CN117603430A - Light response three-section shape memory polyurethane material and preparation method thereof - Google Patents
Light response three-section shape memory polyurethane material and preparation method thereof Download PDFInfo
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- CN117603430A CN117603430A CN202410085712.1A CN202410085712A CN117603430A CN 117603430 A CN117603430 A CN 117603430A CN 202410085712 A CN202410085712 A CN 202410085712A CN 117603430 A CN117603430 A CN 117603430A
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- shape memory
- polyurethane material
- stilbene
- diisocyanate
- memory polyurethane
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000004814 polyurethane Substances 0.000 title claims abstract description 59
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 59
- 230000004298 light response Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims abstract description 36
- 235000021286 stilbenes Nutrition 0.000 claims abstract description 36
- 150000002334 glycols Chemical class 0.000 claims abstract description 32
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 24
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 24
- 150000002009 diols Chemical class 0.000 claims abstract description 21
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 46
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- KQPXJFAYGYIGRU-ONEGZZNKSA-N 3,3'-dimethoxy-trans-stilbene-4,4'-diol Chemical group C1=C(O)C(OC)=CC(\C=C\C=2C=C(OC)C(O)=CC=2)=C1 KQPXJFAYGYIGRU-ONEGZZNKSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- -1 chloroalkyl alcohol Chemical compound 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 8
- 230000007334 memory performance Effects 0.000 abstract description 4
- 239000012781 shape memory material Substances 0.000 abstract description 2
- 239000007777 multifunctional material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000012780 transparent material Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000004997 Liquid crystal elastomers (LCEs) Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 6
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 6
- 235000012141 vanillin Nutrition 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- QIJGACRZQSWKNB-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-diol Chemical compound OC1=CC=CC(C=CC=2C=CC=CC=2)=C1O QIJGACRZQSWKNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- OSASVXMJTNOKOY-UHFFFAOYSA-N chlorobutanol Chemical compound CC(C)(O)C(Cl)(Cl)Cl OSASVXMJTNOKOY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- LORZEOQACCXJLI-UHFFFAOYSA-N 1-chlorodecan-1-ol Chemical compound CCCCCCCCCC(O)Cl LORZEOQACCXJLI-UHFFFAOYSA-N 0.000 description 1
- CFDRQRFAQCJPBZ-UHFFFAOYSA-N 1-chlorohexan-1-ol Chemical compound CCCCCC(O)Cl CFDRQRFAQCJPBZ-UHFFFAOYSA-N 0.000 description 1
- HUBPTZAIVRQPLP-UHFFFAOYSA-N 1-chlorooctan-1-ol Chemical compound CCCCCCCC(O)Cl HUBPTZAIVRQPLP-UHFFFAOYSA-N 0.000 description 1
- ZZZXZQQRTBBNHT-UHFFFAOYSA-N 1-chloropentan-1-ol Chemical compound CCCCC(O)Cl ZZZXZQQRTBBNHT-UHFFFAOYSA-N 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010541 McMurry coupling reaction Methods 0.000 description 1
- 238000006519 Mcmurry reaction Methods 0.000 description 1
- 235000014150 Myroxylon pereirae Nutrition 0.000 description 1
- 244000302151 Myroxylon pereirae Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229960004926 chlorobutanol Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003722 gum benzoin Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001157 myroxylon pereirae klotzsch resin Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a photoresponsive three-section shape memory polyurethane material and a preparation method thereof. The invention relates to the technical field of light response shape memory materials, in particular to a light response shape memory polyurethane material and a preparation method thereof. The photoresponse three-section shape memory polyurethane material is formed by polymerizing glycol derivatives of stilbene, diisocyanate, polycaprolactone diol and pentaerythritol according to the molar ratio of 0.5-0.9:0.05-0.5:1:0.01-0.1. The polyurethane material provided by the invention is a colorless transparent material, and can realize the deformation of the material under 365 and nm ultraviolet irradiation; the introduction of polycaprolactone and pentaerythritol endows the material with excellent three-section shape memory performance and energy storage performance, and the fixation rate and the recovery rate are both more than 95 percent. The polyurethane material is a transparent multifunctional material and has wide application prospects in the fields of energy storage, soft robots, intelligent switches, information encryption and the like.
Description
Technical Field
The invention relates to the technical field of light response shape memory materials, in particular to a light response three-section shape memory polyurethane material and a preparation method thereof.
Background
The light response liquid crystal elastomer material is a liquid crystal elastomer with response behavior to light stimulus, and the light response liquid crystal elastomer has the advantages of no contact, no pollution, adjustable performance parameters and the like, so that the light response liquid crystal elastomer becomes a hot spot for researching the liquid crystal elastomer from a plurality of stimulus response liquid crystal elastomers. However, most of the photoresponsive liquid crystal elastomers use azobenzene as a photoresponsive group, and the photoresponsive group has few optional types and single performance. Furthermore, azo-structure containing polymers are often colored, limiting their use.
In recent years, the substitution of green pollution-free bio-based polymer materials for traditional petroleum-based polymer materials has become a new development trend. Vanillin is widely present in vanilla beans, sugar beet, benzoin gum, peru balsam, tobacco leaves, asparagus and coffee, and is an important flavour. Vanillin undergoes McMurry coupling reaction under the catalysis of titanium tetrachloride, and further reacts to generate glycol derivatives of stilbene. The invention takes the glycol derivative of biological source stilbene as raw material, and prepares a transparent light response polyurethane material through the polymerization reaction with polycaprolactone glycol, diisocyanate and pentaerythritol. Under 365nm ultraviolet irradiation condition, the trans-structure of the stilbene can be isomerized into cis-structure, thereby realizing the rapid light response performance of the resin. By introducing easily crystallized soft-segment polycaprolactone diol and chemical cross-linking agent pentaerythritol into the polymer, the material is endowed with excellent three-segment shape memory performance and energy storage performance. Compared with the existing polymer containing the stilbene structure, the invention synthesizes the glycol derivative of the stilbene by taking vanillin as the raw material, which is more environment-friendly; the double bond of the glycol derivative of the stilbene does not contain substituent groups such as phenyl, methyl, cyano and the like, the steric hindrance is small, and the rapid photoresponse of the material can be realized; the benzene ring of the glycol derivative of the stilbene contains methoxy groups which push electrons strongly, so that the electron density of double bonds is higher, and the photoresponsive performance is more sensitive.
The reported polymerization containing the stilbene structure mainly researches the liquid crystal performance, heat resistance, fluorescence performance and photocrosslinking performance of the polymer, and rarely researches the light response deformation, shape memory and energy storage performance of the material. According to the invention, through innovative structural design, the glycol derivative of the stilbene, the easily crystallized soft-segment polycaprolactone diol and the chemical crosslinking agent pentaerythritol are simultaneously introduced into the polymer, and the light response deformation performance, the three-segment shape memory and the energy storage performance of the material are realized, so that the multifunctional application of the material is expected.
Disclosure of Invention
The invention provides a transparent light-responsive polyurethane material based on a stilbene structure, which aims at the problems that the light-responsive group structure of the existing light-responsive polyurethane material is single and is usually provided with color. Under the condition of ultraviolet irradiation, the quick light response performance of the material is realized through cis-trans isomerism of olefin in the stilbene.
The photoresponse three-section shape memory polyurethane material is prepared by polymerizing glycol derivatives of stilbene, polycaprolactone diol, diisocyanate and pentaerythritol according to a molar ratio of 0.5-0.9:0.05-0.5:1:0.01-0.1. The glycol derivative of the stilbene is derived from vanillin of biological origin under the catalysis of titanium tetrachloride.
The molecular weight of the polycaprolactone diol ranges from 1000 to 8000; the diisocyanate is one of hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, m-xylylene diisocyanate and toluene-2, 6-diisocyanate.
The preparation method of any one of the light response three-section shape memory polyurethane materials is characterized by comprising the following steps:
s1, glycol derivative of stilbene: in a round bottom flask, according to a molar ratio of 1:2:3: (E) -1, 2-di (3-methoxy-4-hydroxyphenyl) ethylene, chloroalkyl alcohol, potassium carbonate and potassium iodide were added in a ratio of 0.12, and after dissolution with N, N-dimethylformamide, the temperature was raised to 90℃for reaction for 12 hours. After the completion of the reaction, the mixture was extracted with ethyl acetate, washed with water, washed with saturated brine, and dried over anhydrous sodium sulfate. Evaporating the organic solvent by using a rotary evaporator, and performing column chromatography to obtain a stilbene derivative;
s2, light response three-section shape memory polyurethane material: adding polycaprolactone diol into a three-port round-bottom furnace, heating to 70 ℃, vacuum drying for 30min, adding diisocyanate, reacting for 1h under the protection of nitrogen, and adding N, N-dimethylformamide for dilution. Then adding glycol derivative of stilbene and N, N-dimethylformamide solution of dibutyl tin dilaurate, reacting for 1h, adding N, N-dimethylformamide solution of pentaerythritol, stirring for 5min, pouring into a mould, and drying the solvent to obtain the light response three-section shape memory polyurethane material.
Compared with the prior art, the invention has the following advantages:
firstly, the invention prepares the light-responsive polyurethane material by introducing the light-responsive stilbene structure into polyurethane. Compared with the existing light response polyurethane based on the azobenzene structure, the polyurethane material is colorless and transparent, and the application range of the light response polyurethane is widened. Meanwhile, the types of the light-responsive polyurethane are enriched, and a new thought and method are provided for the preparation of the light-responsive polyurethane.
The light response three-section shape memory polyurethane material is obtained by polymerizing glycol derivatives of stilbene, polycaprolactone diol, diisocyanate and pentaerythritol. The glycol derivative of the stilbene is derived from the vanillin of biological origin through McMurry reaction, and the raw material source is more environment-friendly. Compared with the prior polymer containing the stilbene structure, the double bond of the stilbene structure introduced by the invention does not contain substituent groups, and the steric hindrance is smaller. Meanwhile, the methoxy group on the stilbene structure makes the electron density of the double bond higher, so that the stilbene has the capability of quick light response.
Thirdly, the photoresponsive three-section shape memory polyurethane material of the invention simultaneously introduces the photoresponsive glycol derivative of the stilbene, the easily crystallized flexible chain segment polycaprolactone diol and the chemical crosslinking agent pentaerythritol during preparation, so that the photoresponsive property of the polyurethane is realized, and meanwhile, the excellent three-section shape memory property and the energy storage property of the material are endowed, and the multifunctionalization of the material is realized.
Drawings
FIG. 1 shows nuclear magnetic resonance hydrogen spectrum of glycol derivative of stilbene;
FIG. 2 shows an infrared spectrum of a glycol derivative of stilbene;
FIG. 3 is an infrared spectrogram of the light response three-section shape memory polyurethane material;
FIG. 4 is a DSC graph of a photoresponsive three-segment shape memory polyurethane material;
FIG. 5 is a photograph of a photo-responsive deformation process of a photo-responsive three-stage shape memory polyurethane material, wherein: FIG. 5a is a photograph of a light-responsive three-stage shape memory polyurethane material after being stretched and oriented, and FIG. 5b is a photograph of a light-responsive three-stage shape memory polyurethane material after being irradiated by 365nm ultraviolet light;
FIG. 6 is a photograph of a two-stage shape memory process for a light responsive three-stage shape memory polyurethane material;
FIG. 7 is a photograph of a three-stage shape memory process for a light responsive three-stage shape memory polyurethane material.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Example 1: (1) Synthesis of (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene:
under the protection of nitrogen, adding 100mL of anhydrous tetrahydrofuran and 2.35 g of magnesium powder into a 250mL round bottom flask, cooling to the temperature of minus 78 ℃, slowly dropwise adding 10.6mL of titanium tetrachloride under magnetic stirring, taking out from a low-temperature reactor after dropwise adding, continuously stirring at normal temperature, returning to the room temperature, and dropwise adding 7.02g of vanillin 50mL of anhydrous tetrahydrofuran solution into the mixed solution; after the completion of the dropwise addition, the temperature was raised to 80℃and the mixture was refluxed for 3 hours. After the reaction is finished, cooling to room temperature, removing the organic solvent by using a rotary evaporator, adding 12.5mL of concentrated hydrochloric acid, standing for 0.5 hour, and performing suction filtration to obtain a tan (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene solid, wherein the reaction process is as follows:
；
(2) Synthesis of glycol derivatives of stilbene
In a 100mL round bottom flask, 15mLN, N-dimethylformamide, 2g (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene, 3.04g potassium carbonate, 0.15g potassium iodide, 2.11g chlorohexanol, and the temperature was raised to 90℃and reacted for 12 hours; after the completion of the reaction, the mixture was extracted with ethyl acetate, washed with water, washed with saturated brine, and dried over anhydrous sodium sulfate. Evaporating the organic solvent by using a rotary evaporator, and performing column chromatography to obtain a stilbene derivative;
；
wherein m=3 to 10;
FIG. 1 is a nuclear magnetic resonance spectrum of a diol derivative of stilbene in deuterated chloroform (7.26 ppm) as solvent; 6.839ppm-7.053ppm are absorption peaks of hydrogen atoms on benzene ring and double bond, and 4.035ppm is Ar-O-CH 2 The upper hydrogen atom absorption peak, 3.992ppm is methoxy (Ar-OCH) on benzene ring 3 ) The absorption peak of the upper hydrogen atom is 3.641ppm of the absorption of the upper hydrogen atom of the alcoholic hydroxyl groupCollecting peaks;
FIG. 2 is an infrared spectrum of a glycol derivative of stilbene at 3548cm -1 The position is the telescopic vibration absorption peak of the alcoholic hydroxyl group, 3064cm -1 Is characterized by Ar-H and unsaturated C-H telescopic vibration absorption peak of 2946cm -1 The position is a methylene telescopic vibration absorption peak of 2862cm -1 is-CH 3 Is 1607cm -1 、1583cm -1 、1519cm -1 、1461cm -1 Around are the stretching vibration peaks of the aromatic ring skeleton, 1415 and 1391cm -1 Two points are asymmetric in-plane vibration of methyl and shear vibration absorption peak of methylene; 1295cm -1 The position is a telescopic vibration absorption peak of Ar-O, 1240cm -1 The aromatic ether has a telescopic vibration absorption peak of 1134cm -1 The position is the telescopic vibration absorption peak of alcohol-OH, 1070cm -1 The C-O bond has a telescopic vibration absorption peak of 950cm -1 The out-of-plane bending vibrations of trans-ch=ch-enehydro, 845 and 800cm -1 Two are the out-of-plane bending vibration absorption peaks of the aromatic hydrogen;
(3) Synthesis of photoresponsive three-section shape memory polyurethane material
2g (1.65 mmol) of polycaprolactone diol having a molecular weight of 4500 are introduced into a three-necked flask with heating and mechanical stirring, heated to 70℃and dried in vacuo for 30min, then 0.84g (8.2 mmol) of Hexamethylene Diisocyanate (HDI) are introduced into the reaction system and reacted for 1h at 70 ℃; 10mLN, N-dimethylformamide was then added for dilution, and then 1.89g (6.6 mmol) of a 10mLN, N-dimethylformamide solution of stilbene diol and 3. Mu.L of dibutyltin dilaurate was added dropwise, followed by further reaction at 70℃for 1 hour; adding 27.23mg (0.2 mmol) of pentaerythritol in 5mM LN, N-dimethylformamide, stirring for 5min, pouring the reaction solution into a mold, and drying the solvent at 80 ℃ by a forced air oven to obtain a polymer film;
；
where h=8-70 and m=3-10.
FIG. 3 is a light-responsive three-stage shape memory polyurethaneInfrared spectrogram of the ester material; CLPCL4000-Stilben-1:6 is a light-responsive three-section shape memory polyurethane material, wherein the ratio of polycaprolactone diol to glycol derivative of stilbene is 1:6; as shown in the figure, 3319cm -1 The absorption peak of the active hydrogen of the secondary amine in the polyurethane is 3077cm -1 Is characterized by an expansion vibration absorption peak of aromatic hydrogen bond and unsaturated carbon hydrogen bond, 2998cm -1 The position is a methylene telescopic vibration absorption peak of 2834cm -1 A telescopic vibration absorption peak of 1759cm and a methyl group -1 The characteristic absorption peak of carbon-oxygen double bond in amide bond is 1583cm -1 The position is the characteristic absorption peak of benzene ring, 1553cm -1 Is a characteristic absorption peak of an amide bond;
FIG. 4 is a DSC graph of a light-responsive three-segment shape-memory polyurethane material; CLPCL4000-Stilben-1:4 is a light-responsive three-section shape memory polyurethane material, wherein the ratio of polycaprolactone diol to glycol derivative of stilbene is 1:4; CLPCL4000-Stilben-1:6 is a light-responsive three-section shape memory polyurethane material, wherein the ratio of polycaprolactone diol to glycol derivative of stilbene is 1:6; CLPCL4000-Stilben-1:8 is a light-responsive three-section shape memory polyurethane material, wherein the ratio of polycaprolactone diol to glycol derivative of stilbene is 1:8; as shown in the figure, the melting point of polycaprolactone appears in the three photoresponsive three-section shape memory polyurethane materials at about 50 ℃, which indicates that the materials can be used as energy storage materials; the melting point of the stilbene crystal appears at 110 ℃, which proves that the material can be used as a liquid crystal elastomer;
FIG. 5 is a photograph of a photo-responsive deformation process of the photo-responsive three-stage shape memory polyurethane material, FIG. 5a is a photograph of the photo-responsive three-stage shape memory polyurethane material after being stretched and oriented, and FIG. 5b is a photograph of the photo-responsive three-stage shape memory polyurethane material after being irradiated by 365nm ultraviolet light; as shown in the figure, under 365nm ultraviolet irradiation, the photoresponsive three-section shape memory polyurethane material is rapidly deformed;
FIG. 6 is a photograph of a two-stage shape memory process for a light-responsive three-stage shape memory polyurethane material; as shown in the figure, the photoresponsive three-section shape memory polyurethane material has excellent shape memory performance;
FIG. 7 is a photograph of a three-stage shape memory process for a light-responsive three-stage shape memory polyurethane material; as shown, the light-responsive three-stage shape memory polyurethane material has excellent shape memory properties.
Example 2: (1) The synthesis method of (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene is the same as step (1) in embodiment 1;
(2) Synthesis of glycol derivatives of stilbene
In a 100mL round bottom flask, 15mLN, N-dimethylformamide, 2g (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene, 3.04g potassium carbonate, 0.15g potassium iodide, 1.89g chloropentanol was added, and the temperature was raised to 90℃and reacted for 12 hours. After the reaction is finished, ethyl acetate is used for extraction, water washing, saturated saline water washing, anhydrous sodium sulfate drying are carried out, and after an organic solvent is evaporated by a rotary evaporator, column chromatography is carried out to obtain the stilbene derivative;
(3) Synthesis of photoresponsive three-section shape memory polyurethane material
2g (1.65 mmol) of polycaprolactone diol having a molecular weight of 4500 are introduced under nitrogen into a three-necked flask with heating and mechanical stirring, heated to 70℃and dried under vacuum for 30min, 1.25g (8.2 mmol) of diphenylmethane diisocyanate (MDI) are subsequently added to the reaction system and reacted for 1h at 70 ℃. 10mLN, N-dimethylformamide was then added for dilution, and then 1.78g (6.6 mmol) of a 10mLN, N-dimethylformamide solution of stilbene diol and 3. Mu.L of dibutyltin dilaurate was added dropwise, followed by further reaction at 70℃for 1 hour; a solution of 27.23mg (0.2 mmol) of pentaerythritol in 5mL, N-dimethylformamide was added, and after stirring for 5 minutes, the reaction solution was poured into a mold, and the solvent was dried at 80℃with a forced air oven to obtain a polymer film.
Example 3: (1) The synthesis method of (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene is the same as step (1) in embodiment 1;
(2) Synthesis of glycol derivatives of stilbene
15mLN, N-dimethylformamide, 2g (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene, 3.04g potassium carbonate, 0.15g potassium iodide, 2.54g chlorooctanol were added to a 100mL round bottom flask, and the mixture was heated to 90℃and reacted for 12 hours; after the completion of the reaction, the mixture was extracted with ethyl acetate, washed with water, washed with saturated brine, and dried over anhydrous sodium sulfate. Evaporating the organic solvent by using a rotary evaporator, and performing column chromatography to obtain a stilbene derivative;
(3) Synthesis of photoresponsive three-section shape memory polyurethane material
2g (1.65 mmol) of polycaprolactone diol having a molecular weight of 4500 are introduced into a three-necked flask with heating and mechanical stirring under nitrogen, heated to 70℃and dried in vacuo for 30min, 1.11g (8.2 mmol) of isophorone diisocyanate (IPDI) are subsequently introduced into the reaction system and reacted for 1h at 70 ℃; subsequently, 10mLN, N-dimethylformamide was added for dilution, then, 2.00g (6.6 mmol) of a 10mLN, N-dimethylformamide solution of diphenyl glycol and 3. Mu.L of dibutyltin dilaurate was added dropwise, the reaction was continued at 70℃for 1 hour, and after 27.23mg (0.2 mmol) of a 5mLN, N-dimethylformamide solution of pentaerythritol was added, and after stirring for 5 minutes, the reaction solution was poured into a mold and the solvent was dried at 80℃with a forced air oven to obtain a polymer film.
Example 4: (1) The synthesis method of (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene is the same as step (1) in embodiment 1;
(2) Synthesis of glycol derivatives of stilbene
In a 100mL round bottom flask, 15mL of N, N-dimethylformamide, 2g of (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene, 3.04g of potassium carbonate, 0.15g of potassium iodide, 1.675g of chlorobutanol was added, and the temperature was raised to 90℃and the reaction was carried out for 12 hours. After the completion of the reaction, the mixture was extracted with ethyl acetate, washed with water, washed with saturated brine, and dried over anhydrous sodium sulfate. Evaporating the organic solvent by using a rotary evaporator, and performing column chromatography to obtain a stilbene derivative;
(3) Synthesis of photoresponsive three-section shape memory polyurethane material
2g (1.65 mmol) of polycaprolactone diol having a molecular weight of 4500 are introduced into a three-necked flask with heating and mechanical stirring under nitrogen protection, heated to 70℃and dried under vacuum for 30min, then 0.84g (8.2 mmol) of Hexamethylene Diisocyanate (HDI) are introduced into the reaction system, then reacted at 70℃for 1h, then 10mLN, N-dimethylformamide are added for dilution, then 1.665g (6.6 mmol) of 10mLN, N-dimethylformamide solution of diphenyl glycol and 3. Mu.L of dibutyltin dilaurate are added dropwise, after continuing the reaction at 70℃for 1h, a solution of 5mLN, N-dimethylformamide of 27.23mg (0.2 mmol) of pentaerythritol is added, after stirring for 5min, the reaction solution is poured into a mold, the solvent is dried at 80℃with a blast oven to obtain a polymer film,
example 5: (1) The synthesis method of (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene is the same as step (1) in embodiment 1;
(2) Synthesis of glycol derivatives of stilbene
In a 100mL round bottom flask, 15mLN, N-dimethylformamide, 2g (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene, 3.04g potassium carbonate, 0.15g potassium iodide, 2.98g chlorodecanol was added, and the temperature was raised to 90℃and reacted for 12 hours. After the reaction is finished, ethyl acetate is used for extraction, water washing, saturated saline water washing, anhydrous sodium sulfate drying are carried out, and after an organic solvent is evaporated by a rotary evaporator, column chromatography is carried out to obtain the stilbene derivative;
(3) Synthesis of photoresponsive three-section shape memory polyurethane material
2g (1.65 mmol) of polycaprolactone diol having a molecular weight of 4500 was introduced into a three-necked flask with heating and mechanical stirring, heated to 70℃and dried under vacuum for 30 minutes, then 0.87g (8.2 mmol) of Toluene Diisocyanate (TDI) was introduced into the reaction system, then reacted at 70℃for 1 hour, then 10mLN, N-dimethylformamide was added for dilution, then 2.34g (6.6 mmol) of 10mLN, N-dimethylformamide solution of stilbene diol and 3. Mu.L of dibutyltin dilaurate was added dropwise, the reaction was continued at 70℃for 1 hour, then 27.23mg (0.2 mmol) of 5mLN, N-dimethylformamide solution of pentaerythritol was added, after stirring for 5 minutes, the reaction solution was poured into a mold, and the solvent was dried at 80℃with a blast oven to obtain a polymer film.
In summary, the transparent light response polyurethane material is obtained through the polymerization reaction of the glycol derivative of the stilbene, the polycaprolactone diol, the diisocyanate and the pentaerythritol, and has excellent three-section shape memory performance and energy storage performance, so that the multifunctionalization of the material is realized.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical matters of the present invention can be made by those skilled in the art without departing from the scope of the present invention.
Claims (4)
1. The light response three-section shape memory polyurethane material is characterized by being prepared by polymerizing a glycol derivative of stilbene, polycaprolactone diol, diisocyanate and pentaerythritol according to a molar ratio of 0.5-0.9:0.05-0.5:1:0.01-0.1, wherein the structural formula of the glycol derivative of the stilbene is as follows:
；
where m=3 to 10.
2. The light-responsive three-stage shape memory polyurethane material of claim 1, wherein the polycaprolactone diol has a molecular weight ranging from 1000 to 8000 and a structural formula as follows:
；
where h=8-70.
3. The light-responsive three-stage shape memory polyurethane material of claim 1, wherein the diisocyanate is one of hexamethylene diisocyanate, isophorone diisocyanate, paraphenylene diisocyanate, m-xylylene diisocyanate, toluene-2, 6-diisocyanate.
4. A method for preparing a light-responsive three-stage shape memory polyurethane material as claimed in any one of claims 1 to 3, comprising the steps of:
s1, glycol derivative of stilbene: adding (E) -1, 2-bis (3-methoxy-4-hydroxyphenyl) ethylene, chloroalkyl alcohol, potassium carbonate and potassium iodide into a round bottom flask according to the mol ratio of 1:2:3:0.12, dissolving with N, N-dimethylformamide, and heating to 90 ℃ to react 12h; after the reaction, ethyl acetate is used for extraction, water washing, saturated saline water washing and anhydrous sodium sulfate drying are carried out; evaporating the organic solvent by a rotary evaporator, and performing column chromatography to obtain a glycol derivative of the stilbene;
s2, light response three-section shape memory polyurethane material: adding polycaprolactone diol into a three-neck round-bottom flask, heating to 70 ℃, vacuum drying for 30min, adding diisocyanate, reacting for 1h under the protection of nitrogen, and adding N, N-dimethylformamide for dilution; then adding glycol derivative of stilbene and N, N-dimethylformamide solution of dibutyl tin dilaurate, reacting for 1h, adding N, N-dimethylformamide solution of pentaerythritol, stirring for 5min, pouring into a mould, and drying the solvent to obtain the light response three-section shape memory polyurethane material.
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