CN112552273A - Preparation method of photoresponse phase-change material - Google Patents
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- 239000012782 phase change material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012074 organic phase Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 15
- 238000006467 substitution reaction Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000010828 elution Methods 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical group CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 4
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 claims description 4
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000002576 ketones Chemical group 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 description 16
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 12
- 238000011907 photodimerization Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- 239000011162 core material Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- -1 isopentenyl Chemical group 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006349 photocyclization reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QFCCZMLMZPLKAQ-MDZDMXLPSA-N 1-[(e)-2-phenylethenyl]pyrene Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1\C=C\C1=CC=CC=C1 QFCCZMLMZPLKAQ-MDZDMXLPSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical class [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to the field of phase-change materials, in particular to a preparation method of a photoresponse phase-change material.
Description
Technical Field
The invention relates to the field of phase-change materials, in particular to a preparation method of a photoresponse phase-change material.
Background
A new energy revolution characterized by replacing fossil energy with clean energy and improving energy efficiency, and energy storage technology is an ultimate solution for human to solve energy problems. United states, United kingdom, dayEnergy storage is taken as an important component of the industrial strategy of the countries, and a series of policies are issued to accelerate the development of the energy storage industry. China has a large population and complex regional environment, more than half of energy utilization depends on the entrance, and the promotion of the development of energy storage technology is imperative. The phase change energy storage technology has the advantages of no energy consumption, low cost, reliable performance and the like, and developed countries in the western world invest huge investments in developing new phase change energy storage technology and energy storage materials so as to continuously improve the heat storage performance, the economy and the reliability, for example, the U.S. department of energy (DOE) invests 6200 ten thousand dollars in developing novel phase change energy storage materials. The phase-change energy storage material is the core and the foundation of a phase-change energy storage technology, wherein the solid-liquid phase-change material has the advantages of low cost, mild phase-change process, easy control and the like, and is the most commonly used phase-change heat storage material at present. However, such materials have problems of easy leakage, strong corrosiveness and the like, and in order to effectively improve the practicability of the solid-liquid phase change material, it is a well-known solution to encapsulate a phase change core material in a carrier such as a porous material or a shell layer to construct a shaped composite phase change material. However, the energy storage density of the phase-change energy storage material depends on the physical phase-change enthalpy value of the core material and the load of the phase-change core material, and the latent heat value obtained is usually-102J/g is a difficult problem to overcome how to improve the energy storage density of the phase change material and enable the phase change material to play a greater role.
Under the irradiation of light with proper wavelength, some compounds can generate [4p +4p ] or [2p +2p ] cycloaddition reaction, and generate dimerization reaction between two carbon-carbon double bonds to form cyclobutane dimer. The dimer can be reversed under the action of light with proper wavelength, and a photocleavage reaction is carried out to form a compound before dimerization. Reversible photodimerization reactions have led to great interest in the development of new photoresponsive polymerization systems for different applications. By incorporating a photodimerizing group into a polymer, various polymer structures having reversibility can be produced. In the last decade, great progress has been made due to the ease of use and reversibility of the reversible polymerization reaction of photodimerization. Specific molecules are known to have the ability to undergo this reaction, such as cinnamic acid, stilbene, thymine, coumarin, anthracene, and styryl pyrene.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a photoresponse phase-change material.
In order to realize the purpose of the invention, the technical scheme is as follows:
the invention provides a preparation method of a photoresponse phase-change material, which at least comprises the following steps:
s1, compound of formula IA and R1-Br is subjected to substitution reaction;
wherein R is1The aryl is selected from alkyl with 12-24 carbon atoms, and R' is independently selected from hydroxyl, alkyl with 1-12 carbon atoms, alkenyl with 2-12 carbon atoms, alkoxy with 1-12 carbon atoms, aryl or heteroaryl; n is an integer of 0 to 5;
s2, carrying out post-treatment on the product of the substitution reaction to obtain the compound shown in the formula I;
optionally, the compound shown in the formula IA is 7-hydroxycoumarin; the R is1-Br is selected from bromo-n-dodecane, bromo-n-tetradecane and bromo-n-octadecane;
preferably, R1Selected from dodecyl, tetradecyl or octadecyl; n is 0.
Optionally, the conditions of the substitution reaction are as follows: a compound of formula IA and R1-Br is refluxed in a basic organic solvent;
the temperature of the reflux is preferably 50-70 ℃; the refluxing time is preferably 12-36 h; the substitution reaction is preferably carried out under an inert atmosphere;
preferably, the IA compound, said R1-Br and OH-The molar ratio of (A) to (B) is 5-7: 8-10: 7-11; the OH group-From potassium hydroxide or sodium hydroxide, preferably potassium hydroxide;
the organic solvent is selected from ketone organic solvent, alcohol organic solvent and ether organic solvent, preferably acetone.
Optionally, the post-processing step at least includes:
s21, extracting an organic phase of the reaction product to obtain a mixed organic phase;
s22, neutralizing the mixed organic phase, washing and drying to obtain an organic phase;
s23, concentrating the organic phase to obtain a crude product;
s24, separating and purifying the crude product to obtain the compound shown in the formula I.
Optionally, the extraction is performed by using an ester organic solvent, and the ester organic solvent is preferably ethyl acetate;
preferably, the extraction step is: adding water to the mixture obtained by the substitution reaction, and then extracting with ethyl acetate;
more preferably, the volume ratio of water to ethyl acetate is 1: 1-2;
further preferably, the number of times of extraction is 3-5.
Optionally, the neutralization is adding dilute hydrochloric acid into the mixed organic phase, and the cleaning is adding water and a saline solution;
preferably, the volume ratio of the dilute hydrochloric acid to the water to the saline solution is 1: 0.5-1.5: 1.2 to 1.8;
more preferably, the drying is drying by a drying agent, and the drying agent is preferably at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate;
further preferably, the concentration is performed under reduced pressure.
Optionally, the separation is performed by column chromatography; the eluent is preferably a mixed solvent I of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane in the mixed solvent I is 1: 2-5, preferably 1: 3-4;
the elution speed is preferably 5-10 mL/min, and the elution time is preferably 300-600 min.
Optionally, the purification method is recrystallization, and a solvent adopted by recrystallization is a mixed solvent II of dichloromethane and n-hexane; the volume ratio of the dichloromethane to the normal hexane is 1: 1-2, preferably 1: 1 to 1.5;
further preferably, the recrystallization method comprises: and drying the product of the column chromatography separation, adding the product into the mixed solvent II, raising the temperature to 50 ℃ while stirring, and cooling to room temperature after the product is completely dissolved.
The invention has at least the following beneficial effects:
the invention provides a preparation method of a photoresponse phase-change material, the prepared photoresponse phase-change material can perform two phase-change reactions, can be stored step by step so as to effectively improve the enthalpy value, and has a function of controlled release so as to control the melting and crystallization of the phase-change material by light. The preparation method of the photoresponse phase-change material provided by the invention has the advantages of cheap and easily available raw materials, simple process and mild reaction conditions, and is suitable for large-scale production.
Drawings
One or more embodiments are illustrated in respective figures of the drawings and are not to be construed as limiting the embodiments. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is an infrared spectrum of the photoresponse phase-change material obtained in example 2 of the present invention and 7-hydroxycoumarin.
FIG. 2 is a DSC chart of the photo-dimerization and photo-cleavage of the photo-responsive phase change material obtained in example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention. Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component. The embodiment of the invention develops a novel photoresponse phase-change material by utilizing the reversible photodimerization and photocleavage properties of a specific compound, not only improves the mass storage density of the phase-change material, but also has the controlled release function.
The embodiment of the invention provides a photoresponse phase-change material, and a novel photoresponse phase-change material is created by adding molecules with reversible cycloaddition capability into a main chain structure of the phase-change material. When the phase-change material is irradiated by light with a specific wavelength, a photocyclization addition reaction can occur, so that the molecules of the phase-change material are polymerized together, and the melting point and the freezing point of the phase-change material can be changed; when irradiated with light of another specific wavelength, a photocleavage reaction occurs, and the dimerized phase change material molecules are restored to the previous structure, and the melting point and the freezing point are restored to the previous levels. In the phase change process, the phase change material with a lower melting point is subjected to a photocracking reaction to generate the phase change material with a high melting point, so that two phase changes can be performed, more energy is stored, and the mass storage density of the phase change material is improved. Furthermore, this dependence on light, the phase change material is able to be controllably released and store energy by light. That is, the embodiment of the present invention provides a novel photoresponse phase change material, which not only improves the mass storage density of the phase change material, but also has a controllable release function. The structural formula of the phase-change material of the embodiment of the invention is shown as formula I:
wherein R is1The aryl is selected from alkyl with 12-24 carbon atoms, and R' is independently selected from hydroxyl, alkyl with 1-12 carbon atoms, alkenyl with 2-12 carbon atoms, alkoxy with 1-12 carbon atoms, aryl or heteroaryl; n is an integer of 0 to 5.
Preferably, R' is independently selected from hydroxyl, C1-6 alkyl, C2-6 alkenyl, C1-6 alkoxy or phenyl; more preferably, R' is independently selected from hydroxyl, isopentenyl, C1-C6 alkoxy or phenyl.
Preferably, R1Selected from n-dodecyl, n-tetradecyl or n-octadecyl, and n is 0.
The embodiment of the invention also relates to a preparation method of the photoresponse phase-change material, which at least comprises the following steps:
s1, compound of formula IA and R1-Br is subjected to substitution reaction;
wherein R is1The aryl is selected from alkyl with 12-24 carbon atoms, and R' is independently selected from hydroxyl, alkyl with 1-12 carbon atoms, alkenyl with 2-12 carbon atoms, alkoxy with 1-12 carbon atoms, aryl or heteroaryl; n is an integer of 0 to 5;
the chemical reaction equation is shown in formula II:
s2, and carrying out post-treatment on the product of the substitution reaction to obtain the compound shown in the formula I.
The preparation method provided by the embodiment of the invention has the advantages of cheap and easily available raw materials, simple process and mild reaction conditions, and is suitable for large-scale production.
Preferably, the compound of formula IA is 7-hydroxycoumarin; r1-Br is selected from bromo-n-dodecane, bromo-n-tetradecane and bromo-n-octadecane.
Specifically, in S1, the conditions of the substitution reaction are: a compound of formula IA and R1-Br is refluxed in a basic organic solvent;
preferably, the compound represented by IA and R1-Br and OH-The molar ratio of (A) to (B) is 5-7: 8-10: 7 to 11.
Wherein the reflux temperature is 50-70 ℃; the refluxing time is 12-36 h; the substitution reaction is carried out under an inert atmosphere, preferably a nitrogen atmosphere; OH group-From potassium hydroxide or sodium hydroxide, and preferably potassium hydroxide; the organic solvent is selected from ketone organic solvent, alcohol organic solvent and ether organic solvent, preferably acetone.
In the implementation of the present invention, the step of post-processing of S2 at least includes:
s21, extracting an organic phase of the reaction product, and washing to obtain a mixed organic phase;
s22, neutralizing the mixed organic phase, and drying to obtain an organic phase;
s23, concentrating the organic phase to obtain a crude product;
s24, separating and purifying the crude product to obtain the compound shown in the formula I.
Specifically, in S21, the extraction is performed using an ester organic solvent, and ethyl acetate is preferred as the ester organic solvent.
Preferably, the extraction step is: water was added to the mixture obtained in S1, followed by extraction with ethyl acetate. The volume ratio of water to ethyl acetate is 1: 1-2 times of extraction, and 3-5 times of extraction.
Specifically, in S22, dilute hydrochloric acid is added into the mixed organic phase for neutralization,with the aim of neutralizing OH-And the dilute hydrochloric acid is selected to be hydrochloric acid with the mass fraction of less than 20%. Washing by adding water and saline solution; water and brine solution are added for the purpose of removing excess hydrochloric acid; preferably, the volume ratio of the dilute hydrochloric acid to the water to the saline solution is 1: 0.5-1.5: 1.2 to 1.8. Wherein the brine is a saturated sodium chloride solution.
Specifically, in S22, the drying is performed using a drying agent, and the drying agent is preferably at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate.
Specifically, in S23, concentration was performed under reduced pressure.
Specifically, in S24, a crude product is separated by column chromatography; the eluent is preferably a mixed solvent I of dichloromethane and n-hexane, and the volume ratio of the dichloromethane to the n-hexane in the mixed solvent I is 1: 2-5, preferably 1: 3-4; the elution speed is preferably 5-10 mL/min, and the elution time is preferably 300-600 min.
Specifically, in S24, the purification method is to purify by recrystallization, and the solvent used for recrystallization is a mixed solvent II of dichloromethane and n-hexane; the volume ratio of the dichloromethane to the normal hexane is 1: 1 to 2, preferably 1: 1 to 1.5.
Among them, the recrystallization method is more preferably: drying the product separated by column chromatography, adding into the mixed solvent II, stirring while raising the temperature to 50 deg.C, and cooling to room temperature after the product is completely dissolved.
Preferably, the preparation method implemented by the invention specifically comprises the following steps:
(1) a compound shown as IA and R1mixing-Br and potassium hydroxide in acetone, refluxing the obtained mixed solution in an inert atmosphere, and cooling to room temperature after the reaction is finished;
(2) adding water into the mixture obtained in the step (1), and extracting with ethyl acetate to obtain a mixed organic phase;
(3) adding dilute hydrochloric acid, water and a saline solution into the mixed organic phase obtained in the step (2) to obtain a mixed solution; drying and filtering the obtained mixed solution to obtain an organic phase;
(4) carrying out reduced pressure concentration to obtain a crude product;
(5) performing column chromatography separation on the crude product obtained in the step (4) by using column chromatography silica gel;
(6) and (5) recrystallizing the product obtained after column chromatography in the step (5) to obtain the final product.
When the phase change material is irradiated by ultraviolet light of 300-400 nm, preferably 365nm, a photocyclization addition reaction can occur, so that the molecules of the phase change material are polymerized together to obtain a dimerized photoresponse phase change material, and the melting point and the freezing point of the dimerized photoresponse phase change material can be changed; when the ultraviolet light with the wavelength of 100-299 nm, preferably 254nm is used for irradiation, a photocracking reaction can occur, the dimerized phase-change material molecules can be restored to the former structure, the photoresponse phase-change material after photocracking is obtained, and the melting point and the freezing point are restored to the former level. In the phase change process, the phase change material with a lower melting point is subjected to photocracking reaction after dimerization to generate the phase change material with a high melting point, so that two phase changes can be generated, more energy is stored, and the mass storage density of the phase change material is improved. Specifically, taking coumarin as an example, the photodimerization and photocleavage schematic diagram is shown as formula III:
example 1
(1) Mixing 7mmol of 7-hydroxycoumarin, 10mmol of bromododecane and 9mmol of potassium hydroxide in 50mL of acetone to obtain a mixed solution, refluxing the mixed solution at 68 ℃ for 24 hours in a nitrogen atmosphere, and cooling the reacted mixture to room temperature;
(2) adding 70mL of water into the mixture obtained above, and extracting with 70mL of ethyl acetate for three times to obtain a mixed organic phase;
(3) adding 70mL of dilute hydrochloric acid, 70mL of water and 70mL of saline solution into the mixed organic phase to obtain a mixed solution;
(4) drying the mixed solution by using anhydrous sodium sulfate, stirring while adding, filtering out solids after complete drying to obtain an organic phase, and further concentrating under reduced pressure to evaporate the organic solvent to obtain a crude product;
(5) using a mixture of 1: 4, taking dichloromethane/n-hexane mixed solution as an eluent, performing column chromatography separation on the obtained crude product at an elution speed of 7mL/min for 400min, and performing reduced pressure evaporation on the obtained eluent containing the target product after elution to obtain a purified product;
(6) slowly adding the product obtained in the previous step into a mixture of dichloromethane and normal hexane in a volume ratio of 1: 1, slowly raising the temperature to 50 ℃ while stirring, cooling to room temperature after the product is completely dissolved, and finally recrystallizing the product from the solution. The structural formula of the obtained compound is shown as formula 1:
example 2
(1) Mixing 7mmol of 7-hydroxycoumarin, 9mmol of bromotetradecane and 9mmol of potassium hydroxide in 50mL of acetone, refluxing the obtained mixed solution at 68 ℃ for 24h in a nitrogen atmosphere, and cooling the reacted mixture to room temperature;
(2) adding 70mL of water into the mixture obtained above, and extracting with 70mL of ethyl acetate for three times to obtain a mixed organic phase;
(3) adding 70mL of dilute hydrochloric acid, 70mL of water and 80mL of saline solution into the mixed organic phase to obtain a mixed solution;
(4) drying the mixed solution by using anhydrous sodium sulfate, stirring while adding, filtering out solids after complete drying to obtain an organic phase, and further concentrating under reduced pressure to evaporate the organic solvent to obtain a crude product;
(5) using a mixture of 1: 3, taking dichloromethane/n-hexane mixed solution as an eluent, carrying out column chromatography separation on the obtained crude product at the elution speed of 7mL/min and the elution time of 300min, and evaporating the obtained eluent containing the target product under reduced pressure after elution to dryness to obtain a purified product;
(6) slowly adding the product obtained in the previous step into a mixture of dichloromethane and normal hexane in a volume ratio of 1: 1.2, slowly raising the temperature to 50 ℃ while stirring, cooling to room temperature after the product is completely dissolved, and finally recrystallizing the product from the solution. The structural formula of the obtained compound is shown as formula 2:
the infrared spectrum of the prepared photoresponse phase-change material is shown in figure 1.
The nuclear magnetic resonance hydrogen spectrum data are as follows: 1H NMR (400MHz, Chloroform-d) δ 7.65(d, J ═ 9.4Hz,1H),7.38(d, J ═ 8.5Hz,1H),6.85(dd, J ═ 8.5,2.4Hz,1H),6.83(d, J ═ 2.4Hz,1H),6.26(d, J ═ 9.5Hz,1H),4.03(t, J ═ 6.5Hz,2H), 1.89-1.78 (m, 2H), 1.55-1.19 (m,22H),0.90(t, J ═ 6.7Hz,3H).
Example 3
(1) Mixing 7mmol of 7-hydroxycoumarin, 9mmol of bromooctadecane and 10mmol of potassium hydroxide in 50mL of acetone, refluxing the obtained mixed solution at 68 ℃ for 24h in a nitrogen atmosphere, and cooling the reacted mixture to room temperature;
(2) adding 70mL of water into the mixture obtained above, and extracting with 70mL of ethyl acetate for three times to obtain a mixed organic phase;
(3) adding 70mL of dilute hydrochloric acid, 75mL of water and 85mL of saline solution into the mixed organic phase to obtain a mixed solution;
(4) drying the mixed solution by using anhydrous sodium sulfate, stirring while adding, filtering out solids after complete drying to obtain an organic phase, and further concentrating under reduced pressure to evaporate the organic solvent to obtain a crude product;
(5) using a mixture of 1: 3, taking dichloromethane/n-hexane mixed solution as an eluent, carrying out column chromatography separation on the obtained crude product at the elution speed of 7mL/min and the elution time of 500min, and evaporating the obtained eluent containing the target product under reduced pressure after elution to dryness to obtain a purified product;
(6) slowly adding the product obtained in the previous step into a mixture of dichloromethane and normal hexane in a volume ratio of 1: 1.5, slowly raising the temperature to 50 ℃ while stirringAnd cooling to room temperature after the product is completely dissolved, and recrystallizing the final product from the solution. The structural formula of the obtained compound is shown as a formula 3:
example 4
Preparing the final product phase-change material prepared in the embodiment 2 into a dichloromethane solution of 5g/L, irradiating the dichloromethane solution for 1h with 365nm ultraviolet light under stirring, evaporating the dichloromethane solution under reduced pressure to dryness to obtain a phase-change material subjected to photo-dimerization, and performing DSC (differential scanning calorimetry) test on the phase-change material in the embodiment 1 and the phase-change material subjected to photo-dimerization in the embodiment.
And preparing the prepared phase-change material subjected to photodimerization into a dichloromethane solution of 5g/L, irradiating for 0.5h by using 254nm ultraviolet under stirring to obtain the phase-change material subjected to photocleavage, and carrying out DSC (differential scanning calorimetry) test on the obtained phase-change material subjected to photocleavage.
FIG. 2 is a DSC chart of the photo-dimerization and photo-cleavage of the photo-responsive phase change material obtained in example 4 of the present invention.
As can be seen from FIG. 2, the melting point of the phase-change material after photodimerization is 62.8 ℃, the melting enthalpy is 141.1J/g, the melting point of the phase-change material after photocleavage is 65.3 ℃, and the melting enthalpy is 126.1J/g. When the temperature rises, the phase-change material after photo-dimerization is firstly melted, after the phase-change material is irradiated by 254nm ultraviolet light, the phase-change material is photo-cracked, the melting point is high, and after the temperature continues to rise, the phase-change material after photo-cracking can be subjected to phase change again.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a photoresponse phase-change material is characterized by at least comprising the following steps:
s1, compound of formula IA and R1-Br is subjected to substitution reaction;
wherein R is1Is selected from alkyl with 12-24 carbon atoms, R' is independently selected from hydroxyl, alkyl with 1-12 carbon atoms, alkenyl with 2-12 carbon atoms, alkoxy with 1-12 carbon atoms, aryl or heteroaryl; n is an integer of 0 to 5;
s2, and carrying out post-treatment on the product of the substitution reaction to obtain the compound shown in the formula I:
2. the preparation method according to claim 1, wherein the compound of formula IA is 7-hydroxycoumarin; the R is1-Br is selected from bromo-n-dodecane, bromo-n-tetradecane and bromo-n-octadecane;
preferably, R1Selected from dodecyl, tetradecyl or octadecyl; n is 0.
3. The method according to claim 1, wherein the substitution reaction is carried out under the following conditions: a compound of formula IA and R1-Br is refluxed in a basic organic solvent;
the temperature of the reflux is preferably 50-70 ℃; the refluxing time is preferably 12-36 h; the substitution reaction is preferably carried out under an inert atmosphere;
preferably, the compound represented by IA and the compound represented by R1-Br and OH-The molar ratio of (A) to (B) is 5-7: 8-10: 7-11; the OH group-From potassium hydroxide or sodium hydroxide, preferably potassium hydroxide;
the organic solvent is selected from ketone organic solvents, alcohol organic solvents and ether organic solvents, and is preferably acetone.
4. The method for the preparation according to claim 1, characterized in that the step of post-treatment comprises at least:
s21, extracting an organic phase of the reaction product to obtain a mixed organic phase;
s22, neutralizing the mixed organic phase, washing and drying to obtain an organic phase;
s23, concentrating the organic phase to obtain a crude product;
s24, separating and purifying the crude product to obtain the compound shown in the formula I.
5. The preparation method according to claim 4, wherein the extraction is carried out by using an ester organic solvent, preferably ethyl acetate;
preferably, the extraction step is: adding water to the mixture obtained by the substitution reaction, and then extracting with ethyl acetate;
more preferably, the volume ratio of water to ethyl acetate is 1: 1-2;
further preferably, the number of times of extraction is 3-5.
6. The method according to claim 4, wherein the neutralization is adding dilute hydrochloric acid to the mixed organic phase, and the washing is adding water and a brine solution;
preferably, the volume ratio of the dilute hydrochloric acid to the water to the saline solution is 1: 0.5-1.5: 1.2 to 1.8.
7. The preparation method according to claim 4, wherein the drying is drying with a drying agent, and the drying agent is preferably at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate;
preferably, the concentration is performed under reduced pressure.
8. The preparation method according to claim 4, wherein the separation is performed by column chromatography; the eluent is preferably a mixed solvent I of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane in the mixed solvent I is 1: 2-5, preferably 1: 3-4;
the elution speed is preferably 5-10 mL/min, and the elution time is preferably 300-600 min.
9. The preparation method according to claim 4, wherein the purification method is recrystallization, and the solvent used for recrystallization is a mixed solvent II of dichloromethane and n-hexane; the volume ratio of the dichloromethane to the normal hexane is 1: 1-2, preferably 1: 1 to 1.5.
10. The method according to claim 9, wherein the recrystallization method is: and drying the product of the column chromatography separation, adding the product into the mixed solvent II, raising the temperature to 50 ℃ while stirring, and cooling to room temperature after the product is completely dissolved.
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