CN116535607A - Polymer, process for producing the same, and liquid film deicing material - Google Patents
Polymer, process for producing the same, and liquid film deicing material Download PDFInfo
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- CN116535607A CN116535607A CN202310665728.5A CN202310665728A CN116535607A CN 116535607 A CN116535607 A CN 116535607A CN 202310665728 A CN202310665728 A CN 202310665728A CN 116535607 A CN116535607 A CN 116535607A
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- 239000007788 liquid Substances 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 19
- 230000008569 process Effects 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 230000008859 change Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 47
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 37
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 35
- 238000010992 reflux Methods 0.000 claims description 33
- 229920001223 polyethylene glycol Polymers 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- -1 fluoroalkyl alcohol Chemical compound 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- UFFDSAFACGIVQZ-UHFFFAOYSA-N 1,1,1,2,2,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-tricosafluoroundecan-3-ol Chemical compound FC(F)(F)C(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UFFDSAFACGIVQZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOFKYGUSMPWNY-UHFFFAOYSA-N Athidathion Chemical compound CCOP(=S)(OCC)SCN1N=C(OC)SC1=O QAOFKYGUSMPWNY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FMGBWGWCAQGRLA-UHFFFAOYSA-N 1,1,1,2,2,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluorononan-3-ol Chemical compound FC(F)(F)C(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FMGBWGWCAQGRLA-UHFFFAOYSA-N 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical class 0.000 claims description 2
- DEUJSGDXBNTQMY-UHFFFAOYSA-N 1,2,2-trifluoroethanol Chemical compound OC(F)C(F)F DEUJSGDXBNTQMY-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000011417 postcuring Methods 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 3
- 239000004970 Chain extender Substances 0.000 abstract description 2
- 239000002981 blocking agent Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012782 phase change material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000002265 prevention Effects 0.000 description 11
- 238000005286 illumination Methods 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 230000003075 superhydrophobic effect Effects 0.000 description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GPAMBYNRXCUNML-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GPAMBYNRXCUNML-UHFFFAOYSA-N 0.000 description 2
- JDIJDQNYSUHWJJ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JDIJDQNYSUHWJJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 2
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polymer with a structure of formula (I). According to the invention, the multi-block polymer of the phase-change long-chain block is synthesized through molecular structure design, a chemical covalent bond is formed by utilizing the reaction of hydroxyl and isocyanate groups, the problems of phase-change material interface and leakage are avoided, the hydrophobic photo-thermal phase-change polymer oligomer with an amphipathic chain segment is obtained through the introduction of a chain extender and a blocking agent, and a cross-linking network is formed through a multi-functional group cross-linking agent, so that the system performance is more stable, and the durability is better. The photo-thermal conversion and energy storage capacity of the polymer material are combined, the polymer phase change chain segments are promoted to form a liquid film-like deicing medium layer, the movement of the molecular chain segments promotes the amphiphilic chain segments to form a molecular chain driving force, the deicing efficiency is improved, and the active deicing energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a polymer, a preparation method thereof and a liquid film deicing material.
Background
Aiming at the icing problem of an airplane, active deicing technology is mature at present, and comprises a freezing point inhibition method, a mechanical deicing method and a hot melting method. The freezing point inhibition method mainly reduces the freezing temperature by spraying the deicing agent, but the deicing agent is consumed greatly, and the problems of load increase, environmental pollution, spray hole blockage and the like can occur. The mechanical deicing principle has the problems of large influence on aerodynamic appearance, damaged skin, incomplete deicing, research, development, application, technical barriers and the like. The hot melting method mainly comprises a gas heat deicing technology and an electric heating deicing technology, wherein the gas heat deicing technology is used for draining and utilizing hot gas of an engine to influence the flight performance of an airplane; however, the electrothermal ice control technology is most widely applied because of the mature technology, but has the problem of high electric energy consumption. The electric heating ice control system needs about 2kW/m 2 ～25kW/m 2 The heat quantity of the ice-removing agent can achieve the anti-icing effect, and the heat quantity required for deicing can achieve 5kW/m 2 ～50kW/m 2 The total heat consumed in a boeing 787 passenger aircraft thermoelectric ice control system is approximately 76kW/m 2 。
In order to reduce the "solid-solid contact" adhesion between ice build-up and the material surface, thereby achieving low heat energy saving and efficient deicing, both the academia and industry are developing materials that provide a layer of deicing medium, such as superhydrophobic surfaces, superslippery surfaces, and "liquid film-like barrier" slip anti-icing coatings. In recent years, researchers have utilized the characteristic of non-wettability of the lotus leaf surface, and a layer of micro-nano scale air film is constructed between the water drops and the contact surface through hydrophobicity, so that the adhesion of the water drops on the surface is reduced, and the effects of reducing icing adhesion and preventing icing on the surface are achieved. However, under the environment of low temperature, high humidity and external pressure, the vulnerability of the superhydrophobic layer can lose the deicing effect of the superhydrophobic material, and the service life of the material is reduced. The porous structure super-smooth surface for storing a large amount of lubricating liquid can be constructed in a bionic way, so that a liquid film medium layer can be formed, water drop coagulation can be effectively inhibited, and the adhesive strength of an ice layer is greatly reduced. However, the lubricant is severely lost during use, so that the performance is unstable and environmental pollution is caused.
The method comprises the steps of combining titanium nitride nano particles with a light absorption function and silicon dioxide nano particles with a hydrophobic function by researchers, spraying the titanium nitride nano particles on a first layer of a metal surface in an ultrasonic spraying mode, then spraying an organic polysilazane layer, and then spraying a super-hydrophobic silicon dioxide nano particle layer to prepare the photo-thermal super-hydrophobic coating with low reflectivity. The average solar absorptivity of the icephobic coating is 90%, and the infrared emissivity is only 6%, so that radiation heat loss is greatly inhibited, ice can be slowly ablated on the coated cable from the ice under the irradiation of 1 sunlight within 860 seconds at the temperature of minus 15 ℃, and the ice can be quickly defrosted (515 seconds) at the temperature of minus 15 ℃.
The prior researches mainly use a functional nano material composite system to study the influence rules of macroscopic results such as ice-setting time, deicing efficiency, ice adhesion and the like. However, nano filling still has influence on the durability and the large-scale preparation of the coating, and in addition, the simple photo-thermal effect also has the limited problems of sunlight irradiation duration, irradiation uniformity and the like.
Therefore, the structural performance of the deicing material is still required to be improved, and a new deicing medium layer is constructed, so that the durability of the deicing material and the stability of the deicing effect are improved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polymer, and the photo-thermal phase-change liquid film ice control material prepared by the polymer of the present invention has good durability and stability of ice removal efficacy.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean that a exists alone, a and B exist together, and B exists alone. Wherein A, B may be singular or plural.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s).
It should be understood that, in various embodiments of the present application, the sequence number of each process described below does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
Unless defined otherwise herein, scientific and technical terms used in connection with the present invention shall have the meaning as understood by one of ordinary skill in the art.
Furthermore, unless otherwise indicated herein, terms in the singular herein shall include the plural and terms in the plural shall include the singular. More specifically, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise.
The terms "comprising," "including," and "having" are used interchangeably herein to mean that the elements are included in an arrangement, meaning that the arrangement may exist in addition to the elements listed. It should also be understood that the use of "including," "comprising," and "having" descriptions herein also provides a "consisting of … …" scheme.
The term "and/or" as used herein includes the meaning of "and", "or" and "all or any other combination of the elements linked by the term of interest".
The invention provides a polymer with a structure of formula (I):
wherein: m1 and m2 are the polymerization degree of the first-step linear alkyl, branched alkyl and cycloalkyl prepolymers and are independently selected from 1 to 30; preferably 2-20.
k1 and k2 are the polymerization degree of the first-step aryl prepolymer and are independently selected from 1-30; preferably 2-20. n1 and n2 are the polymerization degree of polyethylene glycol and are independently selected from 90-454; preferably 130-320.
C3-C12F-substituted alkyl or 3- (trifluoromethyl) phenyl-substituted C1-C5 alkyl of X; preferably, the C3 to C10F-substituted alkyl group of X or the C1 to C3 alkyl group substituted by 3- (trifluoromethyl) phenyl group;
wherein the number of F is 3-20; preferably 3 to 15;
in a preferred embodiment of a part of the present invention, said X is selected from the group consisting of formula (X-1), formula (X-2), formula (X-3), formula (X-4), formula (X-5) and formula (X-6);
q1 is a C5-C10 linear alkyl group, a C5-C10 branched alkyl group or a C7-C20 cycloalkyl group;
preferably, Q1 is a C6-C8 straight chain alkyl, a C6-C9 branched alkyl or a C10-C15 cycloalkyl;
in a preferred embodiment of a part of the invention, Q1 is formula 101, formula 102 or formula 103;
q2 is aryl of C6-C20; preferably, Q2 is a C8-C15 aryl group;
in a preferred embodiment of a part of the present invention, Q2 is formula 104 or formula 105;
a is a branched alkyl group having 5 to 13 carbon atoms, a branched alkyl group having 5 to 15 carbon atoms and having an ether bond, or a formula 207;
preferably, A is a C5-C12 branched alkyl group, a C7-C12 branched alkyl group containing an ether linkage, or formula 207;
in a preferred embodiment of some of the present invention, a is any one of formulas 201 to 207:
in a preferred embodiment of the present invention, the polymer-based liquid film deicing material having the structure of formula (I) has the following structure:
the invention provides a preparation method of a polymer with a structure of a formula (I), which comprises the following steps:
a) Mixing polyethylene glycol, aromatic diisocyanate, aliphatic diisocyanate and a solvent, and heating and refluxing for reaction to obtain a prepolymer;
b) Mixing the 1, 5-dihydroxynaphthalene solution and the prepolymer in a reaction system, and continuing to heat and reflux the mixture for reaction;
c) Mixing a polyol, a fluoroalkyl alcohol-containing end-capping agent and a solvent, adding the mixture into a reaction system, and stirring the mixture to obtain a mixed solution;
d) And heating and curing the mixed solution to obtain the product.
The invention provides a preparation method of a polymer with a structure shown in a formula (I). Firstly, polyethylene glycol, aromatic diisocyanate, aliphatic diisocyanate and a solvent are mixed, heated and subjected to reflux reaction to obtain a prepolymer.
The molecular weight of the polyethylene glycol is 4000-20000.
The polyethylene glycol is preferably dried in a vacuum oven for 2-12 h.
Polyethylene glycol, aromatic diisocyanate and aliphatic diisocyanate are dissolved in a reaction vessel filled with an organic solvent and heated for reflux reaction.
The reaction vessel of the present invention includes, but is not limited to, a three-necked flask.
The aromatic diisocyanate is selected from Toluene Diisocyanate (TDI) or diphenylmethane diisocyanate (MDI);
the aliphatic diisocyanate is selected from isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI) or Hexamethylene Diisocyanate (HDI);
the solvent is selected from N, N dimethylformamide, N dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, petroleum ether or ethyl acetate.
The sources of the above raw materials are not limited, and the present invention is commercially available.
The mass ratio of the polyethylene glycol, the aromatic diisocyanate and the aliphatic diisocyanate according to the present invention is preferably (40 to 200): (1.0-5.0): (0.89-5.24); more preferably: (80-120): (1.74-2.50): (0.89-5.24).
The molar ratio of flexible long chain dihydric alcohol to total diisocyanate is 1:2, namely: molar value of polyethylene glycol: total molar value of aromatic diisocyanate plus aliphatic diisocyanate = 1:2.
molar value of polyethylene glycol: total molar value of aromatic diisocyanate plus aliphatic diisocyanate = 1:2,
the molar ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 1: 4-4: 1, a step of; including but not limited to 1:4, 4:1, 1:1.
The temperature of the heating reflux reaction is 40-100 ℃ and the time is 3-12 h; more preferably, the temperature of the heating reflux reaction is 50-100 ℃ and the time is 4-12 h;
the 1, 5-dihydroxynaphthalene solution and the prepolymer are mixed in a reaction system, and the heating reflux reaction is continued.
The invention preferably drops the 1, 5-dihydroxynaphthalene solution into the prepolymer, and the heating reflux reaction is continued; the temperature of the heating reflux reaction is 40-120 ℃ and the time is 2-6 h; more preferably, the temperature of the heating reflux reaction is 50-120 ℃ and the time is 2-6 h. The reaction is carried out under the protection of inert gas, preferably under the protection of high-purity nitrogen.
According to the invention, the 1, 5-dihydroxynaphthalene solution is obtained by adding 1, 5-dihydroxynaphthalene into a solvent, stirring and dissolving. The solvent is selected from N, N dimethylformamide, N dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, petroleum ether or ethyl acetate.
Wherein the mass g and volume mL ratio of the 1, 5-dihydroxynaphthalene and the solvent is (1.6-3.2): (10-50); preferably (1.6 to 3.2): (25-50);
the molar ratio of flexible long-chain dihydric alcohol to 1, 5-dihydroxynaphthalene is 1:1. wherein the flexible long chain dihydric alcohol refers to polyethylene glycol.
Mixing the polyol with the fluoroalkyl alcohol end-capping agent and the solvent, adding the mixture into a reaction system, and stirring the mixture to obtain a mixed solution.
According to the invention, the polyalcohol is selected from one or more of 2-hydroxy methane-2-methyl-1, 3-propanediol, glycerol, pentaerythritol, dipentaerythritol, xylitol, sorbitol and alkaline lignin;
the fluorine-containing alkyl alcohol end-capping agent is selected from one of perfluorooctyl alcohol, perfluorooctyl propanol, 3- (trifluoromethyl) phenethyl alcohol, 2-trifluoroethanol, perfluorohexyl alcohol or perfluorohexyl propanol.
The solvent is selected from N, N dimethylformamide, N dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, petroleum ether or ethyl acetate.
According to the invention, the mass g-to-volume mL ratio of the polyol to the fluoroalkyl alcohol-capping agent to the solvent is (0.23 to 1.2): (0.95-4.78): (20-50); preferably, the mass g-to-volume mL ratio of the polyol to the fluoroalkyl alcohol-capping agent to the solvent is (0.4 to 1.2): (0.95-4.78): (25-50);
the reaction of the reaction system is stirred for 10 to 30 minutes at the temperature of between 40 and 80 ℃.
And heating and curing the mixed solution to obtain the product.
In the invention, the heating and curing is specifically vacuum heating post-curing treatment; the vacuum heating is carried out for 2 to 4 hours at the temperature of 30 to 50 ℃; the curing treatment is specifically carried out for 2-4 hours at 60-120 ℃.
The invention also provides a liquid film ice prevention and removal material, which comprises the polymer according to any one of the technical schemes or is prepared by the preparation method according to any one of the technical schemes.
Compared with the prior art, the invention provides a polymer with a structure of formula (I). According to the invention, the multi-block polymer of the phase-change long-chain block is synthesized through molecular structure design, a chemical covalent bond is formed by utilizing the reaction of hydroxyl and isocyanate groups, the problems of phase-change material interface and leakage are avoided, the hydrophobic photo-thermal phase-change polymer oligomer with an amphipathic chain segment is obtained through the introduction of a chain extender and a blocking agent, and finally a cross-linking network is formed through a multi-functional group cross-linking agent, so that the system performance is more stable, and the durability is better.
Drawings
FIG. 1 is a synthetic reaction scheme for L1 samples in the examples;
FIG. 2 is a diagram of L1 sample in the example;
FIG. 3 is a graph of the water contact angle of the L1 sample in the example;
FIG. 4 is a graph showing the change in illumination time-temperature of the L1 sample in the example;
FIG. 5 is the mechanical properties of the L1 sample in the examples;
FIG. 6 is a graph of the solvent resistance of the L1 sample in the examples;
FIG. 7 is a graph showing the water contact angle versus temperature for the L1 sample in the example.
Detailed Description
The invention provides a polymer, a preparation method thereof and a liquid film deicing material, and the technical parameters can be properly improved by the person skilled in the art by referring to the content of the invention. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a preparation strategy of multi-block polyurethane which integrates a phase change function, a photo-thermal function, a hydrophobic function and a hydrophilic function through covalent bonds.
The invention avoids the problem of the interface layer of the nano material by directly coating the polymer, so that the stability of the dielectric layer is better, and the mechanical property of the material is better.
According to the invention, a photo-thermal group containing naphthalene and a hydrophobic group containing fluoroalkyl are introduced to provide photo-thermal effect and hydrophobic driving force, a dynamic bond topological structure and a soft and hard chain segment alternating structure are introduced to improve the chain segment movement capability, so that movement and aggregation under the photo-thermal effect of the phase change chain segment are promoted, a deicing medium layer taking the polymer chain segment as a liquid-like film is formed, and the stability of the medium layer is improved.
According to the preparation method of the polymer liquid film ice prevention and removal material provided by the invention, a block skeleton chain structure with a flexible molecular chain is prepared through molecular structure design, and a surface liquid film layer is formed through polymer chain segment micro-phase change and fluoroalkyl end capping agent control.
According to the preparation method of the polymer liquid film, provided by the invention, the existence of the amphiphilic molecular chain segment can promote the formation of an internal driving force of the polymer soft connecting segment so as to achieve the purpose of preventing and removing ice.
The polymer liquid film ice preventing and removing material prepared by the invention can effectively solve the problem of poor durability of the ice preventing and removing material due to the self cross-linked stable structure, solves the problems of structural damage and the like in the deicing process, realizes long service life and improves the durability of the material.
In order to further illustrate the present invention, a polymer, a method for preparing the same, and a liquid film deicing material according to the present invention will be described in detail with reference to examples.
Example 1
40.0g of polyethylene glycol (PEG 4000,0.01 mol) having a molecular weight of 4000 was dried in a vacuum oven at 120℃for 1 hour, 3.55g of isophorone diisocyanate (0.016 mol) and 1.00g of diphenylmethane diisocyanate (0.004 mol) were further added to dissolve in a three-necked flask containing an ultra-dry tetrahydrofuran solvent, and the molar ratio of PEG4000 to diisocyanate was controlled to be 1:2. heating and refluxing for 6 hours under the condition of uniform stirring at the temperature of 60 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 20ml of tetrahydrofuran solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the mole ratio of PEG4000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 6 hours at the temperature of 60 ℃ under the protection of high-purity nitrogen.
0.98g of 2-hydroxymethyl-2-methyl-1, 3-propanediol and 2.32g of perfluorooctyl ethanol were added to 20ml of tetrahydrofuran solvent and dissolved by stirring to obtain a homogeneous solution, and the obtained solution was added to the above solution and stirred for 30 minutes to obtain a homogeneous liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 40 ℃ for heating for 2 hours, and then adjusting the temperature to 60 ℃ for curing treatment for 12 hours to obtain the polymer liquid film ice prevention and removal material. The polymer liquid film ice control material is named L1, and the specific synthetic reaction equation is shown in figure 2. The performance test shows that the L1 is successfully synthesized, and has good crystallization capability, heat absorption and release capability, photo-thermal conversion capability, hydrophobic capability and ice prevention and removal capability. And under the temperature change, the movement of the phase change chain segment can promote the decrease of the surface water contact angle with the decrease of the temperature, and the water contact angle is not increased until the temperature reaches 20 ℃. Indicating that the change of the phase change chain segment from the crystalline state to the amorphous state increases the hydrophilicity of the material and changes the hydrophobicity of the surface of the coating. As the temperature continues to rise, the water contact angle reaches a maximum (125.7 °) at 60 ℃. The above trend indicates that the phase change chain segment has motion capability, and the amphiphilic chain segment can form molecular chain driving force under the action of temperature. The water contact angle is 124 degrees (room temperature condition), and the deicing time under the sun illumination condition is 247 seconds. The polymer liquid film deicing material is named as L1 and has the following molecular formula:
example 2
80.0g of polyethylene glycol (PEG 8000,0.01 mol) having a molecular weight of 8000 was dried in a vacuum oven at 120℃for 3 hours, and 0.89g of isophorone diisocyanate (0.004 mol) and 2.78g of toluene diisocyanate (0.016 mol) were further added to dissolve in a three-necked flask equipped with a dry N, N dimethylformamide solvent, and the molar ratio of PEG8000 to diisocyanate was controlled to be 1:2. heating and refluxing for 6 hours under the condition of uniform stirring at the temperature of 80 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 10ml of N, N-dimethylformamide solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the molar ratio of PEG8000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 5 hours at the temperature of 80 ℃ under the protection of high-purity nitrogen.
0.69g of 2-hydroxymethyl-2-methyl-1, 3-propanediol and 4.78g of perfluorooctyl propanol were added to 50ml of N, N-dimethylformamide solvent and stirred to dissolve to obtain a homogeneous solution, and then the obtained solution was added to the above solution and stirred for 30 minutes to obtain a homogeneous liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 40 ℃ for heating for 2 hours, and then adjusting the temperature to 120 ℃ for curing treatment for 6 hours to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 93 degrees (room temperature condition), and the deicing time under the sun illumination condition is 347 seconds. The polymer liquid film deicing material is named as L2 and has the following molecular formula:
example 3
200.0g of polyethylene glycol (PEG 10000,0.02 mol) having a molecular weight of 10000 was dried in a vacuum oven at 100℃for 4 hours, and 5.24g of dicyclohexylmethane diisocyanate (0.02 mol) and 5.00g of diphenylmethane diisocyanate (0.02 mol) were further added to dissolve in a three-necked flask equipped with an ultra-dry N, N-dimethylacetamide solvent, and the molar ratio of PEG10000 to diisocyanate was controlled to be 1:2. heating and refluxing for 4 hours under the condition of uniform stirring at the temperature of 80 ℃ to obtain the prepolymer. Then adding 3.20g of 1, 5-dihydroxynaphthalene into 50ml of N, N-dimethylacetamide solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the mole ratio of PEG10000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 4 hours at the temperature of 100 ℃ under the protection of high-purity nitrogen.
1.20g of 2-hydroxymethyl-2-methyl-1, 3-propanediol and 0.95g of 3- (trifluoromethyl) phenethyl alcohol were added to 30ml of N, N dimethylacetamide solvent and stirred to be dissolved to obtain a solution, and then the obtained solution was added to the above solution and stirred for 10 minutes to obtain a uniform liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 50 ℃ for heating for 2 hours, and then adjusting the temperature to 100 ℃ for curing treatment for 1 hour to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 104 degrees (room temperature condition), and the deicing time under the sun illumination condition is 297 seconds. The polymer liquid film deicing material is named as L3 and has the following molecular formula:
example 4
100.0g of polyethylene glycol (PEG 10000,0.01 mol) with molecular weight 10000 is dried in a vacuum oven at 100 ℃ for 4 hours under the protection of high-purity nitrogen, 2.62g of dicyclohexylmethane diisocyanate (0.01 mol) and 2.50g of diphenylmethane diisocyanate (0.01 mol) are added and dissolved in a three-neck flask filled with super-dry N, N-dimethylacetamide solvent, and the molar ratio of PEG10000 to diisocyanate is controlled to be 1:2. heating and refluxing for 4 hours under the condition of uniform stirring at the temperature of 80 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 50ml of N, N-dimethylacetamide solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the mole ratio of PEG10000 and 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 4 hours at the temperature of 100 ℃ under the protection of high-purity nitrogen.
0.23g of alkaline lignin and 0.95g of 3- (trifluoromethyl) phenethyl alcohol are added to 30ml of N, N-dimethylacetamide solvent and stirred to be dissolved to obtain a solution, and then the obtained solution is added to the solution and stirred for 10 minutes to obtain a uniform liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 50 ℃ for heating for 2 hours, and then adjusting the temperature to 100 ℃ for curing treatment for 1 hour to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 117 degrees (room temperature condition), and the deicing time under the sun illumination condition is 268 seconds. The polymer liquid film deicing material is named as L4 and has the following molecular formula:
example 5
120.0g of polyethylene glycol (PEG 12000,0.01 mol) having a molecular weight of 12000 was dried in a vacuum oven at 100℃for 12 hours, and then 2.62g of dicyclohexylmethane diisocyanate (0.01 mol) and 1.74g of toluene diisocyanate (0.01 mol) were added to dissolve in a three-necked flask equipped with an ultra-dry dioxane solvent, and the molar ratio of PEG12000 to diisocyanate was controlled to be 1:2. heating and refluxing for reaction for 12 hours under the condition of uniform stirring at the temperature of 100 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 50ml of dioxane solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the molar ratio of PEG12000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 2 hours at the temperature of 120 ℃ under the protection of high-purity nitrogen.
0.65g of 2-hydroxymethyl-2-methyl-1, 3-propanediol and 1.82g of perfluorohexyl ethanol were added to 30ml of dioxane solvent and stirred to dissolve to obtain a solution, and then the obtained solution was added to the above solution and stirred for 30 minutes to obtain a uniform liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 50 ℃ for heating for 4 hours, and then adjusting the temperature to 120 ℃ for curing treatment for 4 hours to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 114 degrees (room temperature condition), and the deicing time under the sun illumination condition is 269 seconds. The polymer liquid film deicing material is named as L5 and has the following molecular formula:
example 6
120.0g of polyethylene glycol (PEG 12000,0.01 mol) having a molecular weight of 12000 was dried in a vacuum oven at 100℃for 10 hours, and then 2.62g of dicyclohexylmethane diisocyanate (0.01 mol) and 1.74g of toluene diisocyanate (0.01 mol) were added to dissolve in a three-necked flask equipped with an ultra-dry dioxane solvent, and the molar ratio of PEG12000 to diisocyanate was controlled to be 1:2. heating and refluxing for reaction for 12 hours under the condition of uniform stirring at the temperature of 100 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 50ml of dioxane solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the molar ratio of PEG12000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 2 hours at the temperature of 120 ℃ under the protection of high-purity nitrogen.
0.42g of dipentaerythritol and 1.82g of perfluorohexyl ethanol were added to 30ml of dioxane solvent and dissolved with stirring to obtain a solution, and then the obtained solution was added to the above solution and stirred for 90 minutes to obtain a uniform liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 50 ℃ for heating for 4 hours, and then adjusting the temperature to 120 ℃ for curing treatment for 4 hours to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 105 degrees (room temperature condition), and the deicing time under the sun illumination condition is 273 seconds. The polymer liquid film deicing material is named as L6 and has the following molecular formula:
example 7
160.0g of polyethylene glycol (PEG 16000,0.01 mol) having a molecular weight of 16000 was dried in a vacuum oven at 100deg.C for 12 hours, and 1.68g of hexamethylene diisocyanate (0.01 mol) and 2.50g of diphenylmethane diisocyanate (0.01 mol) were further added to dissolve in a three-necked flask equipped with a solvent of ultra-dry dimethyl sulfoxide, and the molar ratio of PEG16000 to diisocyanate was controlled to be 1:2. heating and refluxing for 10 hours under the condition of uniform stirring at the temperature of 100 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 40ml of dimethyl sulfoxide, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the molar ratio of PEG16000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 2 hours at the temperature of 120 ℃ under the protection of high-purity nitrogen.
1.08g of 2-hydroxymethyl-2-methyl-1, 3-propanediol and 1.82g of perfluorohexyl propanol are added into 30ml of dimethyl sulfoxide solvent, and the obtained solution is stirred and dissolved to obtain a solution, and then the obtained solution is added into the solution, and the solution is stirred for 20 minutes to obtain a uniform liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 50 ℃ for heating for 4 hours, and then adjusting the temperature to 120 ℃ for curing treatment for 4 hours to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 113 degrees (room temperature condition), and the deicing time under the sun illumination condition is 291 seconds. The polymer liquid film deicing material is named as L7 and has the following molecular formula:
example 8
200.0g of polyethylene glycol (PEG 20000,0.01 mol) with molecular weight of 20000 is dried in a vacuum oven at 100 ℃ for 12 hours under the protection of high-purity nitrogen, 1.68g of hexamethylene diisocyanate (0.01 mol) and 1.74g of toluene diisocyanate (0.01 mol) are added and dissolved in a three-neck flask filled with petroleum ether solvent, and the molar ratio of PEG20000 to diisocyanate is controlled to be 1:2. heating and refluxing for 10 hours under the condition of uniform stirring at the temperature of 100 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 40ml of petroleum ether, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the molar ratio of PEG20000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 2 hours at the temperature of 120 ℃ under the protection of high-purity nitrogen.
0.60g of 2-hydroxymethyl-2-methyl-1, 3-propanediol and 4.78g of perfluorooctyl propanol are added into 30ml of petroleum ether solvent, and the mixture is stirred and dissolved to obtain a solution, and then the obtained solution is added into the solution, and the stirring is carried out for 20 minutes to obtain a uniform liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the mould in a vacuum oven at 50 ℃ for heating for 4 hours, and then adjusting the temperature to 120 ℃ for curing treatment for 4 hours to obtain the polymer liquid film ice prevention and removal material. The water contact angle is 136 degrees (room temperature condition), and the deicing time under the sun illumination condition is 117 seconds. The polymer liquid film deicing material is named as L8 and has the following molecular formula:
comparative example 1 (reference to example 1, without perfluorooctyl ethanol added, the water contact angle of L1C prepared was reduced to 67.)
40.0g of polyethylene glycol (PEG 4000,0.01 mol) having a molecular weight of 4000 was dried in a vacuum oven at 120℃for 1 hour, 3.55g of isophorone diisocyanate (0.016 mol) and 1.00g of diphenylmethane diisocyanate (0.004 mol) were further added to dissolve in a three-necked flask containing an ultra-dry tetrahydrofuran solvent, and the molar ratio of PEG4000 to diisocyanate was controlled to be 1:2. heating and refluxing for 6 hours under the condition of uniform stirring at the temperature of 60 ℃ to obtain the prepolymer. Then adding 1.60g of 1, 5-dihydroxynaphthalene into 20ml of tetrahydrofuran solvent, stirring and dissolving to obtain 1, 5-dihydroxynaphthalene organic solution, dripping the solution into the prepolymer, and controlling the mole ratio of PEG4000 to 1, 5-dihydroxynaphthalene to be 1:1. heating and refluxing stirring reaction is carried out for 6 hours at the temperature of 60 ℃ under the protection of high-purity nitrogen.
0.98g of 2-hydroxymethyl-2-methyl-1, 3-propanediol was added to 20ml of tetrahydrofuran solvent and dissolved by stirring to obtain a homogeneous solution, and then the obtained solution was added to the above solution and stirred for 30 minutes to obtain a homogeneous liquid. And pouring the obtained liquid into a polytetrafluoroethylene mould, placing the polytetrafluoroethylene mould in a vacuum oven at 40 ℃ for heating for 2 hours, and then adjusting the temperature to 60 ℃ for curing for 12 hours to obtain the L1C, wherein the specific synthetic reaction equation is shown in the following chart. The water contact angle of the L1C complex is reduced to 67 degrees (room temperature condition) and deicing can not be performed under the sun illumination condition.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A polymer of the structure of formula (I):
wherein: m1 and m2 are polymerization degrees and are independently selected from 1-30;
k1 and k2 are polymerization degrees and are independently selected from 1-30;
n1 and n2 are independently selected from 90-454;
C3-C12F-substituted alkyl or 3- (trifluoromethyl) phenyl-substituted C1-C5 alkyl of X;
q1 is a C5-C10 linear alkyl group, a C5-C10 branched alkyl group or a C7-C20 cycloalkyl group;
q2 is aryl of C6-C20;
a is a branched alkyl group having 5 to 13 carbon atoms, a branched alkyl group having 5 to 15 carbon atoms and having an ether bond, or a formula 207;
2. the polymer of claim 1, wherein X is selected from the group consisting of formula (X-1), formula (X-2), formula (X-3), formula (X-4), formula (X-5) and formula (X-6),represents a connecting bond;
3. the polymer of claim 1, wherein Q1 is formula 101, formula 102 or formula 103; q2 is formula 104 or formula 105;
4. the polymer of claim 1, wherein a is any one of formulas 201-207:
5. the polymer according to claim 1, wherein the polymer-based liquid film deicing material having the structure of formula (I) has the following structure:
6. a process for the preparation of a polymer of the structure of formula (I), comprising:
a) Mixing polyethylene glycol, aromatic diisocyanate, aliphatic diisocyanate and a solvent, and heating and refluxing for reaction to obtain a prepolymer;
b) Mixing the 1, 5-dihydroxynaphthalene solution and the prepolymer in a reaction system, and continuing to heat and reflux the mixture for reaction;
c) Mixing a polyol, a fluoroalkyl alcohol-containing end-capping agent and a solvent, adding the mixture into a reaction system, and stirring the mixture to obtain a mixed solution;
d) And heating and curing the mixed solution to obtain the product.
7. The method according to claim 6, wherein,
the aromatic diisocyanate is selected from Toluene Diisocyanate (TDI) or diphenylmethane diisocyanate (MDI);
the aliphatic diisocyanate is selected from isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI) or Hexamethylene Diisocyanate (HDI);
the solvent is selected from N, N dimethylformamide, N dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, petroleum ether or ethyl acetate;
the polyalcohol is selected from one or more of 2-hydroxy methane-2-methyl-1, 3-propanediol, glycerol, pentaerythritol, dipentaerythritol, xylitol, sorbitol and alkaline lignin;
the fluorine-containing alkyl alcohol end-capping agent is selected from one of perfluorooctyl alcohol, perfluorooctyl propanol, 3- (trifluoromethyl) phenethyl alcohol, 2-trifluoroethanol, perfluorohexyl alcohol or perfluorohexyl propanol.
8. The method according to claim 6, wherein,
the mass ratio of the polyethylene glycol to the aromatic diisocyanate to the aliphatic diisocyanate in the step A) is (40-200): (1.0-5.0): (0.89-5.24);
the molar ratio of flexible long chain dihydric alcohol to total diisocyanate is 1:2
The molar ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 1: 4-4: 1, a step of;
the temperature of the heating reflux reaction is 40-100 ℃ and the time is 3-12 h;
the step B) is specifically as follows: dropwise adding the 1, 5-dihydroxynaphthalene solution into the prepolymer, and continuing to perform a heating reflux reaction; the temperature of the heating reflux reaction is 40-120 ℃ and the time is 2-6 h;
the molar ratio of flexible long-chain dihydric alcohol to 1, 5-dihydroxynaphthalene is 1:1.
9. the method according to claim 6, wherein,
the mass g-volume mL ratio of the polyol to the fluoroalkyl alcohol-capping agent to the solvent in the step C) is (0.23-1.2): (0.95-4.78): (20-50); the reaction of the reaction system is that stirring is carried out for 10-30 min at the temperature of 40-80 ℃;
the heating and curing in the step D) is specifically vacuum heating post-curing treatment; the vacuum heating is carried out for 2 to 4 hours at the temperature of 30 to 50 ℃; the curing treatment is specifically carried out for 2-4 hours at 60-120 ℃.
10. A photothermal phase change type liquid film deicing material comprising the polymer according to any one of claims 1 to 5 or prepared by the preparation method according to any one of claims 6 to 9.
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