CN106835319B - A kind of preparation method of photochromic block copolymer - Google Patents
A kind of preparation method of photochromic block copolymer Download PDFInfo
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- CN106835319B CN106835319B CN201611150459.5A CN201611150459A CN106835319B CN 106835319 B CN106835319 B CN 106835319B CN 201611150459 A CN201611150459 A CN 201611150459A CN 106835319 B CN106835319 B CN 106835319B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 32
- 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 11
- 238000000034 method Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 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 45
- 239000002904 solvent Substances 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 15
- 239000003208 petroleum Substances 0.000 claims description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 12
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010257 thawing Methods 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000005406 washing 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
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 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
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 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
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- -1 Dimethyl -6- nitroindoline quinoline Chemical compound 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
- 239000007789 gas Substances 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000000746 purification Methods 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 21
- 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
- 239000002244 precipitate Substances 0.000 description 5
- 206010013786 Dry skin Diseases 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 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
- 238000012512 characterization method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 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
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 238000012661 block copolymerization Methods 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
- 125000004494 ethyl ester group Chemical group 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
- 208000014674 injury Diseases 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 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 methods of photochromic block copolymer, include 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 present invention are: the nano micron fibre prepared by through the invention, it can be realized under the irradiation of different light and realize red, green, yellow color fluorescence transformation under different ultraviolet lights, and fiber becomes darkviolet from colourless after ultraviolet irradiation, it obtains fiber and repeats to convert between purple colourless, so that obtaining can luminous coloration fiber.This method needs not move through printing and dyeing, while avoiding the pollution of environment, and assigns a variety of discolorations of fiber and light-emitting function.
Description
Technical field
The present invention relates to a kind of photochromic luminous coloration fiber producing processes, specifically a kind of photochromic block copolymerizations
The preparation method of object.
Background technique
Today's society with social development, liked by people by the fabric to vary in color, and colorful fabric is main at present
Source is textile and dyeing industry, and the development of printing and dyeing industry brings colorful clothes to enjoy to us.But consequent is life
Environment it is increasingly seriously polluted, contained in dyestuff waste liquid the toxic metals such as heavy metal cadmium, mercury, chromium, lead to people's body
There is a great harm for.So seeking that new to prepare colorful cloth process extremely urgent.
The prior art: being first prepared into and do not have coloured cloth, then carries out industrial printing and dyeing by the dyestuff of different colours, or
Off-color material by adding organic or inorganic is prepared into spinning solution, then sharp spining technology is prepared by solution spinning processes
As fiber.The shortcomings that prior art is that industrial pollution is more serious, bigger to human injury.Existing other technologies discoloration is more
It is single, it is not able to satisfy multifunctional clothes decoration materials demand.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of photochromic block copolymer, to solve above-mentioned background skill
The problem of being proposed in art.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of photochromic block copolymer, includes the following steps:
Step 1,5-6gN- ethoxy -3,3- dimethyl -6- nitroindoline quinoline the preparation of SPMA: is added in three-necked flask
Spiro-pyrans and 60-80ml methylene chloride, moderate-speed mixer under the conditions of 0-5 DEG C of ice-water bath nitrogen protection carry out TLC using solvent
Pyridine 2-5g is added as acid binding agent in contact plate tracking；2-5g methacrylic chloride mixing 10-15ml methylene chloride is measured to be added to
It in constant pressure funnel, is then added dropwise in three-necked flask, within 30min, after 0-5 DEG C of stirring 0.5h, is warming up to 25-
30 DEG C, the reaction was continued, carries out the tracking of TLC contact plate using solvent, until raw material point disappears or does not see substantially；Then it first uses
Deionized water extracting and washing liquid separation removes the hydrochloride of pyridine, and acquired product removes methylene chloride by rotary evaporation,
Gained royal purple product is further purified by column chromatography silica gel flash chromatography column, using volume ratio be 5:1 petroleum ether and
The mixed liquor of ethyl acetate obtains SPMA as eluant, eluent, rotary evaporation；
Step 2, the preparation of PSPMA-Br: first Schlenk bottles of progress flasks-are vacuumized-lead to nitrogen treatment, by monomer
SPMA1.0-1.5g, initiator 2- isobutyl ethyl bromide 15-20 μ l, ligand N, N, N', N, ' N "-five methyl diethylentriamine
44-55 μ l, solvent THF5-6ml and methanol 1-1.5ml are added in Schlenk bottles, rear further degassing, and liquid nitrogen frozen-pumping is true
Sky-thaw cycles three times, weigh rapidly 0.01-0.02g catalyst cuprous bromide after last time freezes and are added thereto, and add
Enter magneton, ultrasound keeps its evenly dispersed, and defrosting is placed in 40-45 DEG C of water-bath to react 4-6h and lead to nitrogen and be protected；Then
Product exposure in air, after being cooled to room temperature, will pour into a large amount of methanol and precipitate after reaction, and repeatedly with tetrahydrofuran and
Methanol washing at least three times to lighter, is centrifugally separating to obtain product, 40-45 DEG C of drying of vacuum obtains final light blue solid
Body PSPMA-Br；
Step 3, the preparation of PSPMA-g-PMMA: nitrogen treatment is first vacuumized-leads to Schlenk bottles of progress flasks-, repeatedly
It recycles three times, to Schlenk bottles of addition monomers methyl methacrylate 10-12ml, initiator PSPMA-Br0.2-0.3g, ligand
PMDETA35-40 μ l, solvent THF10-15ml and methanol 3-5ml, then further degassing, liquid nitrogen frozen-are vacuumized-are thawed and follow
Ring three times, weighs rapidly 0.12-0.15g catalyst CuBr after last time freezes and is added thereto, and magneton is added, using super
Sound wave keeps its evenly dispersed, and defrosting, which is placed in 40-45 DEG C of water-bath, reacts 6-8h and be passed through nitrogen protection；Then mixture is sudden and violent
Dew in air, after being cooled to room temperature, pour into a large amount of methanol and precipitate, be centrifugated, and repeatedly with THF and methanol wash to
Lighter, 40-45 DEG C of drying of vacuum finally obtain the PSPMA-g-PMMA that product is light green solid shape；
Step 4, it the preparation of photochromic fibre: by the resulting PSPMA-g-PMMA of step 3 using DMF as solvent, prepares dense
The spinning solution of 20%-25% is spent, and 1 is added in spinning solution, then 10- Phen-Tb organic rare-earth ligand carries out quiet
Electrospun, spinning voltage 15-22KV, 40-60 μm of fltting speed/min receive distance 15-30cm, to obtain different ultraviolet
More bases discoloration nano micron fibre of the different fluorescence of the lower transmitting of light irradiation.
As a further solution of the present invention, it is 5:1 ratio that the solvent is petroleum ether and ethyl acetate by volume
It is mixed to prepare.
As further scheme of the invention, more bases discoloration nano micron fibres can under the excitation of different ultraviolet wavelengths
Realize more base color changeable effects: it is displayed in red when using 360-367nm ultraviolet light fiber sample；When use 254-
Green is shown when 295nm ultraviolet light；Any wave in any wavelength and 254-295nm in use 360-367nm
Long ultraviolet light then shows yellow when exciting jointly；After removing ultraviolet light, prepared nano micron fibre is rendered as purple
Color；White can instantaneously be become by heating sample；This colourshifting process can recycle infinitely.
Compared with prior art, the beneficial effects of the present invention are: prepared nano micron fibre through the invention, Ke Yi
Lower realize of different light irradiations realizes red, green, yellow color fluorescence transformation under different ultraviolet lights, and fine after ultraviolet irradiation
Dimension from colourless becomes darkviolet, obtains fiber and repeat to convert between purple colourless, so that obtaining can luminous coloration fiber.This
Kind method needs not move through printing and dyeing, while avoiding the pollution of environment, and assigns a variety of discolorations of fiber and light-emitting function.
Detailed description of the invention
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 reaction process.
Fig. 4 is the 1HNMR spectrogram of SPMA.
Fig. 5 is the 1HNMR spectrogram of block copolymer PSPMA-g-PMMA.
Fig. 6 is electrospun fibers SEM photograph.
Fig. 7 fiber fluorescence spectrum under different excitation wavelengths.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
Step 1, the preparation of photochromic monomer (SPMA)
As shown in Figure 1, the specific steps of which are as follows:
(1) in three-necked flask be added 5gN- ethoxy -3,3- dimethyl -6- nitroindoline quinoline spiro-pyrans (SP-OH) and
60ml methylene chloride, moderate-speed mixer under the conditions of 0-5 DEG C of ice-water bath nitrogen protection, the petroleum ether and second for being 5:1 using volume ratio
The mixed liquor of acetoacetic ester carries out the tracking of TLC contact plate as solvent, using solvent, and pyridine 2g is added as acid binding agent；
(2) it measures 2g methacrylic chloride mixing 10ml methylene chloride to be added in constant pressure funnel, then add dropwise
Enter into three-necked flask, within 30min, after 0-5 DEG C of stirring 0.5h, is warming up to 25-30 DEG C, the reaction was continued, utilizes volume ratio
It is the petroleum ether of 5:1 and the mixed liquor of ethyl acetate as solvent, the tracking of TLC contact plate is carried out using solvent, until raw material point
Until disappearing or not seeing substantially；
(3) liquid separation of deionized water extracting and washing is then first used, the hydrochloride of pyridine is removed, acquired product is steamed by rotation
Hair removes methylene chloride, and gained royal purple product is further purified by column chromatography silica gel flash chromatography column, utilizes body
For the mixed liquor of petroleum ether and ethyl acetate that product ratio is 5:1 as eluant, eluent, rotary evaporation obtains SPMA.
Step 2, the preparation of photochromic polymer (PSPMA-Br)
(1) first Schlenk bottles of progress flasks-are vacuumized-lead to nitrogen treatment, by monomer SPMA1.0g, initiator 2- bromine
15 μ l of ethyl isobutyrate, ligand N, N, N', N, ' 44 μ l of N "-five methyl diethylentriamine (PMDETA), solvent THF5ml and first
Alcohol 1ml is added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, it is cold in last time
0.01g catalyst cuprous bromide (CuBr) is weighed after jelly rapidly to be added thereto, and magneton is added, ultrasound keeps its evenly dispersed, solution
Jelly is placed in 40-45 DEG C of water-bath to react 4h and lead to nitrogen and be protected；
(2) product exposure in air, after being cooled to room temperature, is poured into a large amount of methanol and is precipitated after then reacting, from
Heart separation, and washed repeatedly with tetrahydrofuran (THF) and methanol at least three times to lighter, 40-45 DEG C of drying of vacuum obtains
Final light-blue solid PSPMA-Br.
Step 3, the preparation of photochromic block copolymer (PSPMA-g-PMMA)
As shown in Figure 2, the specific steps are as follows:
(1) nitrogen treatment is first vacuumized-leads to Schlenk bottles of progress flasks-, iterative cycles three times, add to Schlenk bottles
Enter monomers methyl methacrylate (MMA) 10ml, initiator PSPMA-Br0.2g, ligand PMDETA35 μ l, solvent THF10ml and
Methanol 3ml, then further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, weighed rapidly after last time freezes
0.12g catalyst CuBr is added thereto, and magneton is added, and keeps its evenly dispersed using ultrasonic wave, and defrosting is placed on 40-45 DEG C of water
8h is reacted in bath and is passed through nitrogen protection.
(2) then mixture is exposed in air, after being cooled to room temperature, pours into a large amount of methanol and precipitate, centrifugation point
From, and washed repeatedly with THF and methanol to lighter, 40-45 DEG C of drying of vacuum, finally obtaining product is light green solid shape
PSPMA-g-PMMA.Fig. 3 is block copolymer PSPMA-g-PMMA infrared spectrum, and 1610cm-1,1457cm-1 are benzene in figure
The feature stretching vibration peak of ring；748cm-1 is the disubstituted characteristic peak in ortho position on phenyl ring；1157cm-1,1089cm-1 characteristic peak is
C-O-C ehter bond characteristic absorption peak；- CH3 and-CH2- are corresponded respectively in the infrared absorption peak of 2960cm-1~2865cm-1 range
Stretching vibration；- OH the stretching vibration peak of SP-OH is located at 3280cm-1.MMA polymerization activity is larger, content phase in final product
To higher, the characteristic absorption peak of MMA ester group appears in 1737cm-1.Thus illustrate that block copolymer is successfully prepared.
Step 4, the preparation of photochromic fibre
By the resulting PSPMA-g-PMMA of step 3 using DMF as solvent, the spinning solution of compound concentration 20%, and in spinning solution
Middle addition 1,10- Phen-Tb organic rare-earth ligand, then carries out electrostatic spinning, spinning voltage 22KV, fltting speed 60
μm/min, distance 22cm is received, so that micron fibre is received in the more bases discoloration for obtaining emitting under different ultraviolet lights different fluorescence
Dimension.
Embodiment 2
Step 1, the preparation of photochromic monomer (SPMA)
(1) in three-necked flask be added 6gN- ethoxy -3,3- dimethyl -6- nitroindoline quinoline spiro-pyrans (SP-OH) and
80ml methylene chloride, moderate-speed mixer under the conditions of 0 DEG C of ice-water bath nitrogen protection, the petroleum ether and acetic acid for being 5:1 using volume ratio
The mixed liquor of ethyl ester carries out the tracking of TLC contact plate as solvent, using solvent, and pyridine 5g is added as acid binding agent；
(2) it measures 5g methacrylic chloride mixing 15ml methylene chloride to be added in constant pressure funnel, then add dropwise
Enter into three-necked flask, within 30min, after 0 DEG C of stirring 0.5h, be warming up to 25 DEG C, the reaction was continued, is 5:1 using volume ratio
Petroleum ether and ethyl acetate mixed liquor as solvent, carry out the tracking of TLC contact plate using solvent, until raw material point disappear or
Substantially until not seeing；
(3) liquid separation of deionized water extracting and washing is then first used, the hydrochloride of pyridine is removed, acquired product is steamed by rotation
Hair removes methylene chloride, and gained royal purple product is further purified by column chromatography silica gel flash chromatography column, utilizes body
For the mixed liquor of petroleum ether and ethyl acetate that product ratio is 5:1 as eluant, eluent, rotary evaporation obtains SPMA.Pass through nuclear-magnetism in Fig. 4
Characterization can prove that products therefrom structure is the structure of target molecule, and monomer SPMA is successfully prepared.
Step 2, the preparation of photochromic polymer (PSPMA-Br)
(1) first Schlenk bottles of progress flasks-are vacuumized-lead to nitrogen treatment, by monomer SPMA1.5g, initiator 2- bromine
20 μ l of ethyl isobutyrate, ligand N, N, N', N, ' 55 μ l of N "-five methyl diethylentriamine (PMDETA), solvent THF6ml and first
Alcohol 1.5ml is added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, in last time
0.02g catalyst cuprous bromide (CuBr) is weighed after freezing rapidly to be added thereto, and magneton is added, ultrasound keeps its evenly dispersed,
Defrosting is placed in 40 DEG C of water-baths to react 4h and lead to nitrogen and be protected；
(2) product exposure in air, after being cooled to room temperature, is poured into a large amount of methanol and is precipitated after then reacting, from
Heart separation, and washed repeatedly with tetrahydrofuran (THF) and methanol at least three times to lighter, 40 DEG C of dryings of vacuum obtain most
Whole light-blue solid PSPMA-Br.
Step 3, the preparation of photochromic block copolymer (PSPMA-g-PMMA)
(1) nitrogen treatment is first vacuumized-leads to Schlenk bottles of progress flasks-, iterative cycles three times, add to Schlenk bottles
Enter monomers methyl methacrylate (MMA) 12ml, initiator PSPMA-Br0.3g, ligand PMDETA40 μ l, solvent THF15ml and
Methanol 5ml, then further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, weighed rapidly after last time freezes
0.15g catalyst CuBr is added thereto, and magneton is added, and keeps its evenly dispersed using ultrasonic wave, and defrosting is placed on 40 DEG C of water-baths
Middle reaction 8h is simultaneously passed through nitrogen protection；
(2) then mixture is exposed in air, after being cooled to room temperature, pours into a large amount of methanol and precipitate, centrifugation point
From, and washed repeatedly with THF and methanol to lighter, 40 DEG C of dryings of vacuum, finally obtaining product is light green solid shape
PSPMA-g-PMMA.Relative to monomer SPMA nuclear magnetic spectrogram in Fig. 5, there is obvious new position in the nuclear magnetic spectrogram of block copolymer
It moves peak to occur, the peak intensity for being prepared into SPMA after block copolymer obviously weakens relative to MMA, this is because MMA monomer reactivity
Higher, the degree of polymerization is far longer than SPMA monomer, and the peak that nuclear-magnetism characterization goes out is the chemical shift of Hydrogen Proton in PMMA structure,
Chemical shift is the proton peak of pendant methyl in methyl methacrylate structure at 1.02ppm；Chemical shift is corresponding at 1.81ppm
The proton peak of methylene-CH2 after double bond is opened after methyl methacrylate polymerization；Chemical shift is methyl-prop at 3.60ppm
Hydrogen Proton peak at CH3-O- after e pioic acid methyl ester polymerization.Pass through atom transfer radical polymerization method, target known to upper map analysis
Block copolymer is successfully prepared.
Step 4, the preparation of photochromic fibre
By the resulting PSPMA-g-PMMA of step 3 using DMF as solvent, the spinning solution of compound concentration 25%, and in spinning solution
Middle addition 1,10- Phen-Tb organic rare-earth ligand, then carries out electrostatic spinning, spinning voltage 20KV, fltting speed 60
μm/min, receive distance 25cm.Micron fibre is received to obtain emitting under different ultraviolet lights more bases discoloration of different fluorescence
Dimension.It can be found that prepared photochromic nano micron fibre surface is relatively smooth by stereoscan photograph in Fig. 6, size distribution
More uniformly, precondition is provided for its application as fabric.
Embodiment 3
(1) in three-necked flask be added 5gN- ethoxy -3,3- dimethyl -6- nitroindoline quinoline spiro-pyrans (SP-OH) and
70ml methylene chloride, moderate-speed mixer under the conditions of 0-5 DEG C of ice-water bath nitrogen protection, the petroleum ether and second for being 5:1 using volume ratio
The mixed liquor of acetoacetic ester carries out the tracking of TLC contact plate as solvent, using solvent, and pyridine 4g is added as acid binding agent；
(2) it measures 4g methacrylic chloride mixing 13ml methylene chloride to be added in constant pressure funnel, then add dropwise
Enter into three-necked flask, within 30min, after 5 DEG C of stirring 0.5h, be warming up to 30 DEG C, the reaction was continued, is 5:1 using volume ratio
Petroleum ether and ethyl acetate mixed liquor as solvent, carry out the tracking of TLC contact plate using solvent, until raw material point disappear or
Substantially until not seeing；
(3) liquid separation of deionized water extracting and washing is then first used, the hydrochloride of pyridine is removed, acquired product is steamed by rotation
Hair removes methylene chloride, and gained royal purple product is further purified by column chromatography silica gel flash chromatography column, utilizes body
For the mixed liquor of petroleum ether and ethyl acetate that product ratio is 5:1 as eluant, eluent, rotary evaporation obtains SPMA.
Step 2, the preparation of photochromic polymer (PSPMA-Br)
(1) first Schlenk bottles of progress flasks-are vacuumized-lead to nitrogen treatment, by monomer SPMA1.3g, initiator 2- bromine
18 μ l of ethyl isobutyrate, ligand N, N, N', N, ' 50 μ l of N "-five methyl diethylentriamine (PMDETA), solvent THF6ml and first
Alcohol 1.3ml is added in Schlenk bottles, rear further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, in last time
0.02g catalyst cuprous bromide (CuBr) is weighed after freezing rapidly to be added thereto, and magneton is added, ultrasound keeps its evenly dispersed,
Defrosting is placed in 45 DEG C of water-baths to react 4h and lead to nitrogen and be protected；
(2) product exposure in air, after being cooled to room temperature, is poured into a large amount of methanol and is precipitated after then reacting, from
Heart separation, and washed repeatedly with tetrahydrofuran (THF) and methanol at least three times to lighter, 45 DEG C of dryings of vacuum obtain most
Whole light-blue solid PSPMA-Br.
Step 3, the preparation of photochromic block copolymer (PSPMA-g-PMMA)
(1) first vacuumize-lead to nitrogen treatment to Schlenk bottles of progress flasks-, iterative cycles three times, to Schlenk bottles
Monomers methyl methacrylate (MMA) 11ml, initiator PSPMA-Br0.3g, ligand PMDETA38 μ l, solvent THF13ml is added
With methanol 4ml, then further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, claim rapidly after last time freezes
Amount 0.15g catalyst CuBr is added thereto, and magneton is added, and keeps its evenly dispersed using ultrasonic wave, and defrosting is placed on 45 DEG C of water
8h is reacted in bath and is passed through nitrogen protection；
(2) then mixture is exposed in air, after being cooled to room temperature, pours into a large amount of methanol and precipitate, centrifugation point
From, and washed repeatedly with THF and methanol to lighter, 45 DEG C of dryings of vacuum, finally obtaining product is light green solid shape
PSPMA-g-PMMA。
Step 4, the preparation of photochromic fibre
By the resulting PSPMA-g-PMMA of step 3 using DMF as solvent, the spinning solution of compound concentration 25%, and in spinning solution
Middle addition 1,10- Phen-Tb organic rare-earth ligand, then carries out electrostatic spinning, spinning voltage 20KV, fltting speed 60
μm/min, distance 25cm is received, so that micron fibre is received in the more bases discoloration for obtaining emitting under different ultraviolet lights different fluorescence
Dimension.Different fluorescence discolorations can be achieved in prepared fiber under ultraviolet light in Fig. 7, its color of irradiation front and back can occur obviously
Variation, gives the photochromic nano micron fibre of multiple bases and excites obtained transmitting light under 256nm and 367nm wavelength
Spectrum, it can be seen that prepared fiber sample shows green light when 256nm wavelength excites, in the excitation of 367nm wavelength
Show red light.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (3)
1. a kind of preparation method of photochromic block copolymer, which comprises the steps of:
Step 1,5-6gN- ethoxy -3,3- the preparation of vinyl spiro-pyrans photochromic monomer (SPMA): is added in three-necked flask
Dimethyl -6- nitroindoline quinoline spiro-pyrans (SP-OH) and 60-80ml methylene chloride, under the conditions of 0-5 DEG C of ice-water bath nitrogen protection
Moderate-speed mixer carries out the tracking of TLC contact plate using solvent, and pyridine 2-5g is added as acid binding agent；Measure 2-5g methacryl
Chlorine mixing 10-15ml methylene chloride is added in constant pressure funnel, is then added dropwise in three-necked flask, 30min it
It is interior, after 0-5 DEG C of stirring 0.5h, it is warming up to 25-30 DEG C, the reaction was continued, the tracking of TLC contact plate is carried out using solvent, until raw material point
Until disappearing or not seeing substantially；Then the liquid separation of deionized water extracting and washing is first used, the hydrochloride of pyridine, acquired product are removed
Methylene chloride is removed by rotary evaporation, gained royal purple product is further by column chromatography silica gel flash chromatography column
Purification, using the mixed liquor of petroleum ether and ethyl acetate that volume ratio is 5:1 as eluant, eluent, rotary evaporation obtains light green color
SPMA；
Step 2, the preparation of spiro-pyrans macromole evocating agent (PSPMA-Br): first Schlenk bottles of progress flasks-are vacuumized-led to
Nitrogen treatment, by monomer SPMA1.0-1.5g, initiator 2- isobutyl ethyl bromide 15-20 μ l, ligand N, N, N ' ,-five first of N ", N "
Base diethylenetriamines 44-55 μ l, solvent THF5-6ml and methanol 1-1.5ml are added in Schlenk bottles, after further take off
Gas, liquid nitrogen frozen-vacuumizes-thaw cycles three times, weigh 0.01-0.02g catalyst bromination rapidly after last time freezes
It is cuprous to be added thereto, and magneton is added, ultrasound keeps its evenly dispersed, and defrosting, which is placed in 40-45 DEG C of water-bath, reacts 4-6h and lead to
Nitrogen is protected；Then product exposure in air, after being cooled to room temperature, is poured into a large amount of methanol and is precipitated after reacting,
And washed at least with tetrahydrofuran and methanol three times to lighter repeatedly, it is centrifugally separating to obtain product, 40-45 DEG C of vacuum is dry
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 to Schlenk bottles into
Row flask-vacuumizing-leads to nitrogen treatment, iterative cycles three times, to Schlenk bottles of addition monomers methyl methacrylate 10-
12ml, initiator PSPMA-Br0.2-0.3g, ligand PMDETA35-40 μ l, solvent THF10-15ml and methanol 3-5ml, then
Further degassing, liquid nitrogen frozen-vacuumizes-thaw cycles three times, weigh 0.12-0.15g rapidly after last time freezes and urge
Agent cuprous bromide is added thereto, and magneton is added, and keeps its evenly dispersed using ultrasonic wave, and defrosting is placed on 40-45 DEG C of water-bath
Middle reaction 6-8h is passed through nitrogen protection；Then in air by mixture exposure, after being cooled to room temperature, pour into a large amount of methanol
Precipitating, centrifuge separation, and washed repeatedly with THF and methanol to lighter, 40-45 DEG C of drying of vacuum, finally obtaining product is
The PSPMA-g-PMMA of light green solid shape；
Step 4, the preparation of photochromic fibre: by the resulting PSPMA-g-PMMA of step 3 using DMF as solvent, compound concentration
The spinning solution of 20%-25%, and 1 is added in spinning solution, then 10- Phen-Tb organic rare-earth ligand carries out electrostatic
Spinning, spinning voltage 15-22KV, 40-60 μm of fltting speed/min receive distance 15-30cm, to obtain in different ultraviolet lights
More bases discoloration nano micron fibre of the different fluorescence of the lower transmitting of irradiation.
2. a kind of preparation method of photochromic block copolymer according to claim 1, which is characterized in that the expansion
Agent is that petroleum ether and ethyl acetate are mixed to prepare by the volume ratio of 5:1.
3. a kind of preparation method of photochromic block copolymer according to claim 1, which is characterized in that more bases
More base color changeable effects can be achieved under the excitation of different ultraviolet wavelengths in discoloration nano micron fibre: when use 360-367nm ultraviolet lighting
It is displayed in red when penetrating fiber sample；Green is shown when using 254-295nm ultraviolet light；When use 360-367nm
In any wavelength and 254-295nm in the ultraviolet light of any wavelength then show yellow when exciting jointly；When by ultraviolet light
After removing, prepared nano micron fibre is rendered as purple；White can instantaneously be become by heating sample；This colourshifting process can nothing
Limit time circulation.
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| CN102071490A (en) * | 2010-12-11 | 2011-05-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing organic photochromic nanofibers |
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