CN106835319A - A kind of preparation method of photochromic block copolymer - Google Patents
A kind of preparation method of photochromic block copolymer Download PDFInfo
- Publication number
- CN106835319A CN106835319A CN201611150459.5A CN201611150459A CN106835319A CN 106835319 A CN106835319 A CN 106835319A CN 201611150459 A CN201611150459 A CN 201611150459A CN 106835319 A CN106835319 A CN 106835319A
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- China
- Prior art keywords
- photochromic
- preparation
- pspma
- added
- block copolymer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 31
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 19
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 19
- 238000002845 discoloration Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- 229910052757 nitrogen Inorganic materials 0.000 claims description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000009987 spinning Methods 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 11
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 150000002910 rare earth metals Chemical class 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010257 thawing Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 238000003818 flash chromatography Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 claims description 2
- JRQDVRIQJJPHEQ-UHFFFAOYSA-N 3970-35-2 Chemical class OC(=O)C1=CC=CC([N+]([O-])=O)=C1Cl JRQDVRIQJJPHEQ-UHFFFAOYSA-N 0.000 claims description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 2
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- -1 Dimethyl -6- nitroindoline quinolines Chemical class 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 claims 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 claims 1
- 150000003639 trimesic acids Chemical class 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 5
- 238000007639 printing Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 125000001246 bromo group Chemical group Br* 0.000 description 10
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of preparation method of photochromic block copolymer, comprise the following steps：The preparation of SPMA；The preparation of PSPMA Br；The preparation of PSPMA g PMMA, compared with prior art, the beneficial effects of the invention are as follows：By the nano micron fibre prepared by the present invention, can realize realizing red, green, yellow color fluorescence transformation under different ultraviolet lights under different light irradiations, and fiber is changed into darkviolet from colourless after ultraviolet irradiation, obtain fiber and repeat to be changed and between purple colourless, so as to obtain can luminous coloration fiber.This method needs not move through printing and dyeing, it is to avoid while the pollution of environment, and the various discolorations of fiber and lighting function are assigned again.
Description
Technical field
The present invention relates to a kind of photochromic luminous coloration fiber producing processes, specifically a kind of photochromic block copolymerization
The preparation method of thing.
Background technology
Today's society is liked that colorful fabric is main at present with social development, the fabric for varying in color by people
Source is textile and dyeing industry, and the development of printing and dyeing industry brings colorful clothes to enjoy to us.But the thing followed is life
Environment it is increasingly seriously polluted, the toxic metals such as contained heavy metal cadmium, mercury, chromium, lead are to people's body in dyestuff waste liquid
Injury is very big.So seeking that new to prepare colorful cloth process extremely urgent.
Prior art：First it is prepared into and does not have coloured cloth, industrial printing and dyeing is then carried out by the dyestuff of different colours, or
Being prepared by the off-color material for adding organic or inorganic turns into spinning solution, then sharp spining technology is prepared by solution spinning processes
As fiber.The shortcoming of prior art is more serious industrial pollution, to human injury than larger.Existing other technologies discoloration is more
It is single, it is impossible to meet multifunctional clothes decoration materials demand.
The content of the invention
It is an object of the invention to provide a kind of preparation method of photochromic block copolymer, to solve above-mentioned background skill
The problem proposed in art.
To achieve the above object, the present invention provides following technical scheme：
A kind of preparation method of photochromic block copolymer, comprises the following steps：
Step 1, the preparation of SPMA：5-6gN- ethoxy -3,3- dimethyl -6- nitroindoline quinolines are added in there-necked flask
Spiro-pyrans and 60-80ml dichloromethane, the moderate-speed mixer under 0-5 DEG C of ice-water bath nitrogen protective condition, TLC points plate are followed the trail of, and are added
Pyridine 2-5g is used as acid binding agent；Measure 2-5g methacrylic chloride mixing 10-15ml dichloromethane and be added to constant pressure funnel
In, then it is added dropwise in there-necked flask, within 30min, after 0-5 DEG C of stirring 0.5h, 25-30 DEG C is warming up to, continue anti-
Should, TLC points plate is followed the trail of, disappearing or do not see substantially to raw material point；Then first with deionized water extracting and washing point liquid, removal
The hydrochloride of pyridine, resulting product removes methylene chloride, gained royal purple product, by post layer by rotary evaporation
Analysis flash chromatography on silica gel post is further purified, and is 5 using volume ratio:1 petroleum ether and the mixed liquor of ethyl acetate are used as wash-out
Agent, rotary evaporation obtains SPMA；
Step 2, the preparation of PSPMA-Br：Flask-vacuumize-lead to nitrogen treatment, by monomer is first carried out to Schlenk bottles
SPMA1.0-1.5g, initiator 2- isobutyl ethyl bromide 15-20 μ l, part N, N, N', N, ' N "-five methyl diethylentriamine
44-55 μ l, solvent THF5-6ml and methyl alcohol 1-1.5ml are added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-take out true
Sky-thaw cycles three times, the rapid 0.01-0.02g catalyst cuprous bromides that weigh are added thereto after last time is freezed, and add
Enter magneton, ultrasound makes its dispersed, be placed in 40-45 DEG C of water-bath to react 4-6h and lead to nitrogen after defrosting and protected；Then
Product exposure in atmosphere, after being cooled to room temperature, will pour into a large amount of methyl alcohol and precipitate after reaction, and repeatedly with tetrahydrofuran and
Methyl alcohol washs at least three times to lighter, is centrifugally separating to obtain product, and 40-45 DEG C of drying of vacuum obtains final light blue solid
Body PSPMA-Br；
Step 3, the preparation of PSPMA-g-PMMA：Flask-vacuumize-lead to nitrogen treatment, repeatedly is first carried out to Schlenk bottles
Circulation three times, monomers methyl methacrylate 10-12ml, initiator PSPMA-Br 0.2-0.3g are added to Schlenk bottles, are matched somebody with somebody
Body PMDETA 35-40 μ l, solvent THF10-15ml and methyl alcohol 3-5ml, then further degassing, liquid nitrogen frozen-vacuumize-solve
Freeze circulation three times, the rapid 0.12-0.15g catalyst CuBr that weighs is added thereto after last time is freezed, and adds magneton, makes
Make its dispersed with ultrasonic wave, be placed in 40-45 DEG C of water-bath to react 6-8h and be passed through nitrogen after defrosting and protect；Then will mixing
Thing exposes in atmosphere, after being cooled to room temperature, pours into a large amount of methyl alcohol and precipitates, centrifugation, and is washed with THF and methyl alcohol repeatedly
Wash to lighter, 40-45 DEG C of drying of vacuum finally gives the PSPMA-g-PMMA that product is light green solid shape；
Step 4, the preparation of photochromic fibre：By the PSPMA-g-PMMA of step 3 gained with DMF as solvent, prepare dense
The spinning solution of 20%-25% is spent, and 1,10- Phen-Tb organic rare-earth ligands are added in spinning solution, then carried out quiet
Electrospun, spinning voltage 15-22KV, 40-60 μm of fltting speed/min is received apart from 15-30cm, ultraviolet in difference so as to obtain
Launch many bases discoloration nano micron fibre of different fluorescence under light irradiation.
As further scheme of the invention：A kind of system of photochromic block copolymer according to claim 1
Preparation Method, it is characterised in that the eluant, eluent and solvent are petroleum ether and ethyl acetate by 5:1 ratio is mixed to prepare.
As further scheme of the invention：A kind of photochromic block copolymer according to claim 1, its
It is characterised by, the rare earth terbium luminescent material is with the organic RE from the centre of luminescence and its part by the preparation that chemically reacts
Thing.
As further scheme of the invention：Described a kind of photochromic block copolymer, it is characterised in that according to
A kind of photochromic block copolymer described in claim 1, it is characterised in that the rare earth terbium luminescent material, its part bag
Include benzoic acid, p-methylbenzoic acid, p-aminobenzoic acid, paranitrobenzoic acid, P-methoxybenzoic acid, 1,3,5 equal benzene front threes
Acid, 3- nitros-PABA, the chloro- 3- nitrobenzoic acids of 4-, TTA, 1,10- Phen, 2,2 '-
Bipyridyl, 4,4 '-bipyridyl.
As further scheme of the invention：5. a kind of multiple bases according to claim 1 it is photochromic receive it is micro-
The preparation method of rice fiber, it is characterised in that the spinning voltage 15-22KV of the electrostatic spinning, 40-60 μm of fltting speed/
Min, receives apart from 15-30cm.
As further scheme of the invention：Described a kind of photochromic block copolymer, it is characterised in that described
The photochromic nano micron fibre of multiple bases excites lower achievable many base color changeable effects in different ultraviolet wavelengths：When using 360-
Its display is red during 367nm ultraviolet light fiber samples；Green is shown when using 254-295nm ultraviolet lights；When
Huang is then shown when being excited jointly using the ultraviolet light of any wavelength in any wavelength and 254-295nm in 360-367nm
Color；After ultraviolet light is removed, prepared nano micron fibre is rendered as purple；Can instantaneously be changed into white by heating sample.
This colourshifting process can be circulated infinitely.
Compared with prior art, the beneficial effects of the invention are as follows：By the nano micron fibre prepared by the present invention, Ke Yi
Realize realizing red, green, yellow color fluorescence transformation under different ultraviolet lights under different light irradiations, and it is fine after ultraviolet irradiation
Dimension is changed into darkviolet from colourless, obtains fiber and repeat to be changed and between purple colourless, so as to obtain can luminous coloration fiber.This
The method of kind needs not move through printing and dyeing, it is to avoid while the pollution of environment, and the various discolorations of fiber and lighting function are assigned again.
Brief description of the drawings
Fig. 1 is the synthetic route chart of SPMA.
Fig. 2 is the synthetic route chart of PSPMA-g-PMMA.
Fig. 3 is each stage infrared spectrogram in course of reaction.
Fig. 4 is SPMA's1HNMR spectrograms.
Fig. 5 is block copolymer PSPMA-g-PMMA's1HNMR spectrograms.
Fig. 6 is electrospun fibers SEM photograph.
Fig. 7 fibers fluorescence spectrum under different excitation wavelengths
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
Step 1, the preparation of photochromic monomer (SPMA)
As shown in figure 1, it is comprised the following steps that：
(1) in there-necked flask add 5gN- ethoxys -3,3- dimethyl -6- nitroindoline quinolines spiro-pyrans (SP-OH) and
60ml dichloromethane, the moderate-speed mixer under 0-5 DEG C of ice-water bath nitrogen protective condition, TLC points plate is followed the trail of, and adds pyridine 2g as tiing up
Sour agent；
(2) measure 2g methacrylic chloride mixing 10ml dichloromethane to be added in constant pressure funnel, then dropwise add
Enter in there-necked flask, within 30min, after 0-5 DEG C of stirring 0.5h, be warming up to 25-30 DEG C, continue to react, TLC point plates are chased after
Track, disappearing or do not see substantially to raw material point；
(3) and then first with deionized water extracting and washing point liquid, the hydrochloride of pyridine is removed, resulting product steams by rotation
Hair removes methylene chloride, and gained royal purple product is further purified, using body by column chromatography silica gel flash chromatography post
Product is than being 5:, used as eluant, eluent, rotary evaporation obtains SPMA for 1 petroleum ether and the mixed liquor of ethyl acetate.
Step 2, the preparation of photochromic polymer (PSPMA-Br)
(1) flask-vacuumize-lead to nitrogen treatment, by monomer SPMA 1.0g, initiator 2- bromines is first carried out to Schlenk bottles
The μ l of ethyl isobutyrate 15, part N, N, N', N, ' N " the μ l of-five methyl diethylentriamine (PMDETA) 44, solvent THF5ml and first
Alcohol 1ml is added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, cold in last time
Rapid 0.01g catalyst cuprous bromide (CuBr) that weighs is added thereto after jelly, and adds magneton, and ultrasound makes its dispersed, solution
It is placed in 40-45 DEG C of water-bath to react 4h and lead to nitrogen after jelly and is protected；
(2) and then by product exposure after reaction in atmosphere, after being cooled to room temperature, precipitation in a large amount of methyl alcohol is poured into, from
The heart is separated, and is washed at least three times to lighter with tetrahydrofuran (THF) and methyl alcohol repeatedly, and 40-45 DEG C of drying of vacuum is obtained
Final light-blue solid PSPMA-Br.
Step 3, the preparation of photochromic block copolymer (PSPMA-g-PMMA)
As shown in Fig. 2 comprising the following steps that:
(1) first carry out to Schlenk bottles flask-vacuumize-lead to nitrogen treatment, iterative cycles three times, to Schlenk bottles plus
Enter monomers methyl methacrylate (MMA) 10ml, initiator PSPMA-Br0.2g, part PMDETA35 μ l, solvent THF10ml and
Methyl alcohol 3ml, then further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, weigh rapidly after last time is freezed
0.12g catalyst CuBr is added thereto, and adds magneton, makes its dispersed using ultrasonic wave, and 40-45 DEG C of water is placed in after defrosting
8h is reacted in bath and nitrogen protection is passed through.
(2) and then by mixture exposure in atmosphere, after being cooled to room temperature, precipitation in a large amount of methyl alcohol, centrifugation point are poured into
From, and washed with THF and methyl alcohol repeatedly to lighter, 40-45 DEG C of drying of vacuum finally gives product for light green solid shape
PSPMA-g-PMMA.Fig. 3 is block copolymer PSPMA-g-PMMA infrared spectrums, 1610cm in figure-1、1457cm-1It is phenyl ring
Feature stretching vibration peak；748cm-1It is the disubstituted characteristic peak in ortho position on phenyl ring；1157cm-1, 1089cm-1Characteristic peak is C-O-C
Ehter bond characteristic absorption peak；In 2960cm-1~2865cm-1The infrared absorption peak of scope corresponds respectively to-CH3With-CH2- stretch and shake
It is dynamic；- OH the stretching vibration peaks of SP-OH are located at 3280cm-1Place.MMA polymerization activities are larger, and content is of a relatively high in final product,
The characteristic absorption peak of MMA ester groups appears in 1737cm-1.Thus explanation block copolymer is successfully prepared.
Step 4, the preparation of photochromic fibre
By the PSPMA-g-PMMA of step 3 gained with DMF as solvent, the spinning solution of compound concentration 20%, and in spinning solution
Middle addition 1,10- Phen-Tb organic rare-earth ligands, then carry out electrostatic spinning, spinning voltage 22KV, fltting speed 60
μm/min, and receive apart from 22cm, so as to many bases discoloration for obtaining launching under different ultraviolet lights different fluorescence, to receive micron fine
Dimension.
Embodiment 2
Step 1, the preparation of photochromic monomer (SPMA)
(1) in there-necked flask add 6gN- ethoxys -3,3- dimethyl -6- nitroindoline quinolines spiro-pyrans (SP-OH) and
80ml dichloromethane, the moderate-speed mixer under 0 DEG C of ice-water bath nitrogen protective condition, TLC points plate is followed the trail of, and adds pyridine 5g as tiing up acid
Agent；
(2) measure 5g methacrylic chloride mixing 15ml dichloromethane to be added in constant pressure funnel, then dropwise add
Enter in there-necked flask, within 30min, after 0 DEG C of stirring 0.5h, be warming up to 25 DEG C, continue to react, TLC points plate is followed the trail of, extremely former
Untill shots disappear or do not see substantially；
(3) and then first with deionized water extracting and washing point liquid, the hydrochloride of pyridine is removed, resulting product steams by rotation
Hair removes methylene chloride, and gained royal purple product is further purified, using body by column chromatography silica gel flash chromatography post
Product is than being 5:, used as eluant, eluent, rotary evaporation obtains SPMA for 1 petroleum ether and the mixed liquor of ethyl acetate.Pass through nuclear-magnetism in Fig. 4
Sign may certify that the structure that products therefrom structure is target molecule, and monomer SPMA is successfully prepared.
Step 2, the preparation of photochromic polymer (PSPMA-Br)
(1) flask-vacuumize-lead to nitrogen treatment, by monomer SPMA1.5g, initiator 2- bromines is first carried out to Schlenk bottles
The μ l of ethyl isobutyrate 20, part N, N, N', N, ' N " the μ l of-five methyl diethylentriamine (PMDETA) 55, solvent THF 6ml and
Methyl alcohol 1.5ml is added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, at last
Rapid 0.02g catalyst cuprous bromide (CuBr) that weighs is added thereto after secondary freezing, and adds magneton, and ultrasound makes its uniform point
Dissipate, be placed in 40 DEG C of water-baths to react 4h and lead to nitrogen after defrosting and protected；
(2) and then by product exposure after reaction in atmosphere, after being cooled to room temperature, precipitation in a large amount of methyl alcohol is poured into, from
The heart is separated, and is washed at least three times to lighter with tetrahydrofuran (THF) and methyl alcohol repeatedly, and 40 DEG C of dryings of vacuum are obtained most
Whole light-blue solid PSPMA-Br.
Step 3, the preparation of photochromic block copolymer (PSPMA-g-PMMA)
(1) first carry out to Schlenk bottles flask-vacuumize-lead to nitrogen treatment, iterative cycles three times, to Schlenk bottles plus
Enter monomers methyl methacrylate (MMA) 12ml, the μ l of initiator PSPMA-Br 0.3g, part PMDETA 40, solvent THF15ml
With methyl alcohol 5ml, then further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, claim rapidly after last time is freezed
Amount 0.15g catalyst CuBr is added thereto, and adds magneton, makes its dispersed using ultrasonic wave, and 40 DEG C of water are placed in after defrosting
8h is reacted in bath and nitrogen protection is passed through；
(2) and then by mixture exposure in atmosphere, after being cooled to room temperature, precipitation in a large amount of methyl alcohol, centrifugation point are poured into
From, and washed with THF and methyl alcohol repeatedly to lighter, 40 DEG C of dryings of vacuum, it is light green solid shape to finally give product
PSPMA-g-PMMA.Relative to monomer SPMA nuclear magnetic spectrograms in Fig. 5, there is substantially new position in the nuclear magnetic spectrogram of block copolymer
Move peak to occur, the peak intensity for being prepared into SPMA after block copolymer substantially weakens relative to MMA, and this is due to MMA monomer reactivities
Higher, the degree of polymerization is far longer than SPMA monomers, and nuclear-magnetism characterizes the chemical shift that peak is Hydrogen Proton in PMMA structures,
Chemical shift is the proton peak of pendant methyl in methyl methacrylate structure at 1.02ppm；Chemical shift correspondence at 1.81ppm
Methylene-the CH after double bond after methyl methacrylate polymerization is opened2Proton peak；Chemical shift is methyl-prop at 3.60ppm
CH after e pioic acid methyl ester polymerization3- O- places Hydrogen Proton peak.Understood by atom transfer radical polymerization method, target by upper map analysis
Block copolymer is successfully prepared.
Step 4, the preparation of photochromic fibre
By the PSPMA-g-PMMA of step 3 gained with DMF as solvent, the spinning solution of compound concentration 25%, and in spinning solution
Middle addition 1,10- Phen-Tb organic rare-earth ligands, then carry out electrostatic spinning, spinning voltage 20KV, fltting speed 60
μm/min, receive apart from 25cm.So as to many bases discoloration for obtaining launching under different ultraviolet lights different fluorescence, to receive micron fine
Dimension.It can be found that prepared photochromic nano micron fibre surface is relatively smooth by stereoscan photograph in Fig. 6, Size Distribution
It is more uniform, for it provides precondition as the application of fabric.
Embodiment 3
(1) in there-necked flask add 5gN- ethoxys -3,3- dimethyl -6- nitroindoline quinolines spiro-pyrans (SP-OH) and
70ml dichloromethane, the moderate-speed mixer under 0-5 DEG C of ice-water bath nitrogen protective condition, TLC points plate is followed the trail of, and adds pyridine 4g as tiing up
Sour agent；
(2) measure 4g methacrylic chloride mixing 13ml dichloromethane to be added in constant pressure funnel, then dropwise add
Enter in there-necked flask, within 30min, after 5 DEG C of stirring 0.5h, be warming up to 30 DEG C, continue to react, TLC points plate is followed the trail of, extremely former
Untill shots disappear or do not see substantially；
(3) and then first with deionized water extracting and washing point liquid, the hydrochloride of pyridine is removed, resulting product steams by rotation
Hair removes methylene chloride, and gained royal purple product is further purified, using body by column chromatography silica gel flash chromatography post
Product is than being 5:, used as eluant, eluent, rotary evaporation obtains SPMA for 1 petroleum ether and the mixed liquor of ethyl acetate.
Step 2, the preparation of photochromic polymer (PSPMA-Br)
(1) flask-vacuumize-lead to nitrogen treatment, by monomer SPMA1.3g, initiator 2- bromines is first carried out to Schlenk bottles
The μ l of ethyl isobutyrate 18, part N, N, N', N, ' N " the μ l of-five methyl diethylentriamine (PMDETA) 50, solvent THF6ml and first
Alcohol 1.3ml is added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, in last time
Rapid 0.02g catalyst cuprous bromide (CuBr) that weighs is added thereto after freezing, and adds magneton, and ultrasound makes its dispersed,
It is placed in 45 DEG C of water-baths to react 4h and lead to nitrogen after defrosting and is protected；
(2) and then by product exposure after reaction in atmosphere, after being cooled to room temperature, precipitation in a large amount of methyl alcohol is poured into, from
The heart is separated, and is washed at least three times to lighter with tetrahydrofuran (THF) and methyl alcohol repeatedly, and 45 DEG C of dryings of vacuum are obtained most
Whole light-blue solid PSPMA-Br.
Step 3, the preparation of photochromic block copolymer (PSPMA-g-PMMA)
(1) first to carrying out flask-vacuumize-lead to nitrogen treatment, iterative cycles three times, to Schlenk bottles to Schlenk bottles
Add monomers methyl methacrylate (MMA) 11ml, initiator PSPMA-Br0.3g, part PMDETA38 μ l, solvent THF13ml
With methyl alcohol 4ml, then further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, claim rapidly after last time is freezed
Amount 0.15g catalyst CuBr is added thereto, and adds magneton, makes its dispersed using ultrasonic wave, and 45 DEG C of water are placed in after defrosting
8h is reacted in bath and nitrogen protection is passed through；
(2) and then by mixture exposure in atmosphere, after being cooled to room temperature, precipitation in a large amount of methyl alcohol, centrifugation point are poured into
From, and washed with THF and methyl alcohol repeatedly to lighter, 45 DEG C of dryings of vacuum, it is light green solid shape to finally give product
PSPMA-g-PMMA。
Step 4, the preparation of photochromic fibre
By the PSPMA-g-PMMA of step 3 gained with DMF as solvent, the spinning solution of compound concentration 25%, and in spinning solution
Middle addition 1,10- Phen-Tb organic rare-earth ligands, then carry out electrostatic spinning, spinning voltage 20KV, fltting speed 60
μm/min, and receive apart from 25cm, so as to many bases discoloration for obtaining launching under different ultraviolet lights different fluorescence, to receive micron fine
Dimension.Prepared fiber is capable of achieving different fluorescence discolorations under ultraviolet light in Fig. 7, and its color can occur substantially after pre-irradiation
Change, gives the photochromic nano micron fibre of multiple bases and resulting launching light is excited under 256nm and 367nm wavelength
Spectrum, it can be seen that prepared fiber sample shows green light when 256nm wavelength is excited, when 367nm wavelength is excited
Show red light.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be in other specific forms realized.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires to be limited rather than described above, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as the claim involved by limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each implementation method is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Specification an as entirety, the technical scheme in each embodiment can also be formed into those skilled in the art through appropriately combined
May be appreciated other embodiment.
Claims (7)
1. a kind of preparation method of photochromic block copolymer, it is characterised in that comprise the following steps：
Step 1, the preparation of vinyl spiro-pyrans photochromic monomer (SPMA)：5-6gN- ethoxys -3,3- is added in there-necked flask
Dimethyl -6- nitroindoline quinolines spiro-pyrans (SP-OH) and 60-80ml dichloromethane, under 0-5 DEG C of ice-water bath nitrogen protective condition
Moderate-speed mixer, TLC points plate is followed the trail of, and adds pyridine 2-5g as acid binding agent；Measure 2-5g methacrylic chloride mixing 10-15ml bis-
Chloromethanes is added in constant pressure funnel, is then added dropwise in there-necked flask, within 30min, 0-5 DEG C of stirring 0.5h
Afterwards, 25-30 DEG C is warming up to, continuation is reacted, TLC points plate is followed the trail of, disappearing or do not see substantially to raw material point；Then first spend
Ionized water extracting and washing point liquid, removes the hydrochloride of pyridine, and resulting product removes methylene chloride, institute by rotary evaporation
Royal purple product is obtained, is further purified by column chromatography silica gel flash chromatography post, be 5 using volume ratio:1 petroleum ether and second
Used as eluant, eluent, rotary evaporation obtains light green color SPMA to the mixed liquor of acetoacetic ester；
Step 2, the preparation of spiro-pyrans macromole evocating agent (PSPMA-Br)：Flask-vacuumize-lead to first is carried out to Schlenk bottles
Nitrogen treatment, by monomer SPMA1.0-1.5g, initiator 2- isobutyl ethyl bromide 15-20 μ l, part N, N, N', N, ' N "-five first
Base diethylenetriamines 44-55 μ l, solvent THF5-6ml and methyl alcohol 1-1.5ml are added in Schlenk bottles, after further take off
Gas, liquid nitrogen frozen-vacuumize-thaw cycles three times are rapid after last time is freezed to weigh 0.01-0.02g catalyst brominations
It is cuprous to be added thereto, and magneton is added, ultrasound makes its dispersed, is placed in after defrosting in 40-45 DEG C of water-bath and reacts 4-6h and lead to
Nitrogen is protected；Then product exposure in atmosphere, after being cooled to room temperature, pours into precipitation in a large amount of methyl alcohol after reacting,
And repeatedly with tetrahydrofuran and methyl alcohol at least three times are washed to lighter, and product is centrifugally separating to obtain, 40-45 DEG C of vacuum is done
It is dry, obtain final light-blue solid PSPMA-Br；
Step 3, the preparation of spiro-pyrans methyl methacrylate segmented copolymer (PSPMA-g-PMMA)：First Schlenk bottles is entered
Row flask-vacuumize-lead to nitrogen treatment, iterative cycles three times add monomers methyl methacrylate 10- to Schlenk bottles
12ml, initiator PSPMA-Br0.2-0.3g, part PMDETA35-40 μ l, solvent THF10-15ml and methyl alcohol 3-5ml, then
Further degassing, liquid nitrogen frozen-vacuumize-thaw cycles three times, the rapid 0.12-0.15g that weighs is urged after last time is freezed
Agent cuprous bromide is added thereto, and adds magneton, makes its dispersed using ultrasonic wave, and 40-45 DEG C of water-bath is placed in after defrosting
Middle reaction 6-8h is passed through nitrogen protection；Then by mixture exposure in atmosphere, after being cooled to room temperature, in pouring into a large amount of methyl alcohol
Precipitation, centrifugation, and washed with THF and methyl alcohol repeatedly to lighter, 40-45 DEG C of drying of vacuum, finally giving product is
The PSPMA-g-PMMA of light green solid shape.
2. step 4, the preparation of photochromic fibre：By the PSPMA-g-PMMA of step 3 gained with DMF as solvent, compound concentration
The spinning solution of 20%-25%, and 1,10- Phen-Tb organic rare-earth ligands are added in spinning solution, then carry out electrostatic
Spinning, spinning voltage 15-22KV, 40-60 μm of fltting speed/min is received apart from 15-30cm, so as to obtain in different ultraviolet lights
Many bases discoloration nano micron fibre of the irradiation different fluorescence of lower transmitting.
3. a kind of preparation method of photochromic block copolymer according to claim 1, it is characterised in that the wash-out
Agent and solvent are petroleum ether and ethyl acetate by 5:1 ratio is mixed to prepare.
4. a kind of photochromic block copolymer according to claim 1, it is characterised in that the rare earth terbium luminescent material
It is the organic rare-earth ligand prepared by chemically reacting by the centre of luminescence and its part.
5. a kind of photochromic block copolymer according to claim 3, it is characterised in that according to claim 1
A kind of photochromic block copolymer, it is characterised in that the rare earth terbium luminescent material, its part is including benzoic acid, to methyl
Benzoic acid, p-aminobenzoic acid, paranitrobenzoic acid, P-methoxybenzoic acid, 1,3,5 trimesic acids, 3- nitro -4- amino
The chloro- 3- nitrobenzoic acids of benzoic acid, 4-, TTA, 1,10- Phen, 2,2 '-bipyridyl, 4,4 '-connection pyrrole
Pyridine.
6. a kind of preparation method of the photochromic nano micron fibre of multiple bases according to claim 1, compound concentration 20%-
25% spinning solution, and 1,10- Phen-Tb organic rare-earth ligands are added in spinning solution, electrostatic spinning is then carried out,
Spinning voltage 15-22KV, 40-60 μm of fltting speed/min is received apart from 15-30cm.
7. a kind of photochromic block copolymer according to claim 1, it is characterised in that the multiple bases are photochromic
Nano micron fibre excites lower achievable many base color changeable effects in different ultraviolet wavelengths：When fine using 360-367nm ultraviolet lights
Its display is red during dimension sample；Green is shown when using 254-295nm ultraviolet lights；In using 360-367nm
The ultraviolet light of any wavelength in any wavelength and 254-295nm then shows yellow when exciting jointly；Removed when by ultraviolet light
Afterwards, prepared nano micron fibre is rendered as purple；Can instantaneously be changed into white by heating sample.This colourshifting process can be unlimited
Circulation.
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| CN113024570A (en) * | 2021-03-22 | 2021-06-25 | 浙江理工大学 | Spiropyran-loaded metal-organic framework photochromic material and preparation method thereof |
| CN113122947A (en) * | 2021-04-25 | 2021-07-16 | 江苏新视界先进功能纤维创新中心有限公司 | Multi-base color-changing luminescent fiber with antibacterial property and preparation method thereof |
| CN114316285A (en) * | 2021-11-30 | 2022-04-12 | 中国科学院福建物质结构研究所 | Inorganic-organic hybrid compound crystal KCuIL and preparation method and application thereof |
| CN114940844A (en) * | 2022-06-16 | 2022-08-26 | 西北工业大学 | Liquid crystal type anti-counterfeiting ink based on photoresponse and preparation method thereof |
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| CN113024570A (en) * | 2021-03-22 | 2021-06-25 | 浙江理工大学 | Spiropyran-loaded metal-organic framework photochromic material and preparation method thereof |
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| CN114316285A (en) * | 2021-11-30 | 2022-04-12 | 中国科学院福建物质结构研究所 | Inorganic-organic hybrid compound crystal KCuIL and preparation method and application thereof |
| CN114940844A (en) * | 2022-06-16 | 2022-08-26 | 西北工业大学 | Liquid crystal type anti-counterfeiting ink based on photoresponse and preparation method thereof |
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