CN117964824A - Multiple stimulus responsive homopolymer and preparation method and application thereof - Google Patents
Multiple stimulus responsive homopolymer and preparation method and application thereof Download PDFInfo
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- CN117964824A CN117964824A CN202410371853.XA CN202410371853A CN117964824A CN 117964824 A CN117964824 A CN 117964824A CN 202410371853 A CN202410371853 A CN 202410371853A CN 117964824 A CN117964824 A CN 117964824A
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- 229920001519 homopolymer Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 58
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 36
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003814 drug Substances 0.000 claims abstract description 30
- -1 hydroxy-N-methylamino acrylamide Chemical compound 0.000 claims abstract description 26
- 229940079593 drug Drugs 0.000 claims abstract description 23
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000376 reactant Substances 0.000 claims abstract description 15
- LHNPFNSPHRFXAB-UHFFFAOYSA-N (2-methylprop-2-enoylamino) acetate Chemical compound CC(=C)C(=O)NOC(C)=O LHNPFNSPHRFXAB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000001459 lithography Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000693 micelle Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000002829 reductive effect Effects 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010898 silica gel chromatography Methods 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- FJKBCAOWAMDSOI-UHFFFAOYSA-N C(#N)C(CCC(=O)O)(C)SCSSCCCCCCCCCCCC Chemical group C(#N)C(CCC(=O)O)(C)SCSSCCCCCCCCCCCC FJKBCAOWAMDSOI-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- PXWASTUQOKUFKY-UHFFFAOYSA-N 2-(methylamino)propan-1-ol Chemical compound CNC(C)CO PXWASTUQOKUFKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 230000001225 therapeutic effect Effects 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 238000002834 transmittance Methods 0.000 description 17
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 14
- 230000008859 change Effects 0.000 description 11
- 230000004043 responsiveness Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZHFLZTSMYXVEKG-UHFFFAOYSA-N (prop-2-enoylamino)methyl acetate Chemical compound CC(=O)OCNC(=O)C=C ZHFLZTSMYXVEKG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Epidemiology (AREA)
- Pharmacology & Pharmacy (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a multi-stimulus-responsive homopolymer, a preparation method and application thereof, wherein the preparation method of the multi-stimulus-responsive homopolymer comprises the following steps: mixing N-methylol acrylamide, acetic anhydride, alkali and a first solvent, reacting to obtain N-acetoxy methacrylamide, mixing N-acetoxy methacrylamide, an acid binding agent, 2-methylamino alcohol and a second solvent, reacting to obtain hydroxy-N-methylamino acrylamide, mixing hydroxy-N-methylamino acrylamide, a reactant, 4-dimethylaminopyridine and a third solvent, dropwise adding a dichloromethane solution of dicyclohexylcarbodiimide, reacting to obtain R-N-m-AM, mixing R-N-m-AM, a RAFT chain transfer reagent, a fourth solvent and an initiator, and reacting in nitrogen or inert gas atmosphere to obtain a multi-stimulus-responsive homopolymer which can be applied to drug release and also can be applied to lithography patterns.
Description
Technical Field
The invention belongs to the technical field of stimulus-responsive intelligent materials, and particularly relates to a multiple stimulus-responsive homopolymer, a preparation method and application thereof.
Background
The stimulus-responsive polymer is a macromolecular system with intelligent behaviors, has various stimulus signals (such as temperature, pH value, CO 2, light and the like), and has good application in the fields of self-assembly, biological medicine, intelligent devices and the like. Currently, single stimulus responsive polymers have failed to meet the evolving needs and multiple stimulus responsive polymers have evolved. The steps of the multi-stimulus-responsive copolymer prepared by the copolymerization method are complex, and the structure of the multi-stimulus-responsive copolymer cannot be accurately regulated due to different reactivity ratios of the monomers during copolymerization, so that the response behavior of the multi-stimulus-responsive copolymer is affected. The above disadvantages can be overcome by a multiple stimulus-responsive homopolymer prepared by homopolymerization of monomers containing multiple responsive groups, but how to precisely set the spatial arrangement of different responsive groups in the multiple stimulus-responsive homopolymer and make it exhibit respective response properties is a difficulty in designing in this field, and in addition, the number and type of multiple stimulus-responsive homopolymers are not large. Therefore, it is important to develop new multi-stimulus responsive homopolymers and methods for their preparation.
Among different external stimuli, the optical stimulus has the characteristics of easy acquisition, high sensitivity and reversibility, strong remote control and the like. The characteristics lead the light stimulus responsive polymer to have wide application value in the fields of light control self-assembly, light control medicine release, optical storage and the like. The combination of the photo-stimulus-responsive polymer with plain paper can produce a paper material based on a "write-erase-write" mode that can be erased repeatedly. The excellent erasable paper needs to undergo color conversion under external environmental stimulus, the conversion needs to have sensitivity and reversibility, and each state needs to have certain stability, which presents certain challenges for the loaded photo-stimulus responsive polymer.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a multiple stimulus responsive homopolymer.
It is another object of the present invention to provide a method for producing the above-mentioned multiple stimulus-responsive homopolymer.
It is a further object of the present invention to provide the use of the above-described multiple stimulus-responsive homopolymers for non-diagnostic or therapeutic purposes in controlling drug release.
It is another object of the present invention to provide the use of the above-mentioned multi-stimulus-responsive homopolymer in lithographic patterns, which can be used for producing erasable paper, can be used for pattern writing under ultraviolet conditions by mold masking, can be used for pattern erasing under heating/blue light irradiation conditions, and is reversible.
The aim of the invention is achieved by the following technical scheme.
A multiple stimulus-responsive homopolymer having the structural formula:
wherein m=1 or 2, and n=10 to 200.
The preparation method of the multi-stimulus responsive homopolymer comprises the following steps:
Step 1, mixing N-methylol acrylamide, acetic anhydride (Ac 2 O), alkali and a first solvent, stirring at room temperature for 5-8 hours, carrying out suction filtration, and carrying out reduced pressure distillation to remove the first solvent to obtain white solid N-acetoxy methacrylamide (OAc-AM), wherein the ratio of the N-methylol acrylamide to the acetic anhydride to the alkali is 1 in parts by weight: (2.0 to 2.5): (2.0-2.5);
In the step 1, the ratio of the parts by weight of the N-methylolacrylamide substance to the parts by volume of the first solvent is 1: (0.8-1.0), wherein the unit of the parts by weight of the substances is mmo1, and the unit of the parts by volume is mL.
In step 1, the first solvent is Dichloromethane (DCM).
In step 1, the base is potassium carbonate or triethylamine.
Step 2, mixing the N-acetoxy methacrylamide (OAc-AM), an acid binding agent, 2-methylamino alcohol and a second solvent, stirring at 30-35 ℃ for 6-8 hours, carrying out suction filtration, carrying out reduced pressure distillation to remove the second solvent, and purifying to obtain hydroxyl-N-methylamino acrylamide (OH-N-m-AM), wherein the ratio of the N-acetoxy methacrylamide (OAc-AM), the acid binding agent and the 2-methylamino alcohol is 1 according to the parts by weight of substances: (1.3 to 1.5): (1.3-1.5), wherein the acid binding agent is potassium carbonate, and the 2-methylamino alcohol is 2-methylamino ethanol or 2-methylamino propanol;
In step 2, the ratio of the parts by weight of the substance of the N-acetoxy methacrylamide (OAc-AM) to the parts by volume of the second solvent is 1: (2.0-2.3), wherein the unit of the parts by weight of the substances is mmo1, and the unit of the parts by volume is mL.
In step 2, the second solvent is acetonitrile (CH 3 CN).
In step2, the purification is performed by silica gel column chromatography.
In the above technical scheme, the eluent adopted in the silica gel column chromatography in the step 2 is a mixture of methanol and ethyl acetate, and the ratio of the methanol to the ethyl acetate is 1 (8-10) in parts by volume.
Step 3, mixing the hydroxyl-N-methylamino acrylamide (OH-N-m-AM), a reactant, 4-Dimethylaminopyridine (DMAP) and a third solvent to obtain a first mixture, dropwise adding a dichloromethane solution of Dicyclohexylcarbodiimide (DCC) into the first mixture at 0-10 ℃, heating to room temperature after dropwise adding, stirring at room temperature for 12-24 hours, suction filtering, distilling under reduced pressure to remove the third solvent, and purifying to obtain R-N-m-AM, wherein the ratio of the Dicyclohexylcarbodiimide (DCC) to the 4-Dimethylaminopyridine (DMAP) in the dichloromethane solution of the hydroxyl-N-methylamino acrylamide (OH-N-m-AM), the reactant and the Dicyclohexylcarbodiimide (DCC) is 1 according to the parts by weight of substances: (1.1 to 1.3): (1.1 to 1.3): (0.1-0.3), wherein the reactant is azobenzene-4-benzoic acid, and the structural formula of R-N-m-AM (AM is acrylamide) isM=1 or 2;
In the step 3, the ratio of the parts by weight of the substances of the hydroxyl-N-methylaminoacrylamide (OH-N-m-AM) to the parts by volume of the third solvent is 1: (2.0-2.3), wherein the unit of the parts by weight of the substances is mmo1, and the unit of the parts by volume is mL.
In step 3, the third solvent is dichloromethane.
In step 3, the purification is performed by silica gel column chromatography.
In the above technical scheme, the eluent adopted in the silica gel column chromatography in the step3 is a mixture of petroleum ether and ethyl acetate, and the ratio of petroleum ether to ethyl acetate is 1: (1-3).
In the step 3, the concentration of Dicyclohexylcarbodiimide (DCC) in the dichloromethane solution of Dicyclohexylcarbodiimide (DCC) is 2.0 to 2.5mmol/mL.
Step 4, mixing the R-N-m-AM, the RAFT chain transfer reagent, a fourth solvent and an initiator, stirring for 18-24 hours at 65-70 ℃ in nitrogen or inert gas atmosphere, quenching with ice water, settling, centrifuging, washing and drying to obtain a multi-stimulus-responsive homopolymer (P (R-N-m-AM) n), wherein the initiator is Azodiisobutyronitrile (AIBN), and the ratio of the R-N-m-AM to the RAFT chain transfer reagent to the initiator is (30-600) according to the parts by weight of substances: 3: (1-1.5), wherein the RAFT chain transfer agent is 4-cyano-4- [ [ (dodecylthio) thiomethyl ] thio ] pentanoic acid (CDTPA).
In step 4, the fourth solvent is 1, 4-dioxane.
In the step 4, the ratio of the R-N-m-AM to the fourth solvent is 1 in parts by weight: (1-1.5).
In the step 4, the sedimentation agent adopted in the sedimentation is n-hexane, diethyl ether or methanol.
In the step 4, the rotation speed of the centrifugation is 7000-10000 r/min, and the centrifugation time is 3-5 min.
The use of the above-described multiple stimulus-responsive homopolymers for the controlled release of a drug for non-diagnostic or therapeutic purposes.
According to the technical scheme, the multi-stimulus-responsive homopolymer and the medicament are dissolved in tetrahydrofuran, the multi-stimulus-responsive homopolymer and the medicament are dripped into distilled water under the stirring condition of 600-800 r/min, the dripping is Bi Jiaoban-48 h, the medicament is removed through centrifugation, and the medicament-carrying homopolymer micelle solution is obtained, and is subjected to ultraviolet irradiation or acid addition to stimulate the medicament release.
The use of the above-described multiple stimulus-responsive homopolymers in lithographic patterning.
In the above technical scheme, the multi-stimulus responsive homopolymer is loaded on paper to obtain erasable paper, a part of the erasable paper is irradiated by ultraviolet light, the color of the erasable paper is deepened by the ultraviolet light irradiation part relative to a part which is not irradiated by ultraviolet light, the edge of the deepened part of the erasable paper encloses a pattern, and when the erasable paper is irradiated by blue light or heated, the pattern disappears.
Compared with the prior art, the invention has the beneficial effects that:
1. The preparation method is simple, and solves the problems of small quantity and variety of the existing multi-stimulus responsive homopolymers and limited application range;
2. the multi-stimulus responsive homopolymer can respond to four stimulus, has multi-stimulus responsiveness, and has high sensitivity, reversibility and stability in response behavior;
3. The multi-stimulus responsive homopolymer has multiple purposes, can be applied to controlling drug release, can also be applied to photoetching patterns, can be used for reversibly recording and erasing various patterns during photoetching, and has good stability and cyclicity.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of CH 3 -N-1-AM and P (CH 3-N-1-AM)26;
FIG. 2 is a nuclear magnetic resonance spectrum of Ph-N-1-AM and P (Ph-N-1-AM) 25;
FIG. 3 is a nuclear magnetic resonance spectrum of Azo-N-1-AM, P (Azo-N-1-AM) 20、P(Azo-N-1-AM)32, and P (Azo-N-1-AM) 58;
FIG. 4 is a nuclear magnetic resonance spectrum of Azo-N-2-AM and P (Azo-N-2-AM) 21;
FIG. 5 is a Gel Permeation Chromatography (GPC) diagram of a multiple stimulus-responsive homopolymer;
FIG. 6 is a graph of temperature versus light transmittance for solution A;
FIG. 7 is a temperature-transmittance curve;
FIG. 8 is an ultraviolet visible absorption spectrum of a homopolymer tetrahydrofuran solution;
FIG. 9 is a TEM image of micelles;
FIG. 10 is a graph showing the cumulative release of nile red from a nile red-loaded homopolymer micelle solution over time;
fig. 11 is a photograph of a rewritable paper.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
N-methylolacrylamide, acetic anhydride, 2-methylaminoethanol, 2-methylaminopropanol, potassium carbonate, acetic acid, benzoic acid, azobenzene-4-benzoic acid, dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP), 4-cyano-4- [ [ (dodecylthio) thiomethyl ] thio ] pentanoic acid (CDTPA, RAFT chain transfer reagent), azobisisobutyronitrile (AIBN), and Nile Red (NR) are all commercially available.
The synthetic routes for the multiple stimulus-responsive homopolymers of examples 1-6 were as follows:
。
transmittance versus temperature curve: the rate of temperature rise in the change curve of transmittance with temperature rise is 1 ℃/min, and the rate of temperature drop in the change curve of transmittance with temperature drop is 1 ℃/min.
In the following examples, ultraviolet lamps were used for ultraviolet irradiation, and the power of all the ultraviolet lamps in the examples was 90W (365 nm); blue light is a blue light lamp, and the power of all blue light lamps in this embodiment is 30W (wavelength 430 nm).
Example 1 (comparative)
A method for preparing a multiple stimulus-responsive homopolymer (P (CH 3-N-1-AM)26), comprising the steps of:
Step 1, dissolving N-methylol acrylamide (6.0 g,60 mmol), a base (16.5 g,120 mmol) and acetic anhydride (12.2 g,120 mmol) in 60mL of a first solvent, stirring at room temperature for reaction for 5h, suction filtering, and distilling under reduced pressure to remove the first solvent to obtain white solid N-acetoxy methacrylamide (OAc-AM) (7.8 g, 92%) to obtain N-acetoxy methacrylamide (OAc-AM) without further purification, wherein the first solvent is Dichloromethane (DCM), and the base is potassium carbonate;
The nuclear magnetism of N-acetoxy methyl acrylamide (OAc-AM) is ：1H NMR (400 MHz, CDCl3) δ 6.70 (s, 1H), 6.37 (dd,J= 17.0, 1.0 Hz, 1H), 6.20 – 5.99 (m, 1H), 5.76 (dd,J= 10.4, 1.0 Hz, 1H), 5.33 (d,J= 7.3 Hz, 2H), 2.08 (s, 3H).
Step 2, N-acetoxymethacrylamide (OAc-AM) (7.8 g,55 mmol), an acid-binding agent (9.9 g,72 mmol) and 2-methylamino alcohol (5.4 g,72 mmol) are dissolved in 110mL of a second solvent, stirred at 30 ℃ for reaction for 8 hours, suction filtered, distilled under reduced pressure to remove the second solvent, and the product is purified by silica gel column chromatography (the used eluent is a mixture of methanol and ethyl acetate, the ratio of ethyl acetate to methanol is 10:1 in volume parts) to obtain hydroxy-N-methylaminoacrylamide (6.5 g, 75%), wherein the acid-binding agent is potassium carbonate, the 2-methylamino alcohol is 2-methylaminoethanol, and the second solvent is acetonitrile (CH 3 CN);
In this example, the hydroxy-N-methylaminoacrylamide was N- (((2-hydroxyethyl) (methyl) amino) methyl) acrylamide (OH-N-m-AM) with a nuclear magnetic resonance of ：1H NMR(400MHz,CDCl3) δ 6.64 (s, 1H), 6.31 (dd,J= 17.0, 1.4 Hz, 1H), 6.15 (dd,J= 17.0, 10.2 Hz, 1H), 5.69 (dd,J= 10.2, 1.4 Hz, 1H), 4.25 (d,J= 6.3 Hz, 2H), 3.70 – 3.63 (m, 2H), 2.71 – 2.65 (m, 2H), 2.34 (s, 3H).
Step 3, dissolving hydroxy-N-methylaminoacrylamide (3 g), reactant (1.4 g) and 4-Dimethylaminopyridine (DMAP) (0.46 g) in 40mL of a third solvent to obtain a first mixture, placing the first mixture in an ice-water bath at 0 ℃, dropwise adding a dichloromethane solution of Dicyclohexylcarbodiimide (DCC) into the first mixture at 0 ℃, gradually heating to room temperature after the dropwise addition, stirring at room temperature for reaction for 12h, suction filtration, and reduced pressure distillation to remove the third solvent, purifying the product by a silica gel column chromatography (the used eluent is a mixture of petroleum ether and ethyl acetate, the ethyl acetate and petroleum ether are 3:1 in volume parts), and obtaining R-N-m-AM (3.0 g, 80%), wherein the ratio of Dicyclohexylcarbodiimide (DCC) to 4-Dimethylaminopyridine (DMAP) in the dichloromethane solution of hydroxy-N-methylaminoacrylamide, reactant and Dicyclohexylcarbodiimide (DCC) is 1 in parts by weight: 1.2:1.2:0.2, wherein the ratio of the parts by volume of the hydroxy-N-methylaminoacrylamide to the parts by volume of the third solvent is 1:2.1, the parts by volume of the substances are in mmo1, the parts by volume are in mL, the reactant is acetic acid, the third solvent is dichloromethane, and the concentration of Dicyclohexylcarbodiimide (DCC) in a dichloromethane solution of Dicyclohexylcarbodiimide (DCC) is 2.28mmol/mL;
Step 4, preparing a multiple stimulus-responsive homopolymer by a reversible addition-fragmentation chain transfer (RAFT) polymerization method: dissolving R-N-m-AM and a RAFT chain transfer agent (CDTPA) in a fourth solvent, adding an initiator, carrying out three times of 'vacuumizing-nitrogen filling' circulation, stirring and reacting at 70 ℃ for 18 hours in a nitrogen atmosphere, quenching with ice water, settling in diethyl ether (settling agent), centrifuging for 3 minutes (the rotating speed is 7000R/min), washing with diethyl ether for three times, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain the multi-stimulus-responsive homopolymer. Wherein the initiator is Azodiisobutyronitrile (AIBN), and the ratio of R-N-m-AM, RAFT chain transfer agent and initiator is 90 according to the parts by weight of substances: 3: the RAFT chain transfer agent is 4-cyano-4- [ [ (dodecylthio) thiomethyl ] thio ] pentanoic acid (CDTPA), the fourth solvent is 1, 4-dioxane, and the ratio of R-N-m-AM to the fourth solvent is 1:1 in parts by mass.
Example 2 (comparative)
A method for preparing a multiple stimulus-responsive homopolymer (P (Ph-N-1-AM) 25) was essentially the same as in example 1, except that the reactant in this example was benzoic acid.
Examples 3 to 5
A method for preparing a multiple stimulus-responsive homopolymer was substantially the same as in example 1, except that:
1) The reactant in step 3 of this example is azobenzene-4-benzoic acid;
2) In step 4 of this example, the ratio of R-N-m-AM, RAFT chain transfer agent and initiator is X in parts by weight of the materials, and the X values are shown in Table 1.
TABLE 1
| Examples | X | Multiple stimulus responsive homopolymers |
| Example 3 | 90：3：1 | P(Azo-N-1-AM)20 |
| Example 4 | 150：3：1 | P(Azo-N-1-AM)32 |
| Example 5 | 300：3：1 | P(Azo-N-1-AM)58 |
Example 6
A method for preparing a multiple stimulus-responsive homopolymer (P (Azo-N-2-AM) 21), comprising the steps of:
S1, dissolving N-acetoxymethacrylamide (OAc-AM) (7.8 g,55 mmol) obtained in the step 1 of the example 1, an acid binding agent (9.9 g,72 mmol) and 2-methylamino alcohol (5.4 g,72 mmol) in 110mL of a second solvent, stirring at 30 ℃ for reaction for 8 hours, carrying out suction filtration, distilling under reduced pressure to remove the second solvent, purifying the product by a silica gel column chromatography (the used leaching agent is a mixture of methanol and ethyl acetate, the ratio of the ethyl acetate to the methanol is 10:1 in parts by volume), and obtaining hydroxy-N-methylamino acrylamide (6.8 g, 72%), wherein the acid binding agent is potassium carbonate, the 2-methylamino alcohol is 2-methylamino propanol, and the second solvent is acetonitrile (CH 3 CN);
In this example, the hydroxy-N-methylaminoacrylamide was N- (((2-hydroxypropyl) (methyl) amino) methyl) acrylamide (OH-N-m-AM) and its nuclear magnetic resonance was ：1H NMR(400MHz,CDCl3) δ 6.37 (d,J= 14.7 Hz, 1H), 6.34 – 6.26 (m, 1H), 6.12 (dd,J= 17.0, 10.2 Hz, 1H), 5.67 (dd,J= 10.2, 1.1 Hz, 1H), 4.19 (d,J= 6.4 Hz, 2H), 3.75 (dd,J= 12.6, 7.2 Hz, 2H), 2.66 (t,J= 6.0 Hz, 2H), 2.31 (s, 3H), 1.72 (dt,J= 11.1, 5.7 Hz, 2H).
S2, dissolving the hydroxy-N-methylaminoacrylamide obtained in the step S1, a reactant and 4-Dimethylaminopyridine (DMAP) in a third solvent to obtain a first mixture, placing the first mixture in an ice-water bath at 0 ℃, dropwise adding a dichloromethane solution of Dicyclohexylcarbodiimide (DCC) into the first mixture at 0 ℃, gradually heating to room temperature after the dropwise addition is finished, stirring at room temperature for reacting for 12 hours, suction filtering, and distilling off the third solvent under reduced pressure, purifying the product by a silica gel column chromatography (the used eluent is a mixture of petroleum ether and ethyl acetate, the ratio of the ethyl acetate to the petroleum ether is 2:1 in parts by volume), and obtaining R-N-m-AM, wherein the ratio of the hydroxy-N-methylaminoacrylamide, the reactant and the 4-Dimethylaminopyridine (DMAP) in the dichloromethane solution of Dicyclohexylcarbodiimide (DCC) is 1 in parts by volume: 1.2:1.2:0.2, the ratio of the parts by weight of the substances of the hydroxyl-N-methylaminoacrylamide to the parts by volume of the third solvent is 1:2.1 parts by weight of substances are in mmo1, parts by volume are in mL, the reactant is azobenzene-4-benzoic acid, the third solvent is dichloromethane, and the concentration of Dicyclohexylcarbodiimide (DCC) in a dichloromethane solution of Dicyclohexylcarbodiimide (DCC) is 2.28mmol/mL;
S3, preparing a multi-stimulus-responsive homopolymer by a reversible addition-fragmentation chain transfer (RAFT) polymerization method: dissolving R-N-m-AM and a RAFT chain transfer agent (CDTPA) obtained in the step S2 in a fourth solvent, adding an initiator, carrying out three times of 'vacuumizing-nitrogen filling' circulation, stirring and reacting at 70 ℃ for 18 hours in a nitrogen atmosphere, quenching with ice water, settling in diethyl ether (settling agent), centrifuging for 3 minutes (the rotating speed is 7000R/min), washing with diethyl ether for three times, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain the multi-stimulus-responsive homopolymer. Wherein the initiator is Azodiisobutyronitrile (AIBN), and the ratio of R-N-m-AM, RAFT chain transfer agent and initiator is 90 according to the parts by weight of substances: 3: the RAFT chain transfer agent is 4-cyano-4- [ [ (dodecylthio) thiomethyl ] thio ] pentanoic acid (CDTPA), the fourth solvent is 1, 4-dioxane, and the ratio of R-N-m-AM to the fourth solvent is 1:1 in parts by mass.
In example 1, R-N-m-AM is 2- ((2- (acrylamido) methyl) (N-methyl) amino) -ethyl acetate (CH 3 -N-1-AM,3.0g, 80%); in example 2, R-N-m-AM is ethyl 2- ((2- (acrylamido) methyl) (N-methyl) amino) -benzoate (Ph-N-1-AM, 3.8g, 78%); in examples 3-5, R-N-m-AM was (E) -2- ((2- (acrylamido) methyl) (N-methyl) amino) -4-phenyldiaza-benzoic acid ethyl ester (Azo-N-1-AM, 5.0g, 72%), and in example 6, R-N-m-AM was (E) -2- ((2- (acrylamido) methyl) (N-methyl) amino) -4-phenyldiaza-benzoic acid propyl ester (Azo-N-2-AM, 5.4g, 75%).
FIG. 1 is a nuclear magnetic resonance spectrum (1 H NMR) of CH 3 -N-1-AM and P (CH 3-N-1-AM)26), FIG. 2 is a nuclear magnetic resonance spectrum (1 H NMR) of Ph-N-1-AM and P (Ph-N-1-AM) 25, FIG. 3 is a nuclear magnetic resonance spectrum (1 H NMR) of Azo-N-1-AM, P (Azo-N-1-AM) 20、P(Azo-N-1-AM)32 and P (Azo-N-1-AM) 58, FIG. 4 is a nuclear magnetic resonance spectrum (1 H NMR) of Azo-N-2-AM and P (Azo-N-2-AM) 21, and successful preparation of CH3-N-1-AM、P(CH3-N-1-AM)26、Ph-N-1-AM、P(Ph-N-1-AM)25、Azo-N-1-AM、P(Azo-N-1-AM)20、P(Azo-N-1-AM)32、P(Azo-N-1-AM)58、Azo-N-2-AM and P (Azo-N-2-AM) 21 is demonstrated according to the characteristic peaks noted in FIGS. 1-4.
FIG. 5 is a Gel Permeation Chromatography (GPC) diagram of P(CH3-N-1-AM)26、P(Ph-N-1-AM)25、P(Azo-N-1-AM)20、P(Azo-N-1-AM)32、P(Azo-N-1-AM)58 and P (Azo-N-2-AM) 21, and the molecular weight (M n,gpc) and the molecular weight distribution coefficient Ð of the multi-stimulus-responsive homopolymer can be obtained from FIG. 5, and the values of the molecular weight and the molecular weight distribution coefficient are shown in Table 2. The narrow molecular weight distribution coefficient Ð (Ð < 1.3) indicates that the polymerization reaction is controllable. Conv. (conversion) of the multi-stimulus-responsive homopolymer was obtained by nuclear magnetic resonance spectroscopy, and DP (degree of polymerization) was calculated from the conversion. The molecular weight (M n,gpc), the molecular weight distribution coefficient Ð, conv. And DP are shown in Table 2.
TABLE 2
Temperature stimulus responsiveness experiment: and mixing the homopolymer, the N-butanol and water to prepare a solution A, wherein the concentration of the homopolymer in the solution A is 1mg/mL, the water in the solution A is 25wt% of the sum of the mass of the water and the mass of the N-butanol, and the homopolymer is one of P(CH3-N-1-AM)26、P(Ph-N-1-AM)25、P(Azo-N-1-AM)20、P(Azo-N-1-AM)32、P(Azo-N-1-AM)58 and P (Azo-N-2-AM) 21 prepared in examples 1-6. The transmittance of the solution A was measured by an ultraviolet-visible spectrophotometer as a function of temperature, as shown in FIG. 6. In FIG. 6, "P(CH3-N-1-AM)26"、"P(Ph-N-1-AM)25"、"P(Azo-N-1-AM)20"、"P(Azo-N-1-AM)32"、"P(Azo-N-1-AM)58" and "P (Azo-N-2-AM) 21" are curves showing changes in transmittance with temperature increase, and "P (Azo-N-1-AM) 20 (Reverse)" in FIG. 6 is a curve showing changes in transmittance with temperature decrease. From FIG. 6, it can be seen that the UCST values (highest critical dissolution temperature) of ,P(CH3-N-1-AM)26、P(Ph-N-1-AM)25、P(Azo-N-1-AM)20、P(Azo-N-1-AM)32、P(Azo-N-1-AM)58 and P (Azo-N-2-AM) 21 in the A solution were 32 ℃, 28.5 ℃, 29 ℃, 31 ℃, 33 ℃ and 39 ℃ in this order, demonstrating that P(CH3-N-1-AM)26、P(Ph-N-1-AM)25、P(Azo-N-1-AM)20、P(Azo-N-1-AM)32、P(Azo-N-1-AM)58 and P (Azo-N-2-AM) 21 have temperature responsiveness and are affected by molecular structure. P (Azo-N-1-AM) 20、P(Azo-N-1-AM)32 and P (Azo-N-1-AM) 58 have the same structure and different degrees of polymerization, indicating that UCST values increase with increasing degrees of polymerization. P (Azo-N-1-AM) 20 and P (Azo-N-2-AM) 21 have similar degrees of polymerization, but P (Azo-N-2-AM) 21 is more than one methylene group and more hydrophobic, indicating that UCST increases with increasing hydrophobicity. The phase transition range of the multi-stimulus-responsive homopolymer is 3 ℃, which indicates that the multi-stimulus-responsive homopolymer has very sensitive response to temperature. In addition, basically no hysteresis phenomenon exists in the cooling process, which indicates that the temperature stimulus responsiveness of the multi-stimulus responsive homopolymer has good reversibility.
PH/CO 2 stimulus responsiveness experiment: p (CH 3-N-1-AM)26) was completely dissolved in water, P (Ph-N-1-AM) 25、P(Azo-N-1-AM)20 and P (Azo-N-2-AM) 21 were insoluble in water, so that the pH/CO 2 response property of the multi-stimulus-responsive homopolymer was confirmed by the influence of pH on its UCST value, buOH/H 2 O solution, buOH/HCl solution and BuOH/NaOH solution were prepared by mixing homopolymer, N-butanol and water to obtain BuOH/H 2 O solution, wherein the concentration of homopolymer in BuOH/H 2 O solution was 1mg/mL, the mass of water and N-butanol in BuOH/H 2 O solution was 25wt% and the mass of homopolymer was P (Azo-N-1-AM) 20, respectively.
The homopolymer, the N-butanol and hydrochloric acid (the concentration of HCl in hydrochloric acid is 1M) are mixed to obtain BuOH/HCl solution, wherein the concentration of the homopolymer in the BuOH/HCl solution is 1mg/mL, the mass fraction of the hydrochloric acid in the BuOH/HCl solution is the same as that of water in the BuOH/H 2 O solution, and the homopolymer is P (Azo-N-1-AM) 20.
And mixing the homopolymer, the N-butanol and an aqueous NaOH solution (the concentration of NaOH in the aqueous NaOH solution is 1M) to obtain a BuOH/NaOH solution, wherein the concentration of the homopolymer in the BuOH/NaOH solution is 1mg/mL, the mass fraction of the aqueous NaOH solution in the BuOH/NaOH solution is the same as that of water in the BuOH/H 2 O solution, and the homopolymer is P (Azo-N-1-AM) 20.
The change curves of the transmittance of the BuOH/H 2 O solution, the BuOH/HCl solution and the BuOH/NaOH solution with temperature were measured by an ultraviolet-visible spectrophotometer, the change curve of the transmittance of the BuOH/H 2 O solution with temperature rise is shown as "BuOH/H 2 O" in A of FIG. 7, the change curve of the transmittance of the BuOH/HCl solution with temperature rise is shown as "BuOH/HCl (1M)" in A of FIG. 7, the change curve of the transmittance of the BuOH/HCl solution with temperature drop is shown as "BuOH/HCl (1M)" in A of FIG. 7, the change curve of the transmittance of the BuOH/NaOH solution with temperature rise is shown as "BuOH/NaOH (1M)" in A of FIG. 7, and the change curve of the transmittance of the BuOH/NaOH solution with temperature drop is shown as "BuOH/NaOH (Reverse) (1M)". As shown in FIG. 7A, the UCST values of P (Azo-N-1-AM) 20 in BuOH/H 2 O solution, buOH/HCl solution and BuOH/NaOH solution were 29 ℃, 12 ℃ and 50 ℃, respectively, illustrating that the solubility of P (Azo-N-1-AM) 20 greatly increased due to protonation of amine groups after the addition of acid, resulting in a decrease in UCST values; otherwise, UCST value increases after alkali is added; and basically no hysteresis phenomenon exists in the cooling process no matter the acid or the alkali is added, and the reversibility still exists.
The transmittance of the BuOH/H 2 O solution was tested as a function of temperature rise, as indicated by "Initial" in FIG. 7B; the curve of the transmittance change with temperature rise after introducing CO 2 min into the BuOH/H 2 O solution is shown as "CO 2" in B of FIG. 7; the transmittance was measured as a function of temperature rise after bubbling N 2 min into the BuOH/H 2 O solution as shown in FIG. 7B as "N 2". As can be seen from FIG. 7B, after introducing CO 2 min, the solubility of P (Azo-N-1-AM) 20 is increased due to the formation of bicarbonate, the UCST value is reduced to 25 ℃, after being blown in N 2 min, the UCST value is increased to 28℃.P(CH3-N-1-AM)26、P(Ph-N-1-AM)25、P(Azo-N-1-AM)32、P(Azo-N-1-AM)58, and P (Azo-N-2-AM) 21 has the same rule on acid, alkali and CO 2、N2, thus having the pH/CO 2 stimulus responsiveness.
Light stimulus responsiveness experiments: a homopolymer tetrahydrofuran solution was prepared at a homopolymer concentration of 0.1mg/mL, and the homopolymer was P (Azo-N-1-AM) 20 or P (Azo-N-2-AM) 21. The UV-visible absorption spectrum obtained by measuring the absorbance of the homopolymer tetrahydrofuran solution at 250nm to 600nm by a UV-visible spectrometer (excitation by a UV lamp at 365 nm) is shown in FIG. 8, wherein the homopolymer in A and B of FIG. 8 is P (Azo-N-1-AM) 20, and the homopolymer in C and D of FIG. 8 is P (Azo-N-2-AM) 21. "Initial" means an unirradiated and heated homopolymer tetrahydrofuran solution, "UV 30s" means an ultraviolet-irradiated 30s homopolymer tetrahydrofuran solution, "UV 60s" means an ultraviolet-irradiated 60s homopolymer tetrahydrofuran solution, "UV 90s" means an ultraviolet-irradiated 90s homopolymer tetrahydrofuran solution, "UV 120s" means an ultraviolet-irradiated 120s homopolymer tetrahydrofuran solution, "UV 150s" means an ultraviolet-irradiated 150s homopolymer tetrahydrofuran solution, "Blue light 60s" means that the ultraviolet-irradiated 120s homopolymer tetrahydrofuran solution is further Blue-irradiated 60s, "80 ℃ 60s" means that the ultraviolet-irradiated 120s homopolymer tetrahydrofuran solution is heated at 80 ℃ for 60s, "80 ℃ 120s" means that the ultraviolet-irradiated 120s homopolymer tetrahydrofuran solution is heated at 80 ℃ for 120s.
As can be seen from FIG. 8A, P (Azo-N-1-AM) 20 has two absorption peaks at 325nm and 450 nm. When irradiated by an ultraviolet lamp of 365nm, the absorbance at 325nm representing the pi-pi * electron transition of azobenzene gradually decreases and the absorbance at 450nm representing the n-pi * electron transition gradually increases with the increase of the ultraviolet irradiation time, which indicates that azobenzene is converted from trans to cis structure. In addition, the trithioester end group in P (Azo-N-1-AM) 20 is decomposed under the action of ultraviolet light, so that the absorbance at 325nm is reduced, and no change occurs after 120: 120s ("UV 120s" and "UV 150s" coincide). After the 120s ultraviolet irradiation of the homopolymer tetrahydrofuran solution was further irradiated with Blue light for 60s, the absorbance at 325nm was increased, the absorbance at 450nm was decreased, but the Initial position was not recovered ("Initial" corresponding ordinate), because the decomposition of the trithiolate terminal group was irreversible, but based on the curve after the first "Blue light 60s", the repeated cycles of "Blue light 60s" could be overlapped with the curve after the first "Blue light 60 s". FIG. 8B illustrates that after irradiation with an ultraviolet lamp, P (Azo-N-1-AM) 20 reaches equilibrium at 120s and can also undergo cis-to-trans configuration conversion by heating at 80 ℃. The above process can be cycled multiple times, demonstrating that P (Azo-N-1-AM) 20 has sensitive reversible photo-stimulus responsiveness.
Like C of FIG. 8 and D of FIG. 8, P (Azo-N-2-AM) 21 also have the same properties.
The multiple stimulus-responsive homopolymers prepared in examples 4 to 6 all have technical effects consistent with those of the multiple stimulus-responsive homopolymer prepared in example 3. However, the multiple stimulus-responsive homopolymers prepared in examples 1 and 2 did not possess photo-stimulus responsiveness.
Example 7
5Mg of the homopolymer was dissolved in 1mL of tetrahydrofuran, and the mixture was slowly dropped into 10mL of distilled water under stirring at 600r/min (dropping rate: 100. Mu.L/min) for Bi Jiaoban hours to obtain micelles, wherein the homopolymer was P (Azo-N-1-AM) 20 or P (Azo-N-2-AM) 21.
The A and B of FIG. 9 are morphology graphs of the micelle prepared based on P (Azo-N-1-AM) 20 and the micelle prepared based on P (Azo-N-2-AM) 21 in order, and as can be seen from the A of FIG. 9 and the B of FIG. 9, the micelle prepared based on P (Azo-N-1-AM) 20 and the micelle prepared based on P (Azo-N-2-AM) 21 are spherical with average particle diameters of 180nm and 270nm in order, and the difference in particle diameters is mainly caused by the difference in the lengths of the hydrophobic segments in the homopolymers. Micelles also have stimulus responsiveness, 1M hydrochloric acid is added to the micelles prepared based on P (Azo-N-2-AM) 21 to enable the pH to be 3, as shown in C of FIG. 9, morphology is changed, hydrophilicity is enhanced due to protonation of amino groups, and the morphology of the micelles prepared based on P (Azo-N-2-AM) 21 is changed from a sphere to a vesicle; after ultraviolet light was irradiated for 2 hours to the micelle prepared based on P (Azo-N-2-AM) 21, as shown in D of FIG. 9, although azobenzene configuration was changed, the micelle morphology was spherical and the size was slightly increased.
The nile red simulated drug is adopted, and the cumulative release amount of the nile red is calculated through testing a fluorescence spectrum: 5mg of homopolymer and 0.1mg of Nile Red (NR) were dissolved in 1mL of tetrahydrofuran, and slowly dropped into 10mL of distilled water (dropping rate: 100. Mu.L/min) under stirring of 600r/min for Bi Jiaoban hours, and the unsupported nile red was removed by centrifugation (rotation speed: 1000 r/min) to obtain a drug-loaded homopolymer micelle solution, wherein the homopolymer was P (Azo-N-2-AM) 21. Preparing three drug-loaded homopolymer micelle solutions, wherein the first drug-loaded homopolymer micelle solution is subjected to UV radiation for 4 hours, the second drug-loaded homopolymer micelle solution is added with 1M hydrochloric acid to reach pH 3, the third drug-loaded homopolymer micelle solution is not subjected to any operation, the three drug-loaded homopolymer micelle solutions are respectively tested for the change of the cumulative release amount of nile red with time, as shown in fig. 10, wherein "UV" in fig. 10 represents the first drug-loaded homopolymer micelle solution, "pH=3" represents the second drug-loaded homopolymer micelle solution, and "no-stick" represents the third drug-loaded homopolymer micelle solution, and the cumulative release amounts of nile red through UV radiation for 30 minutes, 45 minutes, 1 hour, 2 hours and 4 hours are respectively 13.5%, 25.4%, 35%, 40.6% and 44%; the cumulative release amounts of nile red in the second drug-loaded homopolymer micelle solution at 1min, 30min, 45min, 1h and 4h are 27.2%, 38.3%, 50%, 52.6% and 56%, respectively; the third drug loaded homopolymer micelle solution had a cumulative release of only 5% after 4 hours. The experimental results prove that: the multi-stimulus-responsive homopolymer has amphipathy, can be self-assembled to form micelle with stimulus response, can wrap hydrophobic medicine nile red, is various and stable in micelle morphology based on the multi-stimulus-responsive homopolymer, and realizes release of nile red under the stimulation of UV radiation or acid.
5Mg of P (CH 3-N-1-AM)26 was dissolved in 1mL of tetrahydrofuran) was slowly dropped into 10mL of distilled water (the dropping rate was 100. Mu.L/min) under stirring at 600r/min, and the solution was dropped for Bi Jiaoban hours, whereby micelles could not be formed.
5Mg of P (Ph-N-1-AM) 25 was dissolved in 1mL of tetrahydrofuran, and the solution was slowly dropped into 10mL of distilled water (at a dropping rate of 100. Mu.L/min) under stirring of 600r/min for Bi Jiaoban hours, whereby micelles were formed, but particles in the micelles were irregularly shaped. Thus, the multiple stimulus-responsive homopolymers prepared in examples 1 and 2 failed to encapsulate the drug and control drug release.
Example 8
The method for preparing the erasable paper comprises the following steps: mixing a multiple stimulus-responsive homopolymer P (Azo-N-1-AM) 20 and a fifth solvent (N, N-dimethylformamide) to obtain a polymer solution, wherein the mass fraction of P (Azo-N-1-AM) 20 in the polymer solution is 2wt%, soaking the pretreated paper in the polymer solution for 10min to enable the polymer solution to be fully adhered to the surface of the paper, and drying the paper in a baking oven at 40 ℃ for 10min to obtain erasable paper (light yellow paper), wherein the pretreatment is as follows: cutting common A4 paper into square with a length of 5×5cm, soaking in ethanol and water for 5min, ultrasonic cleaning, and drying in oven at 40deg.C for 10min.
Reversible lithography patterning experiments (uv lamp power 90W, blue lamp power 30W) were performed using different mold masks: FIG. 11 a is an initial state of the rewritable paper; covering up the five-pointed star mold on the erasable paper, irradiating with ultraviolet lamp (90W) (the linear distance between the ultraviolet lamp and the erasable paper is 5 cm) for 2min, and displaying the pattern; fig. 11 b is a picture after the ultraviolet lamp irradiates for 30min, and the patterns of the five stars can be clearly seen; the pattern of the pentagram can still be clearly seen by removing the uv lamp as in fig. 11 c; the erasable paper in fig. 11 c is irradiated under a blue light of 30W for 1h (the straight line distance between the blue light and the erasable paper is 5 cm), as shown in fig. 11 d, the five-pointed star pattern is completely erased, i.e. the pattern disappears (the five-pointed star pattern can be completely erased when heated at 80 ℃ for 30 min).
The small Xiong Touxiang die is covered on the erasable paper continuously, and the e of fig. 11 is a picture of the erasable paper irradiated by the ultraviolet lamp for 30 minutes and removed, so that the pattern of the little bear head portrait can be seen clearly; fig. 11 f is a picture of the erasable paper of fig. 11 e after being irradiated with blue light for 1h, and the pattern of the bear head portrait is completely erased, i.e. the pattern disappears (the pattern disappearance can be realized by heating at 80 ℃ for 30 min).
Continuing to cover the loving pattern mold on the erasable paper, wherein g of fig. 11 is a picture of the erasable paper irradiated by the ultraviolet lamp for 30min and removed, and the loving pattern can be clearly seen; h of fig. 11 is a picture of the erasable paper of g of fig. 11 after being left for 7 days, the pattern remains clear.
The above demonstrates that the erasable paper has good fatigue resistance and stability. For complex patterns, a better burning effect can be presented. Fig. 11 i is a pattern "safe" apple of a traditional chinese window design, with a clear pattern, demonstrating a high resolution of the erasable paper.
The same properties are also obtained by replacing "P (Azo-N-1-AM) 20 in the above" method for producing erasable paper "with" P (Azo-N-2-AM) 21",P(Azo-N-2-AM)21, and as shown in j of FIG. 11, the erasable paper produced based on P (Azo-N-2-AM) 21 shows a "fish" picture in China traditional year, and there is no obvious difference in irradiation time, stability, picture resolution, etc. and the erasable paper produced based on P (Azo-N-1-AM) 20. The experimental results prove that: the multi-stimulus responsive homopolymer of the invention can be used for preparing erasable paper, and has excellent application prospect in the field of optical storage.
The multiple stimulus-responsive homopolymers prepared in examples 1 and 2 do not have photo stimulus responsiveness, so that the recording-erasing process of the rewritable paper cannot be realized.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. A multiple stimulus responsive homopolymer characterized by the following structural formula:
wherein m=1 or 2, and n=10 to 200.
2. The method for preparing the multiple stimulus-responsive homopolymer as claimed in claim 1, comprising the steps of:
Step 1, mixing N-methylol acrylamide, acetic anhydride, alkali and a first solvent, stirring at room temperature for 5-8 hours, carrying out suction filtration, and carrying out reduced pressure distillation to remove the first solvent to obtain white solid N-acetoxyl methacrylamide, wherein the ratio of the N-methylol acrylamide to the acetic anhydride to the alkali is 1: (2.0 to 2.5): (2.0-2.5);
Step 2, mixing the N-acetoxy methacrylamide, an acid binding agent, 2-methylamino alcohol and a second solvent, stirring for 6-8 hours at 30-35 ℃, carrying out suction filtration, carrying out reduced pressure distillation to remove the second solvent, and purifying to obtain hydroxy-N-methylamino acrylamide, wherein the ratio of the N-acetoxy methacrylamide to the acid binding agent to the 2-methylamino alcohol is 1: (1.3 to 1.5): (1.3-1.5), wherein the acid binding agent is potassium carbonate, and the 2-methylamino alcohol is 2-methylamino ethanol or 2-methylamino propanol;
Step 3, mixing the hydroxy-N-methylamino acrylamide, a reactant, 4-dimethylaminopyridine and a third solvent to obtain a first mixture, dropwise adding a dichloromethane solution of dicyclohexylcarbodiimide into the first mixture at 0-10 ℃, heating to room temperature after dropwise adding, stirring at room temperature for 12-24 hours, carrying out suction filtration, distilling under reduced pressure to remove the third solvent, and purifying to obtain R-N-m-AM, wherein the ratio of dicyclohexylcarbodiimide to 4-dimethylaminopyridine in the dichloromethane solution of hydroxy-N-methylamino acrylamide, reactant and dicyclohexylcarbodiimide is 1: (1.1 to 1.3): (1.1 to 1.3): (0.1-0.3), wherein the reactant is azobenzene-4-benzoic acid, and the structural formula of R-N-m-AM is M=1 or 2;
Step 4, mixing the R-N-m-AM, the RAFT chain transfer reagent, a fourth solvent and an initiator, stirring for 18-24 hours at 65-70 ℃ in nitrogen or inert gas atmosphere, quenching with ice water, settling, centrifuging, washing and drying to obtain a multi-stimulus response homopolymer, wherein the initiator is azodiisobutyronitrile, and the ratio of the R-N-m-AM, the RAFT chain transfer reagent and the initiator is (30-600) according to the parts by weight of substances: 3: (1-1.5), wherein the RAFT chain transfer agent is 4-cyano-4- [ [ (dodecylthio) thiomethyl ] thio ] pentanoic acid.
3. The method according to claim 2, wherein in step 1, the base is potassium carbonate or triethylamine.
4. The preparation method according to claim 2, wherein in step 1, the ratio of the parts by weight of the N-methylolacrylamide substance to the parts by volume of the first solvent is 1: (0.8-1.0), wherein the unit of the parts by weight of the substances is mmo1, and the unit of the parts by volume is mL;
in step 1, the first solvent is dichloromethane;
In the step 2, the ratio of the parts by weight of the N-acetoxy methacrylamide substance to the parts by volume of the second solvent is 1: (2.0-2.3), wherein the unit of the parts by weight of the substances is mmo1, and the unit of the parts by volume is mL;
In step 2, the second solvent is acetonitrile;
in the step 2, the purification adopts a silica gel column chromatography method; the eluting agent adopted in the silica gel column chromatography in the step 2 is a mixture of methanol and ethyl acetate, and the ratio of the methanol to the ethyl acetate is 1 (8-10) in parts by volume.
5. The preparation method according to claim 2, wherein in the step 3, the purification adopts a silica gel column chromatography, and the eluent adopted in the silica gel column chromatography in the step 3 is a mixture of petroleum ether and ethyl acetate, and the ratio of petroleum ether to ethyl acetate is 1 in terms of volume fraction: (1-3).
6. The preparation method according to claim 2, wherein in step 3, the ratio of the parts by weight of the substance of the hydroxy-N-methylaminoacrylamide to the parts by volume of the third solvent is 1: (2.0-2.3), wherein the unit of the parts by weight of the substances is mmo1, and the unit of the parts by volume is mL;
In step 3, the third solvent is dichloromethane;
in the step 3, the concentration of dicyclohexylcarbodiimide in a dichloromethane solution of dicyclohexylcarbodiimide is 2.0-2.5 mmol/mL;
in step 4, the fourth solvent is 1, 4-dioxane;
in the step 4, the ratio of the R-N-m-AM to the fourth solvent is 1 in parts by weight: (1-1.5);
In the step 4, the sedimentation agent adopted in the sedimentation is n-hexane, diethyl ether or methanol.
7. Use of the multiple stimulus-responsive homopolymer of claim 1 for controlling drug release for non-diagnostic or therapeutic purposes.
8. The use according to claim 7, wherein the multi-stimulus-responsive homopolymer and the drug are dissolved in tetrahydrofuran, and the mixture is dropped into distilled water under the stirring condition of 600 to 800r/min, and the mixture is dropped Bi Jiaoban to 48 hours, and centrifuged to remove the unsupported drug, thereby obtaining a drug-loaded homopolymer micelle solution, and the drug release is stimulated by ultraviolet irradiation or by adding acid.
9. Use of the multiple stimulus-responsive homopolymer of claim 1 in lithographic patterning.
10. The use according to claim 9, wherein the multi-stimulus-responsive homopolymer is carried on paper to provide a rewritable paper, a portion of the rewritable paper is irradiated with ultraviolet light, the color of the portion of the rewritable paper which is irradiated with ultraviolet light is darkened relative to a portion which is not irradiated with ultraviolet light, and edges of the darkened portion of the rewritable paper enclose a pattern which disappears when the rewritable paper is irradiated with blue light or heated.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5412079A (en) * | 1993-03-26 | 1995-05-02 | Nippon Paint Co., Ltd. | Liquid crystal monomer compound and polymer obtained therefrom |
| CN102633923A (en) * | 2012-04-12 | 2012-08-15 | 山东交通学院 | Water-soluble triple response intelligent polymer and preparation method thereof |
| CN105601841A (en) * | 2016-02-18 | 2016-05-25 | 厦门大学 | Photo-responsive random copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412079A (en) * | 1993-03-26 | 1995-05-02 | Nippon Paint Co., Ltd. | Liquid crystal monomer compound and polymer obtained therefrom |
| CN102633923A (en) * | 2012-04-12 | 2012-08-15 | 山东交通学院 | Water-soluble triple response intelligent polymer and preparation method thereof |
| CN105601841A (en) * | 2016-02-18 | 2016-05-25 | 厦门大学 | Photo-responsive random copolymer and preparation method thereof |
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