CN103910838B - Contain the Preparation method and use of the di-block copolymer of spiropyran groups - Google Patents
Contain the Preparation method and use of the di-block copolymer of spiropyran groups Download PDFInfo
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- CN103910838B CN103910838B CN201410039513.3A CN201410039513A CN103910838B CN 103910838 B CN103910838 B CN 103910838B CN 201410039513 A CN201410039513 A CN 201410039513A CN 103910838 B CN103910838 B CN 103910838B
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 230000000740 bleeding effect Effects 0.000 claims description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 5
- -1 2-isobutyl ethyl Chemical group 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing 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 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004880 oxines Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Abstract
The invention discloses a kind of Preparation method and use of the di-block copolymer containing spiropyran groups. The step of the method is as follows: step 1) is prepared solid sample P (BMA-<i>Co</i>-SPMA)-Br; Step 2) obtain the di-block copolymer P (BMA-containing spiropyran groups<i>Co</i>-SPMA)-<i>b</i>-PDMAEMA; Step 3) is by block copolymer P (BMA-<i>Co</i>-SPMA)-<i>b</i>-PDMAEMA is dissolved in THF, obtains stable micella dispersion soln. This solution evenly drips and is coated on the scraps of paper, obtains applying the film of 11.5mg micella; Ultraviolet light sees through the surface of the mould irradiation scraps of paper that are carved with word, and the scraps of paper that apply micella demonstrate blue word, and blue font part can also be sent pink colour fluorescence. The less pollution of the present invention to environment is a kind of coating material of environmental protection.
Description
Technical field
The present invention relates to a kind of block polymer, especially relate to a kind of two block copolymerizations containing spiropyran groupsThe Preparation method and use of thing.
Background technology
By the isomerization of photoinduction control photosensitive group, realize the switching over of fluorescence, this fluorescence regulatesMaterial has the important purpose of answering in fields such as false proof, information storage, light-operated switch and bio-medical materialsJustice. Spiro-pyrans is a kind of important photosensitive group, is widely used in preparing the adjustable intellectual material of fluorescence.Spiro-pyrans is introduced in hydrophobic cavity, and the fluorescence of the merocyanine type isomers of spiro-pyrans significantly strengthens, and passes throughThe isomerization reaction of photoinduction control spiropyran groups, cuts with regard to the variation of controllable adjustment color and the switch of fluorescenceChange. [concrete visible ZhuMQ, ZhuL, HanJJ, WuW, HurstJK, LiADQ.J.Am.Chem.Soc.,2006,128(13):4303-4309.ZhuLY,WuWW,ZhuMiQ,HanJJ,HurstJK,LiADQ.J.Am.Chem.Soc.,2007,129(12):3524-3526.ZhuMQ,ZhangGF,LiC,AldredMP,ChangE,DrezekRA,LiADQ.J.Am.Chem.Soc.,2011,133(2):365-372.TianZY,WuWW,WanW,LiADQ.J.Am.Chem.Soc.,2011,133(40):16092-16100.]
Summary of the invention
In order to develop the anti-fake material with dual recognition feature, the object of the present invention is to provide a kind of containing spiral shellThe Preparation method and use of the di-block copolymer of pyrans group, has prepared a kind of water-soluble polymer micella breastLiquid, by photosensitive group spiro-pyrans is introduced to the hydrophobic kernel of micella, significantly improves the fluorescence intensity of micella,By irradiating or close the isomerization of ultraviolet light control spiropyran groups, reversible adjusting micella photochromic andFluorescent switch performance. This water-soluble emulsion is coated on paper, and after being dried, scraps of paper face coat is except toolHave outside photochromic properties, send stronger pink colour fluorescence, regulate coating face by irradiating or closing ultraviolet lightThe variation of look and the switching over of fluorescence.
The technical solution used in the present invention is:
One, a preparation method who contains the di-block copolymer of spiropyran groups, the step of the method is as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate (SPMA) and 0.14g is addedIn two dry neck bottles, get 0.12ml initator 2-isobutyl ethyl bromide, 0.21ml part PMDETA,The monomers B MA of 3.0ml and 3.0ml toluene, join in two neck bottles, initator 2-isobutyl ethyl bromide,The molar ratio of CuBr and part PMDETA remains on 1:1:1, monomers B MA and spiro-pyrans Ji YijijiaThe molar ratio of base acrylate between 1:1000～1000:1, two kinds of initator and BMA, SPMAThe mol ratio of monomer total amount between 1000:1～1:1000, sealing, then the liquid nitrogen frozen thaw cycles of bleedingThree times, two neck bottles are placed in after 90 DEG C of oil baths reaction 10h, open two neck bottles, and in liquid nitrogen cooling stoppingOnly reaction, adds dilution with toluene product solution, and after separating by neutral alumina chromatographic column, collection is flowed out moltenLiquid, and precipitate in-5 DEG C of methyl alcohol of 10 times of volumes that flow out solution, suction filtration collecting precipitation sample, lays equal stress onNewly be dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, and suction filtration is collected solid sampleP (BMA-co-SPMA)-Br, for subsequent use after vacuum drying 24h at 45 DEG C;
2) 0.50g initator P (BMA-co-SPMA)-Br is joined in two dry neck bottles, bleed and fillArgon gas circulation three times, measures 1.0ml monomer DMAEMA and 2.8ml toluene with syringe, and joinsFill in the two neck bottles of P (BMA-co-SPMA)-Br, sealing, after polymer dissolution, cold in liquid nitrogenFreeze the thaw cycles three times of bleeding, then open two neck bottles and pass into argon gas, now add 18 μ l partsPMDETA and 8.4mgCuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, initatorThe molar ratio of P (BMA-co-SPMA)-Br, CuCl and part PMDETA remains on 1:1:1, causesThe mol ratio of agent P (BMA-co-SPMA)-Br and monomer DMAEMA between 1000:1～1:1000,Two neck bottles are placed in to 40～120 DEG C of oil baths reaction, 0.5～24h to be placed in 90 DEG C of oil baths by two neck bottles and to react;After reaction finishes, open two neck bottles, in liquid nitrogen, cooling stopping reacts, and adds dilution with toluene product solution,Separate and remove catalyst by alkali alumina post, collect and flow out solution, and at 10 times of bodies that flow out solutionIn-5 DEG C of methyl alcohol that amass, precipitate, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate,This operation repeats twice, and suction filtration is collected solid sample, obtains the poly-(first of di-block copolymer containing spiropyran groupsBase n-butyl acrylate-co-spiro-pyrans base ethyl-methyl acrylate)-b-polymethylacrylic acid dimethylaminoEthyl ester (its English is abbreviated as P (BMA-co-SPMA)-b-PDMAEMA), vacuum drying at 45 DEG CFor subsequent use after 24h;
3) by step 2) block copolymer P (BMA-co-SPMA)-b-PDMAEMA of making is dissolved in THFIn, the ultrasonic polymer that makes dissolves completely, then deionized water is added drop-wise in polymer THF solution, withIn time, stirs, and continues to stir after deionized water adds, and the mixed solution obtaining is transferred to molecular cut offBe, in 3500 bag filter, in deionized water, to dialyse, change during this time fresh deionized water, after 2 days, obtainStable micella dispersion soln; Concrete reaction equation as shown in Figure 1.
Two, a kind of purposes of the di-block copolymer containing spiropyran groups
The micella dispersion soln that is 2.3mg/ml by the concentration of 5ml evenly drips and is coated on the scraps of paper, water at normal temperatureAfter solvent volatilizees completely, again evenly drip and be coated with, repeat aforesaid operations, obtain applying the thin of 11.5mg micellaFilm; Ultraviolet light sees through the surface of the mould irradiation scraps of paper that are carved with word, and the scraps of paper that apply micella demonstrate blue word,Blue font part can also be sent pink colour fluorescence.
The beneficial effect that the present invention has is:
1) thin polymer film has the photochromic and adjustable performance of fluorescence simultaneously, is that one has dual knowledgeThe anti-fake material of other feature.
2) isomerization of a kind of component of control spiro-pyrans just can regulate and control the photochromic and glimmering of micella simultaneouslyTwo kinds of stimuli responsive features such as luminous intensity.
3) regulate micella change color and fluorescent switch by irradiating or closing ultraviolet light, easy to operate, canRepeatedly to use, stability is higher, and the speed of response is very fast.
4) the synthetic polymer of the present invention obtains micella dispersion soln through self assembly, to the less pollution of environment,It is a kind of coating material of environmental protection.
Brief description of the drawings
Fig. 1 is that reaction equation of the present invention and micella form schematic diagram.
Fig. 2 is the hydrogen of polymer P (BMA-co-SPMA)-Br in chloroformic solution of deuteration that the present invention makes-nuclear magnetic spectrogram.
Fig. 3 is that block polymer P (BMA-co-SPMA)-b-PDMAEMA of making of the present invention is deuteratedHydrogen-nuclear magnetic spectrogram in chloroformic solution.
Fig. 4 is that block polymer P (BMA-co-SPMA)-b-PDMAEMA of making of the present invention is from groupThe transmission electron microscope photo of dress micella.
Fig. 5 is the schematic diagram (A) that block polymer that the present invention makes is coated in the scraps of paper and forms stable coatings.The overcover that ultraviolet lamp sees through hollow out " NANO " printed words irradiates the scraps of paper surface that applies micella, scraps of paper surfaceDemonstrate blueness " NANO " printed words, and " NANO " printed words part demonstrates pink colour fluorescence under ultraviolet light(B)。
Detailed description of the invention
Below by embodiment, the present invention is specifically described, only for the present invention is carried out furtherlyBright, can not be interpreted as limiting the scope of the present invention, person skilled in art can be according to foregoing inventionContent the present invention is made to some nonessential improvement and adjustment.
1. block polymer is synthetic
The CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate (SPMA) and 0.14g is joinedIn two dry neck bottles, measure 2-isobutyl ethyl bromide, the 0.21ml part of 0.12ml with syringeThe monomers B MA of PMDETA, 3.0ml and 3.0ml toluene, join in the two neck bottles that fill CuBr,Sealing, then bleed thaw cycles three times of liquid nitrogen frozen, is placed in two neck bottles after 90 DEG C of oil baths reaction 10h,Open two neck bottles, and in liquid nitrogen cooling stop reaction, add a small amount of dilution with toluene product solution, byProperty alumina chromatographic column separate after, collect flow out solution, and in the methyl alcohol (5 DEG C) of 10 times of volumes precipitate,Suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitating, this operation repeats twice, takes outSolid sample P (BMA-co-SPMA)-Br is collected in filter, for subsequent use after vacuum drying 24h at 45 DEG C, structureAs shown in Figure 2.
0.50g macromole evocating agent P (BMA-co-SPMA)-Br polymer is joined to two dry neck bottlesIn, the applying argon gas of bleeding circulation three times, measures 1.0ml monomer DMAEMA and 2.8ml toluene with syringe,And join in the two neck bottles that fill P (BMA-co-SPMA)-Br, sealing, after polymer dissolution,The freezing thaw cycles three times of bleeding in liquid nitrogen. Then open two neck bottles and pass into argon gas, now adding fast18 μ l part PMDETA and 8.4mgCuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, willTwo neck bottles are placed in 90 DEG C of oil baths and react. After reaction finishes, open two neck bottles, cooling stopping in liquid nitrogenReaction, adds a small amount of dilution with toluene product solution, is separated and is removed catalyst by alkali alumina post, collectsFlow out solution, precipitation in the methyl alcohol (5 DEG C) of 10 times of volumes, suction filtration collecting precipitation sample, and be again dissolved inIn toluene, in methyl alcohol, precipitate, this operation repeats twice, and suction filtration is collected solid sample, obtains containing spiro-pyransDi-block copolymer P (the BMA-co-SPMA)-b-PDMAEMA of group, vacuum drying 24h at 45 DEG CFor subsequent use afterwards, structure as shown in Figure 3.
2. the preparation of block polymer micelle
34mg block copolymer P (BMA-co-SPMA)-b-PDMAEMA is dissolved in the THF of 0.6ml,The ultrasonic polymer that makes dissolves completely, then 15ml deionized water is slowly added drop-wise to the THF solution of polymerIn, vigorous stirring simultaneously, continues after deionized water adds to stir 12h, and the mixed solution obtaining is turnedMove on to (molecular cut off 3500) in bag filter, in deionized water, dialyse 2 days, change during this time fresh go fromSub-water, obtains stable micella dispersion soln after 2 days.
As shown in Figure 4, be block polymer P (BMA-co-SPMA)-b-PDMAEMA that the present invention makesThe transmission electron microscope photo of self-assembled micelle.
3. the preparation of polymer micelle film
As shown in Figure 5, the micella dispersion soln that is 2.3mg/ml by the concentration of 5ml evenly drips and is coated in the scraps of paperUpper, after water at normal temperature solvent volatilizees completely, again evenly drip and be coated with, repeat aforesaid operations, obtain applying 11.5mgThe film of micella; Ultraviolet light sees through the surface of the mould irradiation scraps of paper that are carved with " NANO " printed words, coating adhesiveThe scraps of paper of bundle demonstrate the printed words of blueness " NANO ", as shown in Fig. 5 it (II), blue under ultraviolet lightLook font part can also be sent stronger pink colour fluorescence, as shown in Fig. 5 it (III).
Claims (2)
1. a preparation method who contains the di-block copolymer of spiropyran groups, is characterized in that the methodStep as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate SPMA and 0.14g is addedIn two dry neck bottles, get 0.12ml initator 2-isobutyl ethyl bromide, 0.21ml part PMDETA,The monomers B MA of 3.0ml and 3.0ml toluene, join in two neck bottles, initator 2-isobutyl ethyl bromide,The molar ratio of CuBr and part PMDETA remains on 1:1:1, monomers B MA and spiro-pyrans Ji YijijiaThe molar ratio of base acrylate between 1:1000～1000:1, two kinds of initator and BMA, SPMAThe mol ratio of monomer total amount between 1000:1～1:1000, sealing, then the liquid nitrogen frozen thaw cycles of bleedingThree times, two neck bottles are placed in after 90 DEG C of oil baths reaction 10h, open two neck bottles, and in liquid nitrogen cooling stoppingOnly reaction, adds dilution with toluene product solution, and after separating by neutral alumina chromatographic column, collection is flowed out moltenLiquid, and precipitate in-5 DEG C of methyl alcohol of 10 times of volumes that flow out solution, suction filtration collecting precipitation sample, lays equal stress onNewly be dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, and suction filtration is collected solid sampleP (BMA-co-SPMA)-Br, for subsequent use after vacuum drying 24h at 45 DEG C;
2) 0.50g initator P (BMA-co-SPMA)-Br is joined in two dry neck bottles, bleed and fillArgon gas circulation three times, measures 1.0ml monomer DMAEMA and 2.8ml toluene with syringe, and joinsFill in the two neck bottles of P (BMA-co-SPMA)-Br, sealing, after polymer dissolution, cold in liquid nitrogenFreeze the thaw cycles three times of bleeding, then open two neck bottles and pass into argon gas, now add 18 μ l partsPMDETA and 8.4mgCuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, initatorThe molar ratio of P (BMA-co-SPMA)-Br, CuCl and part PMDETA remains on 1:1:1, causesThe mol ratio of agent P (BMA-co-SPMA)-Br and monomer DMAEMA between 1000:1～1:1000,Two neck bottles are placed in to 40～120 DEG C of oil bath reaction 0.5～24h; After reaction finishes, open two neck bottles, at liquidIn nitrogen, cooling stopping reacts, and adds dilution with toluene product solution, separated and removed catalysis by alkali alumina postAgent, collects and flows out solution, and precipitates in-5 DEG C of methyl alcohol of 10 times of volumes that flow out solution, and suction filtration is collectedDeposit sample, and be again dissolved in toluene, in methyl alcohol, precipitating, this operation repeats twice, and suction filtration is collected solidBody sample, obtains the poly-(n-BMA-co-spiro-pyrans base of di-block copolymer containing spiropyran groupsEthyl-methyl acrylate)-b-polymethylacrylic acid dimethylamino ethyl ester, vacuum drying 24h at 45 DEG CFor subsequent use afterwards;
3) by step 2) block copolymer P (BMA-co-SPMA)-b-PDMAEMA of making is dissolved in THFIn, the ultrasonic polymer that makes dissolves completely, then deionized water is added drop-wise in polymer THF solution, withIn time, stirs, and continues to stir after deionized water adds, and the mixed solution obtaining is transferred to molecular cut offBe, in 3500 bag filter, in deionized water, to dialyse, change during this time fresh deionized water, after 2 days, obtainStable micella dispersion soln.
2. the di-block copolymer containing spiropyran groups that preparation method according to claim 1 obtainsPurposes, it is characterized in that: the micella dispersion soln that is 2.3mg/ml by the concentration of 5ml evenly drips and is coated inOn the scraps of paper, after water at normal temperature solvent volatilizees completely, again evenly drip and be coated with, repeat aforesaid operations, appliedThe film of 11.5mg micella; Ultraviolet light sees through the surface of the mould irradiation scraps of paper that are carved with word, applies the paper of micellaSheet demonstrates blue word, and blue font part can also be sent pink colour fluorescence.
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| CN106835319B (en) * | 2016-12-14 | 2019-08-20 | 天津工业大学 | A kind of preparation method of photochromic block copolymer |
| CN113416287B (en) * | 2021-06-17 | 2023-06-27 | 四川大学 | Block copolymer for photochromic and thermochromic intelligent window, 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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| CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
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| CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
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| Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation;Lei Zhang等;《Journal of Zhejiang University Science A》;20130707;第14卷(第7期);第504-513页 * |
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