最高达到85%,熔融潜热达112.6J/g,具备良好的循环稳定性。
除了上述锐孔-凝固浴法,还有一些方法也用来制备毫米级胶囊。T.Takei等利用液体弹珠制备了直径约2mm的胶囊,通过含有挥发性成分的单体液滴在超两亲粉末上滚动,再进行光固化,从而实现胶囊化。K.Nagai等通过固化乳液的方法制备了高球形度毫米级聚酰胺酸胶囊,其核为聚二甲基硅氧烷,但该方法非常耗时,N,N-二甲基乙酰胺挥发时长达到3天。P.Wang等通过同轴电驱方法,以鱼油为内芯液,以海藻酸钠溶液为外层液体,氯化钙水溶液为凝固浴,在20kV电压下驱动液滴进入凝固浴得到毫米胶囊。该方法将静电纺丝技术与锐孔-凝固浴法相结合,制备出了毫米级胶囊。这几种毫米级胶囊制备方法经过原料和工艺调整后也可用于制备毫米相变胶囊。
目前,上述毫米级核壳胶囊的制备方法中,锐孔-凝固浴法的壳材可选择范围较窄且胶囊的机械强度不高,液体弹珠法的壳材可选择范围有限且制备效率不高,乳液固化法的制备效率极低。因此,亟需一种制备简单、壳材可选择范围广、制备效率高、胶囊的机械性能好的毫米相变胶囊制备方法。
发明内容
本发明的目的在于提供一种简单、高效、原料可选择范围广的毫米级相变胶囊的制备方法。
为了实现上述目的,本发明所采用的技术方案为:基于同轴溶液湿法纺丝技术,通过调节和控制内外层纺丝液的组成和推进速度,在凝固浴中形成胶囊结构。
进一步地,本发明所述的毫米级相变核壳胶囊以石蜡烷烃为核,以可溶性聚合物为壳。
进一步地,本发明所述的胶囊化内外层纺丝液的配方如下:内层为一定量的石蜡烷烃(C14-C20);外层为可溶性聚合物溶液,其中溶质包括PMMA、聚苯乙烯(PS)、聚偏氟乙烯(PVDF)、聚乙烯醇缩丁醛(PVB)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、聚碳酸酯(PC)、热塑性聚氨酯弹性体(TPU)或聚丙烯腈(PAN)等,所用溶剂为甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿、N,N-二甲基甲酰胺(DMF)或其混合溶剂等。
进一步地,本发明所述的毫米相变胶囊制备,其步骤如下:
以甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿、DMF或其混合溶剂等为溶剂,制备质量分数为10%~40%的聚合物溶液(室温机械搅拌0.5~3h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.3~0.7mL/min、芯层0.5~1.2mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。设置推进速度较慢,使针头处无法形成连续溶液,溶液呈水滴状滴落进凝固浴,与去离子水接触时,壳层溶液中溶剂迅速与水交换,形成致密保护壳,将石蜡烷烃包覆在其中,形成相变胶囊。
发明的作用与效果
与现有技术相比,本发明的有益效果是:
1)具有典型的储热/蓄冷功能,无需其它外供能源;2)核/壳质量比高,潜热高;3)适用温度范围无泄漏、循环稳定性好4)相变温度可调,适用温度范围较宽;5)循环稳定性好;6)具备良好的机械性能;7)壳材可选择范围广;8)加工过程无需外加电场;9)本方法加工过程简单、快速、经济,安全,无需使用特殊设备,能够降低成本,提高生产效率。
附图说明
图1实施例1在凝固浴中形成的毫米胶囊照片;
图2实施例2和实施例3所制备的不同壳层材料球形毫米胶囊照片;
图3实施例4和实施例5所制备的不同壳层材料准球形毫米胶囊照片。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明确,以下结合实施例,对本发明进行进一步地详细说明。应当理解,此处所描述的实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:
以DMF为溶剂,制备质量分数为25%的PVDF溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为十八烷,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例2:
以二氯甲烷为溶剂,制备质量分数为30%的SBS溶液(室温机械搅拌3h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例3:
以二氯甲烷与甲苯的1:1混合液为溶剂,制备质量分数为20%的PMMA溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例4:
以二甲苯为溶剂,制备质量分数为30%的PS溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例5:
以DMF为溶剂,制备质量分数为20%的PAN溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例6:
以乙醇为溶剂,制备质量分数为20%的PVB溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例7:
以DMF为溶剂,制备质量分数为20%的ABS溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.6mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例8:
以二氯甲烷为溶剂,制备质量分数为20%的PC溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1.2mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例9:
以DMF溶剂,制备质量分数为20%的TPU溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
以上所述仅为本发明较佳实例,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,通过同轴溶液湿法纺丝制备具有储热/蓄冷功能的毫米级石蜡烷烃/可溶性聚合物核壳相变胶囊。
2.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,基于同轴溶液湿法纺丝技术,通过调节和控制内外层纺丝液的组成和推进速度,在凝固浴中形成胶囊结构。
3.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,以可溶性聚合物为壳层材料,采用石蜡烷烃作为相变材料。
4.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,所用可溶性聚合物至少包括聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、聚乙烯醇缩丁醛、丙烯腈-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、聚碳酸酯、热塑性聚氨酯弹性体或聚丙烯腈;所用溶剂为甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿或N,N-二甲基甲酰胺的任意一种或其混合溶剂。
5.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,以甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿、N,N-二甲基甲酰胺的任意一种或其混合溶剂为溶剂,制备质量分数为10%~40%的聚合物溶液,室温水浴搅拌0.5~3h,得到壳层溶液,芯层溶液为液体石蜡烷烃。
6.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,分别将芯液储罐和壳层溶液储罐与同轴针头两端连通,设置注射泵推进速度为:壳层0.3~0.7mL/min、芯层0.5~1.2mL/min,接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水,纺丝液和凝固浴温度均为室温。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211125149.3A CN115305063A (zh) | 2022-09-15 | 2022-09-15 | 基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211125149.3A CN115305063A (zh) | 2022-09-15 | 2022-09-15 | 基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115305063A true CN115305063A (zh) | 2022-11-08 |
Family
ID=83867088
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211125149.3A Pending CN115305063A (zh) | 2022-09-15 | 2022-09-15 | 基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115305063A (zh) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838520A (zh) * | 2010-04-28 | 2010-09-22 | 清华大学深圳研究生院 | 一种含相变储能微胶囊组装物的制备方法 |
CN107597031A (zh) * | 2017-11-07 | 2018-01-19 | 西南科技大学 | 一种微胶囊相变材料的制备方法及装置 |
CN108374238A (zh) * | 2018-03-16 | 2018-08-07 | 中国科学院广州能源研究所 | 一种利用同轴静电纺丝技术制备的相变储热织物 |
CN108570766A (zh) * | 2018-03-16 | 2018-09-25 | 中国科学院广州能源研究所 | 一种利用同轴静电纺丝技术制备核壳结构的相变储热纤维膜的方法 |
CN110129916A (zh) * | 2019-04-17 | 2019-08-16 | 浙江理工大学 | 一种石蜡/聚丙烯腈智能调温纳米纤维 |
CN110820068A (zh) * | 2019-10-17 | 2020-02-21 | 浙江大学 | 一种相变纤维的制备方法 |
CN111005086A (zh) * | 2019-11-29 | 2020-04-14 | 吉祥三宝高科纺织有限公司 | 相变调温纤维及制备方法 |
CN111253914A (zh) * | 2020-03-04 | 2020-06-09 | 佛山科学技术学院 | 一种核壳结构的相变微胶囊及其制备方法和应用 |
CN113403704A (zh) * | 2021-06-01 | 2021-09-17 | 深圳减字科技有限公司 | 调温纤维的制备方法、调温纤维和织物 |
CN113718367A (zh) * | 2021-09-13 | 2021-11-30 | 同济大学 | 基于湿法纺丝的高弹性相变控温纤维及其制备方法 |
CN114481358A (zh) * | 2022-01-24 | 2022-05-13 | 苏州大学 | 一种调温纤维及其制备方法 |
-
2022
- 2022-09-15 CN CN202211125149.3A patent/CN115305063A/zh active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838520A (zh) * | 2010-04-28 | 2010-09-22 | 清华大学深圳研究生院 | 一种含相变储能微胶囊组装物的制备方法 |
CN107597031A (zh) * | 2017-11-07 | 2018-01-19 | 西南科技大学 | 一种微胶囊相变材料的制备方法及装置 |
CN108374238A (zh) * | 2018-03-16 | 2018-08-07 | 中国科学院广州能源研究所 | 一种利用同轴静电纺丝技术制备的相变储热织物 |
CN108570766A (zh) * | 2018-03-16 | 2018-09-25 | 中国科学院广州能源研究所 | 一种利用同轴静电纺丝技术制备核壳结构的相变储热纤维膜的方法 |
CN110129916A (zh) * | 2019-04-17 | 2019-08-16 | 浙江理工大学 | 一种石蜡/聚丙烯腈智能调温纳米纤维 |
CN110820068A (zh) * | 2019-10-17 | 2020-02-21 | 浙江大学 | 一种相变纤维的制备方法 |
CN111005086A (zh) * | 2019-11-29 | 2020-04-14 | 吉祥三宝高科纺织有限公司 | 相变调温纤维及制备方法 |
CN111253914A (zh) * | 2020-03-04 | 2020-06-09 | 佛山科学技术学院 | 一种核壳结构的相变微胶囊及其制备方法和应用 |
CN113403704A (zh) * | 2021-06-01 | 2021-09-17 | 深圳减字科技有限公司 | 调温纤维的制备方法、调温纤维和织物 |
CN113718367A (zh) * | 2021-09-13 | 2021-11-30 | 同济大学 | 基于湿法纺丝的高弹性相变控温纤维及其制备方法 |
CN114481358A (zh) * | 2022-01-24 | 2022-05-13 | 苏州大学 | 一种调温纤维及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6835334B2 (en) | Macrocapsules containing microencapsulated phase change materials | |
JP5351758B2 (ja) | 高分子電解質で変性されたマイクロカプセル | |
JP5180171B2 (ja) | 天然微小管に封入された相変化物質及びその調製 | |
US8163207B2 (en) | Microcapsules | |
CN104449590A (zh) | 一种相变储能材料的纳米胶囊及其制备方法 | |
US20100068525A1 (en) | Microcapsules | |
CN104762066B (zh) | 复合型相变储能微胶囊及其制备方法 | |
CN106367031A (zh) | 一种高热导率复合相变微胶囊及其制备方法 | |
CN111621265A (zh) | 基于无机物壳层的相变微胶囊及其制造方法和应用 | |
CN108854878A (zh) | 一种癸酸微胶囊及其制备方法 | |
Zhang et al. | Microstructure regulation of microencapsulated bio-based n-dodecanol as phase change materials via in situ polymerization | |
CN107875985A (zh) | 一种潜伏型微胶囊固化剂的制备方法 | |
CN105542724A (zh) | 一种掺杂金属纳米粒子的微胶囊相变材料颗粒及制备方法 | |
CN102676124A (zh) | 一种无机水合盐相变储能微胶囊及其制备方法 | |
CN110819308A (zh) | 相变储能微胶囊及其制备方法和应用 | |
CN106753261A (zh) | 一种微胶囊相变材料及其制备方法 | |
CN104962242A (zh) | 一种低过冷度相变材料微胶囊及其制备方法 | |
CN104804711B (zh) | 嵌入式导热增强相变储能微胶囊及其制备方法 | |
CN115305063A (zh) | 基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 | |
CN112391148A (zh) | 一种高导热和高焓值复合相变微胶囊及制备方法 | |
CN113214795A (zh) | 一种离子液体相变微胶囊的制备方法 | |
TWI411464B (zh) | 一種天然微管包埋的相變化材料的微膠囊及其製備方法 | |
CN114432979B (zh) | 一种金属有机框架材料作为囊壁的相变微胶囊 | |
CN102726383B (zh) | 一种缓释型害虫引诱剂微胶囊及其制备方法 | |
Norooz Kermanshahi et al. | Production, characterization and application of nano-phase change materials: A review |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |