CN114605281B - Photo-responsive polymer and monomer based on azobenzene side group, and synthesis method and application thereof - Google Patents
Photo-responsive polymer and monomer based on azobenzene side group, and synthesis method and application thereof Download PDFInfo
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- CN114605281B CN114605281B CN202210283161.0A CN202210283161A CN114605281B CN 114605281 B CN114605281 B CN 114605281B CN 202210283161 A CN202210283161 A CN 202210283161A CN 114605281 B CN114605281 B CN 114605281B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000178 monomer Substances 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000010948 rhodium Substances 0.000 claims abstract description 7
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000011232 storage material Substances 0.000 claims abstract description 4
- 239000000539 dimer Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- -1 cyclooctadiene proline rhodium Chemical group 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 8
- CVRIWLRSJCDOOX-UHFFFAOYSA-N 4-methyl-n'-(4-methylphenyl)sulfonylbenzenesulfonohydrazide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NNS(=O)(=O)C1=CC=C(C)C=C1 CVRIWLRSJCDOOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000006193 diazotization reaction Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 2
- 238000012721 stereospecific polymerization Methods 0.000 claims 1
- 229920000106 Liquid crystal polymer Polymers 0.000 abstract description 6
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract description 6
- 239000012954 diazonium Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 abstract description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract 2
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 125000006850 spacer group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
- 239000002904 solvent Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- 125000006366 methylene oxy carbonyl group Chemical group [H]C([H])([*:1])OC([*:2])=O 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 4
- LGZMUUBPTDRQQM-UHFFFAOYSA-N 10-Bromo-1-decanol Chemical compound OCCCCCCCCCCBr LGZMUUBPTDRQQM-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- SINRMVNOQUHGRZ-UHFFFAOYSA-N 2-octan-4-yloxy-N-phenylacetamide Chemical compound CCCC(CCCC)OCC(=O)NC1=CC=CC=C1 SINRMVNOQUHGRZ-UHFFFAOYSA-N 0.000 description 3
- ACYGZCHBIGKPGR-UHFFFAOYSA-N 4-octoxyaniline Chemical compound CCCCCCCCOC1=CC=C(N)C=C1 ACYGZCHBIGKPGR-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-DOMIDYPGSA-N 1-bromobutane Chemical group CCC[14CH2]Br MPPPKRYCTPRNTB-DOMIDYPGSA-N 0.000 description 1
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 1
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical group OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- 229930182821 L-proline Natural products 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- XSRWPJFTHDOKTA-UHFFFAOYSA-M [Rh]Cl.C1CC=CCCC=C1 Chemical class [Rh]Cl.C1CC=CCCC=C1 XSRWPJFTHDOKTA-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000006295 amino methylene group Chemical group [H]N(*)C([H])([H])* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical compound CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- 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
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photoresponse polymer based on azobenzene side group, a monomer, a synthesis method and application thereof, and the photoresponse polymer is applied to the fields of liquid crystal materials, optical information storage materials, nonlinear optical materials and the like. It has the following structural formula: Wherein m represents the number of spacer methylene groups; n represents the number of alkoxyl tail chain methylene groups, and x represents the number of repeating units; the apparent relative number average molecular weight M n of such polymers is at least 12kDa or more. The polymer is produced by the carbene directional polymerization reaction of the diazonium monomer catalyzed by rhodium metal. And adding the polymerized solution into a mixed solution of methanol and dichloromethane after stirring at room temperature, stirring again, collecting precipitate, dissolving in dichloromethane, collecting precipitate, repeating the above dissolving precipitation operation for multiple times until oligomer and dimer byproducts are removed, and successfully obtaining a series of corresponding C1 rod-shaped liquid crystal polymers with high-density and high-stereoregularity side-hung azobenzene groups.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to a photoresponse polymer and monomer based on azobenzene side groups, and a synthesis method and application thereof.
Background
Azobenzene polymers have excellent mechanical properties and processability of high molecular materials as well as photoinduced cis-trans isomerization characteristics of azo phenyl groups, and have wide application in various fields such as liquid crystal materials, optical information storage materials, nonlinear optical materials and the like, and have attracted great attention from researchers in recent years. The azobenzene liquid crystal polymer not only has the ordering and fluidity of liquid crystal, but also has the processing formability and defect tolerance, and has good light responsiveness. Meanwhile, the characteristic of the light responsiveness of the azobenzene can also have significant influence on the properties of liquid crystal, such as photo-induced reorientation, photochemical phase transformation, photo-induced molecular cooperative movement and the like, so that the traditional high-molecular liquid crystal material is endowed with special new performances. Therefore, the search and design of azobenzene liquid crystal polymers with novel structures and excellent properties is one of the important subjects in the fields of polymer chemistry and materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a photoresponsive polymer and monomer based on azobenzene lateral group, and a synthesis method and application thereof. The side chain azobenzene polymer prepared by the invention has excellent photochromic effect based on reversible cis-trans isomerization, and is a promising photo-responsive polymer material.
The aim of the invention is achieved by the following technical scheme:
a class of photoresponsive polymers based on azobenzene side groups, the compounds having the structure:
Wherein m=6 to 10; n=1 to 10; the apparent relative weight average molecular weight of the photoresponsive polymer based on the azobenzene side group is more than 32 kDa; the number average molecular weight is 12kDa or more.
Preferably, the azobenzene side group based photoresponsive polymer has the following structure:
Wherein m=6, 10; n=1, 4,8, 10; the number average molecular weight of the photoresponsive polymer of the azobenzene side group is more than 12 kDa.
Preferably, the class of photo-responsive polymers based on azobenzene side groups has one of the following structures:
The preparation method of the photoresponse polymer monomer based on the azobenzene side group comprises the following steps:
when m=6 to 10; when n+.1, see the following chemical equation (formula 1):
step 1, a step of reacting the formula I with a formula C nH2n+1 Br (n is not equal to 1) to generate a formula II;
Step 2, a step of reacting the formula II under an acidic condition to generate a formula III;
step 3, the diazotization reaction of the formula III is followed by the reaction of phenol under acidic conditions to generate a formula IV;
Step 4, a step of reacting the formula IV with a formula Br (CH 2)m OH (m=6-10) to generate a formula V;
Step 5, a step of reacting the formula V with the formula BrCOCH 2 Br to generate a formula VI;
step 6, step of forming formula VII with 1, 2-bis (p-toluenesulfonyl) hydrazine, 1, 8-diazabicyclo [5.4.0] undec-7-ene in THF solution.
Formula 1 is as follows:
when m=6 to 10; when n=1, the p-methoxyaniline is used in the formula III, and the reaction is performed according to the steps 3 to 6.
Preferably, the step 1 is specifically performed as follows: adding the formula I, C nH2n+1Br,K2CO3 and a proper amount of KI into acetone, mechanically stirring, heating in an oil bath at the constant temperature of 70 ℃, stirring until the reaction is finished, transferring the cooled reaction liquid into distilled water, stirring, filtering, collecting the precipitate, and drying in vacuum at 50-60 ℃ to obtain the formula II.
Preferably, the step 2 is specifically performed as follows: transferring the crude product II obtained in the step 1 into a volumetric flask, adding concentrated hydrochloric acid and ethanol into the volumetric flask, heating in an oil bath at constant temperature and stirring for a proper time, placing ice cubes into a large beaker, directly pouring and stirring reaction liquid until the fruit red disappears and milky white precipitation gradually appears, preparing 2mol L -1 NaOH aqueous solution, regulating the pH of the system to 7-8, and carrying out suction filtration after a large amount of precipitation is separated out to obtain solid III.
Preferably, the step 3 is specifically performed as follows: controlling the temperature between-5 ℃ and 5 ℃, and dissolving the solid formula III obtained in the step 2 into a mixed solution of concentrated hydrochloric acid, distilled water and acetone which are properly prepared; adding NaNO 2 into distilled water for dissolution, controlling the temperature, dripping the NaNO 2 into the mixed solution, and stirring until the mixed solution is gradually clarified; dissolving phenol in NaOH solution, dripping the prepared phenol solution into the diazonium salt solution, regulating the pH of the system to 9-10, continuously stirring at room temperature, regulating the pH of the system to 6-7 by diluted concentrated hydrochloric acid, extracting by using CH 2Cl2, collecting an organic layer, removing a solvent to obtain a solid, placing the solid in an oven for vacuum drying, purifying, and drying to obtain the formula IV.
Preferably, the step 4 is specifically performed as follows: adding the obtained formula IV and Br (CH 2)mOH,K2CO3 and a proper amount of KI into acetonitrile, heating in an oil bath at constant temperature, stirring until the reaction is finished, adding saturated NaHCO 3 aqueous solution, stirring for a certain time, extracting, washing, removing solvent, and purifying to obtain the formula V.
Preferably, the step 5 is specifically performed as follows: under the protection of N 2, at the temperature of minus 5 ℃ to 5 ℃, adding the formulas V and K 2CO3 into a solvent, adding BrCOCH 2 Br, stirring at room temperature until the reaction is finished, adding saturated NaHCO 3 aqueous solution into a reaction solution, extracting, washing with salt, removing the solvent, and drying to obtain the formula VI.
Preferably, the step 6 is specifically performed as follows: the obtained formula VI is dissolved in THF, then the THF is added into the THF in which 1, 2-bis (p-toluenesulfonyl) hydrazine is dissolved, the reaction system is cooled to-5 ℃,1, 8-diazabicyclo [5.4.0] undec-7-ene is slowly added into the reaction solution dropwise under the atmosphere of N 2, after stirring at room temperature until the reaction is finished, saturated NaHCO 3 aqueous solution is added into the reaction solution, the mixture is stirred for a certain time, extraction, salt washing, solvent removal, purification and drying are carried out, and the formula VII, namely the diazonium monomer Cn-Azo-Cm-N 2, is obtained.
The synthesis reaction formula of the photoresponsive polymer based on the azobenzene side group is as follows:
Under the atmosphere of N 2, adding a diazo monomer Cn-Azo-Cm-N 2 into a chloroform solution dissolved with a rhodium metal catalyst to carry out carbene stereolithography reaction, and stirring for 24 hours at room temperature; and then adding the polymerized solution into a mixed solution of methanol and dichloromethane, stirring again, collecting precipitate, dissolving in dichloromethane, collecting precipitate, repeating the above dissolving precipitation operation for multiple times until oligomer and dimer byproducts are removed, and obtaining the polymer Pm-Azo-Cn.
The side chain azobenzene polymer is applied to preparation of liquid crystal materials, optical information storage materials and nonlinear optical materials.
Compared with the prior art, the invention has the beneficial effects that:
The invention synthesizes the diazobenzene structural diazonium monomer through the Williamson ether formation reaction, the typical diazotization reaction and the like. Based on the method, the C1 rod-shaped liquid crystal polymer of the side-hanging azo phenyl group with high density and high stereoregularity is successfully obtained through the carbene directional polymerization catalyzed by rhodium metal.
The preparation method of the polymer monomer has reasonable design, mild reaction and simple operation, and the formed product has high yield, less impurities and less oligomers formed during polymerization reaction, is favorable for obtaining the polymer with high stereoregularity, and is suitable for further application development research.
Drawings
FIG. 1 is a comparison of FTIR spectra of monomers C4-Azo-C10-N 2 and their corresponding polymers P10-Azo-C4.
FIG. 2 shows the 1 H NMR and 13 C NMR spectra of the polymer P10-Azo-C4 and the corresponding structure assignment, wherein (a) corresponds to the 1 H NMR spectrum and (b) corresponds to the 13 C NMR spectrum.
FIG. 3 is a diagram of representative orthogonally polarized POM textures of P10-Azo-C1, P10-Azo-C4, P10-Azo-C8, P10-Azo-C10, and P6-Azo-C4.
FIG. 4 is a UV-vis absorption spectrum of a polymer P10-Azo-C1 solid phase spin-coated original film, after reaching photostable by irradiation of incident light at 365nm for 5min, and after reaching photostable by irradiation of visible light at 450nm for 12 min.
FIG. 5 is a UV-vis absorption spectrum of a polymer P10-Azo-C4 solid phase spin-coated original film, after reaching photostable by irradiation with incident light at 365nm for 5min, and after reaching photostable by irradiation with visible light at 450nm for 12 min.
FIG. 6 is a UV-vis absorption spectrum of a polymer P10-Azo-C8 solid phase spin-coated original film, after reaching photostable by irradiation with incident light at 365nm for 5min, and after reaching photostable by irradiation with visible light at 450nm for 12 min.
FIG. 7 is a UV-vis absorption spectrum of a polymer P10-Azo-C10 solid phase spin-coated original film, after reaching photostable by irradiation with incident light at 365nm for 5min, and after reaching photostable by irradiation with visible light at 450nm for 12 min.
FIG. 8 is a UV-vis absorption spectrum of a polymer P6-Azo-C4 solid phase spin-coated original film, after reaching photostable by irradiation with incident light at 365nm for 5min, and after reaching photostable by irradiation with visible light at 450nm for 12 min.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Synthesis of the monomer 4-octyloxy-4' - (10-diazoacetoxydecyloxy) azobenzene (designated C8-Azo-C10-N 2)
(1) Synthesis of 4-octoxyacetanilide:
8.0g (53 mmol) of 4-acetaminophen, 9.30g (48 mmol) of 1-bromooctane, 7.60g (55 mmol) of K 2CO3 and an appropriate amount of KI are added to 120mL of acetone, mechanically stirred, heated in an oil bath at a constant temperature of 70℃and stirred for 48h. After the reaction, transferring the cooled reaction solution into 700mL of distilled water, vigorously stirring for 20min, filtering, washing filter residues with distilled water for multiple times, collecting precipitate, and vacuum drying at 60 ℃ to obtain 11.5g of 4-octoxyacetanilide with the yield 90％.1H NMR(400MHz,CDCl3)δ(ppm):7.34(d,2H,Ar-H),7.05(s,1H,Ar-NH),6.85(d,2H,Ar-H),3.93(t,2H,CH2O),2.14(s,3H,NHCOCH3),1.77(m,2H,CH2CH2CH2O),1.29-1.43(m,10H,CH2),0.88(t,3H,CH3).FT-IR(cm-1):3326,2927,2858,1659,1604,1553,1511,1472,1239.
(2) Synthesis of 4-octoxyaniline:
The crude product 4-octyloxyacetanilide was directly transferred to a 500mL single-necked flask, 45mL of concentrated hydrochloric acid and 160mL of ethanol were added to the single-necked flask, and the mixture was heated in an oil bath at a constant temperature of 80℃and stirred for 24 hours. The reaction liquid system is fruit red. Placing 500g of ice cubes into a large beaker, directly pouring and stirring the fruit red reaction solution, enabling fruit red to disappear and gradually generate milky precipitate, preparing 2mol L - 1 NaOH aqueous solution, regulating the pH of the system to 7-8, after a large amount of white precipitate is separated out, carrying out suction filtration, washing filter residues with distilled water for 2-3 times, collecting filter residues, carrying out vacuum drying at room temperature to obtain 9.2g of white solid 4-octoxyaniline, and obtaining the yield 93％.1H NMR(400MHz,CDCl3)δ(ppm):6.83(d,2H,Ar-H),6.85(d,2H,Ar-H),3.88(t,2H,CH2O),1.76(qn,2H,CH2CH2CH2O),1.27-1.44(m,10H,CH2),0.89(t,3H,CH3).FT-IR(cm-1):2923,2848,1636,1511,1473,1231.
(3) Synthesis of 4-octyloxyphoto:
7.2g (32.5 mmol) of 4-octoxyaniline was dissolved in a mixture of 15mL of concentrated hydrochloric acid, 50mL of distilled water and 150mL of acetone, which was prepared, at a temperature of-5 to 5 ℃. 3.71g (53.8 mmol) of NaNO 2 is added into a mixture of 30mL of distilled water and 10g of ice blocks for ultrasonic dissolution, and the mixture is added into the mixed solution dropwise at the temperature of lower than 5 ℃ to turn the system into red and black, and the mixture is stirred for 30min, and the mixture is gradually clarified. 4.98g (52.9 mmol) of phenol was weighed out and dissolved in 30mL of NaOH solution having a concentration of 2mol/L, and stirred vigorously for 30min. Dripping the prepared phenol solution into the diazonium salt solution, regulating the pH of the system to 9-10 by using 2mol L -1 NaOH solution, continuously stirring for 2h at room temperature, regulating the pH of the system to 6-7 by using diluted concentrated hydrochloric acid, extracting by using CH 2Cl2, collecting an organic layer, washing for many times by using distilled water, removing the solvent by rotary evaporation to obtain a reddish brown solid, drying in a drying oven at the vacuum of 50 ℃, purifying by using a silica gel column, collecting the organic component by leaching, concentrating to remove the solvent, and then drying for 8h at the vacuum of 45 ℃ to obtain 9.51g of the product 4-octoxy azo phenol, wherein the yield is high 91.0％.1H NMR(400MHz,CDCl3)δ(ppm):7.88(d,2H,Ar-H),7.85(d,2H,Ar-H),7.01(d,2H,Ar-H),6.97(d,2H,Ar-H),4.02(t,2H,CH2O),1.81(m,2H,CH2CH2CH2O),1.29-1.40(m,10H,CH2),0.88(t,3H,CH3).FT-IR(cm-1):3467,2922,2856,1601,1584,1501,1475,1248.
(4) Synthesis of 4-octyloxy-4' - (10-hydroxydecyloxy) azobenzene:
The synthesis procedure of 10-bromo-1-decanol (Br (CH 2)10 OH)) was carried out by slowly adding 47g (280 mmol,1.1 eq.) of 48% HBr to 600mL toluene solution in which 44g (255 mmol) of 1, 10-decanediol had been dissolved, heating to reflux for 36h, cooling to room temperature after the reaction was completed, separating by extraction, collecting the organic components, removing the solvent by rotary evaporation, purifying by silica gel column, collecting the target product components, concentrating, removing the solvent to obtain 46g of colorless transparent liquid which was 10-bromo-1-decanol Br (CH 2)10 OH, yield 76%).
4G (12 mmol) of 4-octyloxypazophenol, 3.6g (15 mmol) of 10-bromo-1-decanol, 5g (36 mmol) of K 2CO3 and an appropriate amount of KI are added to 300ml of acetonitrile, heated in an oil bath at constant temperature of 90℃and stirred for 72h, and TLC tracks the progress of the reaction. After the reaction is finished, 50mL of saturated NaHCO 3 aqueous solution is added, the stirring reaction is continued for 0.5h, CH 2Cl2 is used for extraction, the organic phase is washed by concentrated brine, then the solvent is removed by rotary evaporation, the organic phase is purified by a silica gel column, the organic component is collected and eluted, and 5.4g of 4-octoxy-4' - (10-hydroxydecyloxy) azobenzene is obtained after the solvent is removed by concentration, the yield is obtained 90％.1H NMR(400MHz,CDCl3)δ(ppm):7.91(d,4H,Ar-H),7.01(d,4H,Ar-H),4.05(t,4H,ArOCH2),3.65(t,2H,CH2OH),1.84(qn,4H,ArOCH2CH2),1.64-1.32(m,24H,CH2),0.89(t,3H,CH3).FT-IR(cm-1):3276,2919,2850,1601,1580,1473,1463,1245,1150.
(5) Synthesis of 4-octyloxy-4' - (10-bromoacetoxydecyloxy) azobenzene:
5.4g (11.3 mmol) of 4-octyloxy-4' - (10-hydroxydecyloxy) azobenzene and 8.4g (57 mmol) of K 2CO3 were added to 300mL of CH 2Cl2 solvent under N 2 atmosphere at 0℃in ice bath, 6.8g (33.7 mmol) of bromoacetyl bromide was slowly added dropwise, stirred at room temperature for 2.5h, and the progress of the reaction was followed by Thin Layer Chromatography (TLC). After the reaction, 100mL of saturated aqueous NaHCO 3 was added to the reaction mixture, followed by extraction with CH 2Cl2. Washing the organic phase with strong brine, removing solvent by rotary evaporation, purifying with silica gel column, collecting the organic component, concentrating to remove solvent, vacuum drying at 45deg.C for 10 hr to obtain 6.3g brown yellow solid 4-octyloxy-4' - (10-bromoacetoxydecyloxy) azobenzene, and yield 94％.1H NMR(400MHz,CDCl3)δ(ppm):7.93(d,4H,Ar-H),7.01(d,4H,Ar-H),4.24(s,2H,CH2OOC),4.05(m,4H,ArOCH2),3.84(t,2H,CH2Br),1.83-1.30(m,28H,CH2),0.90(t,3H,CH3).FT-IR(cm-1):2919,2851,1754,1601,1581,1473,1294,1181,1149.
(6) Synthesis of 4-octyloxy-4' - (10-diazoacetoxydecyloxy) azobenzene C8-Azo-C10-N 2:
The preparation method of the 1, 2-bis (p-toluenesulfonyl) hydrazine comprises the following steps: reference methods [ E.Ideue, T.Toma, J.Shimokawa and T.Fukuyama, org.Synth.,2012,89,501-509 ]: 65.1g (349.7 mmol) of p-toluenesulfonyl hydrazine and 100.0g (524.5 mmol) of p-toluenesulfonyl chloride were added to a 1000mL three-necked round bottom flask via a solid addition funnel, 250mL of anhydrous CH 2Cl2 solvent was added, and under ice bath conditions, the solution was mechanically stirred (stirring frequency was 700 rpm), when the reaction temperature was lowered to below 3 ℃,80 mL of CH 2Cl2 solution in which 41.5g (524.5 mmol) of pyridine was dissolved was slowly added dropwise to the reaction solution, after completion of the dropwise addition over 10min, and the reaction temperature was controlled not to exceed 10℃during the dropwise addition. The reaction system is yellow transparent solution, white solid is quickly separated out, the rotation speed is adjusted to 1000rpm at the moment, and the reaction is continued for 3 hours. 200mL of ethanol was added and the reaction stirred for 30min. The reaction cloudy solution was transferred to a 1500mL beaker (larger precipitate was sheared with scissors), stirring was continued, 200mL distilled water and 200mL ethanol were added to the reaction solution separately, stirring was continued for 10min after the addition was completed, and then filtration was carried out with a buchner funnel to collect the crude product. The crude product 1, 2-bis (p-toluenesulfonyl) hydrazine was dispersed in 900mL of methanol with mechanical stirring, heated under reflux for 3h and filtered while hot. Washing with 300mL of methanol and 300mL of ethanol respectively, and collecting white filter residues; the slightly yellow filtrate is concentrated to a volume of about 150mL by rotary evaporation, and the filtrate is stood and cooled to room temperature, precipitates are separated out, and is filtered, and filter residues are respectively washed by 200mL of methanol and 200mL of ethanol, and the filter residues are combined with the product collected in the previous step, and are dried in vacuum for 10 hours at 45 ℃ to obtain 97.12g of the product with the yield of 82 percent. Preserving at room temperature for standby .1H NMR(400MHz,DMSO)δ(ppm):9.58(s,2H,NH),7.65(d,4H,Ar-H),7.38(d,4H,Ar-H),2.40(s,6H,CH3).
3.3G (5.5 mmol) of 4-octyloxy-4' - (10-bromoacetoxydecyloxy) azobenzene were dissolved in 11mL of THF, then added to 100mL of THF having dissolved 3.74g (11 mmol) of 1, 2-bis (p-toluenesulfonyl) hydrazine, and the reaction system was cooled to 0℃under N 2 atmosphere, 4.1mL (27.5 mmol) of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) was slowly added dropwise to the reaction solution, and stirred at room temperature for 10 minutes. After the reaction, 100mL of saturated aqueous NaHCO 3 was added to the reaction mixture, and the mixture was extracted with CH 2Cl2. The organic phase is washed by strong brine, the solvent is removed by rotary evaporation, the organic phase is purified by a silica gel column, the organic component is collected and leached out, the organic phase is concentrated to remove the solvent, and then the organic phase is dried for 10 hours at 45 ℃ in vacuum to obtain 2.2g of bright yellow solid powder, namely 4-octyloxy-4' - (10-diazo acetoxy) azobenzene. Yield rate 71％.1H NMR(400MHz,CDCl3)δ(ppm):7.86(d,4H,Ar-H),6.98(d,4H,Ar-H),4.73(s,1H,OOCCHN2),4.13(t,2H,CH2OOC),4.05(t,4H,ArOCH2),1.81(m,4H,ArOCH2CH2),1.67(m,2H,CH2CH2OOC),1.48(m,4H,ArOCH2CH2CH2),1.32(m,18H,CH2),0.89(t,3H,CH3).FT-IR(cm-1):3108,2921,2850,2111,1681,1601,1580,1500,1401,1144.
Synthesis of monomeric 4-methoxy-4' - (10-diazoacetoxydecyloxy) azobenzene (designated C1-Azo-C10-N 2)
The tail chain of C1-Azo-C10-N 2 is directly synthesized from methoxyaniline, and the other steps are the same as those of C8-Azo-C10-N 2.
The yield of C1-Azo-C10-N 2 was 69%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.86(m,4H,Ar-H),6.99(m,4H,Ar-H),4.73(s,1H,OOCCHN2),4.15(t,2H,CH2OOC),4.03(t,2H,ArOCH2),3.89(s,3H,Ar-OCH3),1.81(m,2H,ArOCH2CH2),1.62(m,2H,CH2CH2OOC),1.47(m,2H,ArOCH2CH2CH2),1.32(m,10H,CH2).FT-IR(cm-1):3116,2919,2866,2125,1675,1600,1581,1241,1183,1145,1014.
Synthesis of monomeric 4-butoxy-4' - (10-diazoacetoxydecyloxy) azobenzene (designated C4-Azo-C10-N 2)
1-Bromooctane in the synthesis step of C8-Azo-C10-N 2 is replaced by 1-bromobutane, and the other steps are the same.
The yield of C4-Azo-C10-N 2 was 77%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.86(d,4H,Ar-H),6.99(d,4H,Ar-H),4.73(s,1H,OOCCHN2),4.15(t,2H,CH2OOC),4.02(m,4H,ArOCH2),1.81(m,4H,ArOCH2CH2),1.64(m,2H,CH2CH2OOC),1.51(m,4H,ArOCH2CH2CH2),1.32(m,10H,CH2),0.99(t,3H,CH3).FT-IR(cm-1):3111,2924,2853,2132,1674,1602,1583,1503,1242,1109.
Synthesis of the monomer 4-decyloxy-4' - (10-diazoacetoxydecyloxy) azobenzene (designated C10-Azo-C10-N 2)
1-Bromooctane in the synthesis step of C8-Azo-C10-N 2 is replaced by 1-bromodecane, and the other steps are the same.
The yield of C10-Azo-C10-N 2 was 73%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.86(d,4H,Ar-H),6.98(d,4H,Ar-H),4.73(s,1H,OOCCHN2),4.15(t,2H,CH2OOC),4.02(t,4H,ArOCH2),1.81(m,4H,ArOCH2CH2),1.64(m,2H,CH2CH2OOC),1.47(m,4H,ArOCH2CH2CH2),1.32(m,22H,CH2),0.88(t,3H,CH3).FT-IR(cm-1):3097,2919,2849,2111,1681,1601,1580,1499,1472,1241,1145,1016.
Synthesis of monomeric 4-butoxy-4' - (6-diazoacetoxy) azobenzene (designated C4-Azo-C6-N 2)
The 1-bromooctane in the C8-Azo-C10-N 2 synthesis step was replaced with 1-bromobutane, 10-bromo-1-decanol was replaced with 6-bromo-1-hexanol, and the other steps were identical.
The yield of C4-Azo-C6-N 2 was 73%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.86(d,4H,Ar-H),6.98(d,4H,Ar-H),4.73(s,1H,OOCCHN2),4.18(t,2H,CH2OOC),4.03(m,4H,ArOCH2),1.78(m,4H,ArOCH2CH2),1.69(m,2H,CH2CH2OOC),1.47(m,6H,ArOCH2CH2CH2,CH2CH2CH2OOC),1.00(t,3H,CH3).FT-IR(cm-1):3101,2926,2857,2115,1668,1605,1583,1504,1249,1147.
Synthesis of Polymer P10-Azo-C8: under an atmosphere of N 2, 1.1g (2 mmol) of diazo monomer C8-Azo-C10-N 2 was added to 2mL of a 13mg (equivalent to 0.02eq of monomer) metal catalyst (the metal catalyst was a rhodium cyclooctadiene proline catalyst, prepared by: under N 2 atmosphere, 0.245g (2 mmol) of L-proline and 0.08g (2 mmol) of sodium hydroxide are dissolved in 20mL of anhydrous methanol, stirred at room temperature for 45min, the resulting solution is added to 10mL of an anhydrous methanol yellow suspension containing 0.493g (1 mmol) of (1, 5-cyclooctadiene) rhodium (I) chloride dimer, stirred at room temperature for 60min to obtain a yellow transparent solution, the solvent is removed in vacuo, the resulting solid is dissolved in anhydrous CH 2Cl2, filtered, the insoluble matter is removed to obtain a transparent liquid, the solvent is removed again, dried in vacuo at room temperature to obtain 0.35g of yellow crystals, the chloroform solution with a yield of 52％.1H NMR(400MHz,CDCl3)δ(ppm):4.61-3.50(br s,4H,CH＝CH),3.95(m,1H,COO-CH),3.5(s,1H,NH),3.05(m,2H,NH-CH2),2.60(m,2H,CH＝CH-CH2),2.42(m,2H,CH＝CH-CH2),2.22(m,2H,COO-CH-CH2),2.02(m,1H,NH-CH2-CH2),1.99(m,2H,CH＝CH-CH2),1.75(m,2H,CH＝CH-CH2),1.67(m,1H,NH-CH2-CH2)) is stirred at room temperature for 24h, then the polymerized solution is added dropwise to a mixed solution of 300mL of methanol and CH 2Cl2 (methanol: CH 2Cl2 =1, V/V) with a stirring rate of 300rpm, the precipitate is collected in a small amount of CH 2Cl2, the precipitate is dropwise added to the methanol solvent with a vigorous stirring rate of 400rpm, the precipitate is collected, the precipitate is repeatedly dissolved until the precipitate is completely removed until the two-phase of the yellow by-product is completely removed by GPC (until the 3-produced by-product is completely removed by a polymerization curve of 0.8 g-3, and the 3g of the yellow by-product is completely removed by GPC, and the 3 is completely removed by a side product, and the method is completely removed by completely removing the method from the A0.8 g of the byproduct under conditions, and the conditions of the conditions were completely removed by the conditions were completely and completely removed by the method 61％.1H NMR(400MHz,CDCl3)δ(ppm):7.84(s,4H,Ar-H),6.95(s,4H,Ar-H),4.01(s,6H,CH2OOC,ArOCH2),1.79(s,4H,ArOCH2CH2),1.59(s,2H,CH2CH2OOC),1.45(s,4H,ArOCH2CH2CH2),1.29(s,18H,CH2),0.88(s,3H,CH3).FT-IR(cm-1):2920,2852,1735,1601,1581,1498,1240,1148.
Synthesis of Polymer P10-Azo-C1: the C8-Azo-C10-N 2 in the P10-Azo-C8 synthesis step was replaced with C1-Azo-C10-N 2, and the other steps were the same.
The yield of polymer P10-Azo-C1 was 73%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.75(s,4H,Ar-H),6.85(s,4H,Ar-H),3.99(s,2H,CH2OOC),3.79(s,2H,ArOCH2),3.74(s,3H,Ar-OCH3),3.19(s,1H,OOCCH),1.67(s,4H,ArOCH2CH2,CH2CH2OOC),1.29(s,12H,CH2).FT-IR(cm-1):2922,2851,1731,1598,1580,1498,1245,1145.
Synthesis of Polymer P10-Azo-C4: the C8-Azo-C10-N 2 in the P10-Azo-C8 synthesis step was replaced with C4-Azo-C10-N 2, and the other steps were the same.
The yield of polymer P10-Azo-C4 was 77%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.79(s,4H,Ar-H),6.87(s,4H,Ar-H),3.87(s,6H,CH2OOC,ArOCH2),3.21(s,1H,OOCCH),1.70(s,6H,ArOCH2CH2,CH2CH2OOC),1.30(s,14H,CH2),0.87(m,3H,CH3).FT-IR(cm-1):2923,2852,1732,1600,1580,1498,1240,1146.
Synthesis of Polymer P10-Azo-C10: the C8-Azo-C10-N 2 in the P10-Azo-C8 synthesis step was replaced with C10-Azo-C10-N 2, and the other steps were the same.
The yield of polymer P10-Azo-C10 was 65%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.84(s,4H,Ar-H),6.94(s,4H,Ar-H),3.97(s,6H,ArOCH2,CH2OOC),1.78(s,H,rOCH2CH2),1.63(s,2H,CH2CH2OOC),1.44(m,4H,ArOCH2CH2CH2),1.27(m,22H,CH2),0.88(s,3H,CH3).FT-IR(cm-1):2920,2851,1734,1601,1581,1498,1244,1147.
Synthesis of Polymer P6-Azo-C4C 8-Azo-C10-N 2 in the P10-Azo-C8 synthesis step was replaced with C4-Azo-C6-N 2, and the other steps were the same.
The yield of polymer P6-Azo-C4 was 74%. Characterization results are as follows ：1H NMR(400MHz,CDCl3)δ(ppm):7.75(s,4H,Ar-H),6.79(s,4H,Ar-H),3.91(m,6H,CH2OOC,ArOCH2),3.26(s,1H,OOCCH),1.59(m,6H,ArOCH2CH2,CH2CH2OOC),1.18(s,6H,CH2),0.88(s,3H,CH3).FT-IR(cm-1):2923,2855,1731,1602,1582,1499,1241,1148.
Preparation of sample films
The sample film for UV-vis test characterization was prepared by a solution spin-coating method, and all polymers had good film forming properties. Firstly preparing a polymer sample trichloromethane solution with concentration of 1wt% dissolved by ultrasonic, then dripping the solution on a transparent quartz plate, spin-coating for 10s at a rotating speed of 500rpm, and spin-coating for 40s at a rotating speed of 3000 rpm.
Table 1 shows the yields, molecular characterization results and glass transition temperatures of a series of side chain azobenzene polymers prepared in the examples.
TABLE 1 yield, molecular characterization and glass transition temperature Table
a GPC determination, THF mobile phase, polystyrene standard; b DSC measurement, under N 2 atmosphere, the temperature rising and falling speed is 10 ℃ min -1
The yield of the series of polymers prepared by the invention is about 70 percent. The relative molecular weight and molecular weight distribution were determined by GPC using THF as the mobile phase and polystyrene as the standard. As can be seen from table 1: the apparent relative weight average molecular weight M w is higher than 32kDa, the number average molecular weight M n is at least 12kDa, and the molecular weight polydispersity index PDI is between 2.67 and 2.93.
The composition and structure of the synthesized series of C1 polymers were characterized and confirmed by nuclear magnetic resonance testing and infrared spectroscopic analysis. Taking diazo monomer C4-Azo-C10-N 2 and polymer P10-Azo-C4 as examples, FIG. 1 is a FTIR spectrum comparison of monomer C4-Azo-C10-N 2 and its corresponding polymer P10-Azo-C4. As shown in the figure, the characteristic absorption peak of diazo at 2112cm -1 can be clearly seen in the FTIR spectrum of monomer C4-Azo-C10-N 2, and the characteristic absorption peak of diazo at polymer P10-Azo-C4 is completely disappeared, which shows that the monomer smoothly performs carbene polymerization under the action of Rh complex catalyst.
FIG. 2 shows the 1 H NMR and 13 C NMR spectra of the polymer P10-Azo-C4 and the corresponding structure assignments. The integral ratio of the characteristic absorption peaks at chemical shifts δ=7.79 and 6.87 in fig. 2a is 4:4, corresponding to the characteristic absorption peak of the hydrogen atom on the benzene ring of azobenzene (Azo). The chemical shift is δ=3.21 the characteristic absorption peak at which corresponds to the characteristic absorption peak of a hydrogen atom on the polymer backbone. In b in 13 CNMR spectrum 2 of polymer P10-Azo-C4, the chemical shift was a single peak occurring near δ= 45.10 and near δ= 170.80, respectively, corresponding to the characteristic absorption of the C atom in the main chain and the ester carbonyl C atom in the side chain of the syndiotactic polymer, indicating a very high syndiotacticity of the polymer.
POM was used to observe the thermal properties and liquid crystal phase behavior of liquid crystal polymers. FIG. 3 is a schematic diagram of a typical cross-polarized POM texture of the prepared azobenzene side chain liquid crystal polymer. The film sample prepared by melting and pressing the series of polymers shows remarkable birefringence phenomenon under an orthogonal polarization microscope at room temperature, which shows that an ordered liquid crystal phase structure is formed, and along with the rise of the temperature, the visual field is completely black and enters an isotropic phase. Subsequently, the temperature is gradually lowered, the birefringence phenomenon reappears, and the polymer enters the liquid crystal phase again, and the bidirectional thermotropic liquid crystal phase characteristic is shown.
FIGS. 4 to 8 are UV-vis absorption spectra of a series of azobenzene liquid crystal C1 polymer solid-state spin-coated original films prepared by the invention, UV-vis absorption spectra after reaching a photostable after 5min of irradiation with 365nm incident light, and UV-vis absorption spectra after reaching a photostable after 12min of irradiation with 450nm visible light. It can be seen from the figure that the polymer films all exhibit a phenomenon similar to that of the polymer P10-Azo-C4 film, i.e. a significant photoinduced cis-trans isomerisation characteristic peak occurs under irradiation of 365nm ultraviolet light, followed by at least 95% of the cis-structure of the polymer being converted into trans-structure under irradiation of 450nm visible light. Test results show that the azobenzene liquid crystal C1 polymer has good light responsiveness, and lays a foundation for application in the aspects of optical information storage and the like.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The photoresponsive polymer monomer based on the azobenzene side group is characterized by having the following structure:
wherein m=6 to 10; n=1 to 10.
2. The method for preparing the photo-responsive polymer monomer based on azobenzene side group as defined in claim 1, wherein when m=6-10; when n is not equal to 1, the following reaction process is carried out:
step 1, formula I and formula C nH2n+1 Br, n is not equal to 1; reacting to form a step II;
Step 2, a step of reacting the formula II under an acidic condition to generate a formula III;
Step 3, carrying out diazotization reaction on the formula III and NaNO 2 in HCl, and then reacting with phenol under an acidic condition to generate a formula IV;
Step 4, a step of reacting the formula IV with a formula Br (CH 2)m OH, m=6-10; to generate a formula V;
Step 5, a step of reacting formula V with formula BrCOCH 2Br、K2CO3 under CH 2Cl2 to form formula VI;
Step 6, a step of forming formula VII with 1, 2-bis (p-toluenesulfonyl) hydrazine, 1, 8-diazabicyclo [5.4.0] undec-7-ene in THF solution; wherein 1, 2-bis (p-toluenesulfonyl) hydrazine is designated DTHZ;
when m=6 to 10; when n=1, the p-methoxyaniline is adopted in the formula III, and the reaction is carried out according to the steps 3-6.
3. The photoresponsive polymer based on the azobenzene side group is characterized by being prepared by a carbene stereolithography reaction of the photoresponsive polymer monomer based on the azobenzene side group in the following structure:
Wherein m=6 to 10; n=1 to 10; the number average molecular weight of the photoresponsive polymer of the azobenzene side group is more than 12 kDa.
4. A class of azobenzene side group based photo-responsive polymers according to claim 3, wherein the azobenzene side group based photo-responsive polymers have the structure:
wherein m=6, 10; n=1, 4,8, 10; the number average molecular weight of the photoresponsive polymer of the azobenzene side group is more than 12 kDa.
5. A class of azobenzene side group based photoresponsive polymers according to claim 4, having one of the following structures:
。
6. the preparation method of the photo-responsive polymer based on azobenzene side group as claimed in any one of claims 3 to 5, which is characterized by comprising the following steps: adding the polymer monomer according to claim 1 into chloroform solution dissolved with a rhodium metal catalyst for carbene stereospecific polymerization under the atmosphere of N 2, stirring at room temperature, adding the polymerized solution into a mixed solution of methanol and dichloromethane, stirring again, collecting precipitate, dissolving the precipitate in dichloromethane, collecting precipitate, repeating the above dissolving precipitation operation for a plurality of times until oligomer and dimer byproducts are removed, and obtaining the light-responsive polymer with azobenzene side groups.
7. The method for preparing the photo-responsive polymer based on azobenzene side group as defined in claim 6, wherein the mass-volume ratio of the polymer monomer to chloroform solution is 0.5-0.6 g/mL;
The solubility of the rhodium catalyst in chloroform is 6-7 mg/mL.
8. The method for preparing a class of photoresponsive polymers based on azobenzene side groups according to claim 6, wherein the metal rhodium catalyst is cyclooctadiene proline rhodium catalyst;
And stirring at room temperature for 22-25 h.
9. The method for preparing the photo-responsive polymer based on azobenzene side group according to any one of claims 6 to 8, wherein the volume ratio of methanol to dichloromethane is 2:1 to 1:1;
The mass volume ratio of the polymer monomer to the mixed solution of methanol and dichloromethane is 0.003-0.004 g/mL.
10. The application of the photo-responsive polymers based on azobenzene side groups in preparation of liquid crystal materials, optical information storage materials and nonlinear optical materials according to any one of claims 3-5.
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