CN103910838A - Preparation method and use of spiropyrane group-containing diblock copolymer - Google Patents
Preparation method and use of spiropyrane group-containing diblock copolymer Download PDFInfo
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- CN103910838A CN103910838A CN201410039513.3A CN201410039513A CN103910838A CN 103910838 A CN103910838 A CN 103910838A CN 201410039513 A CN201410039513 A CN 201410039513A CN 103910838 A CN103910838 A CN 103910838A
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Abstract
The invention discloses a preparation method and a use of a spiropyrane group-containing diblock copolymer. The preparation method comprises the following steps of 1, preparing a solid sample P(BMA-co-SPMA)-Br, 2, preparing the spiropyrane group-containing diblock copolymer P(BMA-co-SPMA)-b-PDMAEMA and 3, dissolving the spiropyrane group-containing diblock copolymer P(BMA-co-SPMA)-b-PDMAEMA in THF to obtain a stable micelle dispersed solution. The stable micelle dispersed solution uniformly coats a paper by dripping coating to form a film with 11.5mg of micelle, ultraviolet light goes through a mold engraved with letters and then irradiates the surface of the paper, the paper coated with the micelle displays blue letters, and the blue letter parts give out pink fluorescent light. The spiropyrane group-containing diblock copolymer has small pollution on the environment and is a green environmentally-friendly coating material.
Description
Technical field
The present invention relates to a kind of block polymer, especially relate to a kind of Preparation method and use of the di-block copolymer containing spiropyran groups.
Background technology
By the isomerization of photoinduction control photosensitive group, realize the switching over of fluorescence, this fluorescence regulates material to have important application value in fields such as false proof, information storage, photoswitch and bio-medical materials.Spiro-pyrans is a kind of important photosensitive group, is widely used in preparing the adjustable intelligent material of fluorescence.Spiro-pyrans is introduced in hydrophobic cavity, and the fluorescence of the merocyanine type isomer of spiro-pyrans significantly strengthens, by the isomerization reaction of photoinduction control spiropyran groups, with regard to the variation of controllable adjustment color and the switching over of fluorescence.[concrete visible Zhu M Q, Zhu L, Han J J, Wu W, Hurst J K, Li A D Q.J.Am.Chem.Soc., 2006, 128 (13): 4303-4309.Zhu L Y, Wu W W, Zhu Mi Q, Han J J, Hurst J K, Li A D Q.J.Am.Chem.Soc., 2007, 129 (12): 3524-3526.Zhu M Q, Zhang G F, LiC, Aldred M P, Chang E, Drezek R A, Li A D Q.J.Am.Chem.Soc., 2011, 133 (2): 365-372.Tian Z Y, Wu W W, Wan W, Li A D Q.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 Preparation method and use of the di-block copolymer containing spiropyran groups, prepare a kind of water-soluble polymers micella emulsion, by photosensitive group spiro-pyrans is introduced to the hydrophobic kernel of micella, significantly improve the fluorescence intensity of micella, by irradiating or close the isomerization of UV-light control spiropyran groups, the photochromic and fluorescent switch performance of reversible adjusting micella.This water-soluble emulsion is coated on paper, and after being dried, scraps of paper top coat, except having photochromic properties, sends stronger pink colour fluorescence, regulates the variation of coating color and the switching over of fluorescence by irradiating or closing UV-light.
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 joined in two dry neck bottles, get the initiator 2-isobutyl ethyl bromide of 0.12ml, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml toluene, join in two neck bottles, initiator 2-isobutyl ethyl bromide, the molar ratio of CuBr and part PMDETA remains on 1:1:1, the molar ratio of monomers B MA and spiro-pyrans base ethyl-methyl acrylate is between 1:1000～1000:1, initiator and BMA, the mol ratio of two kinds of monomer total amounts of SPMA is between 1000:1～1:1000, sealing, then bleed thaw cycles three times of liquid nitrogen freezing, two neck bottles are placed in after 90 ℃ of oil bath reaction 10h, open two neck bottles, and in liquid nitrogen cooling stopped reaction, add dilution with toluene product solution, after separating by neutral alumina chromatography column, collect and flow out solution, and precipitate in-5 ℃ of methyl alcohol of 10 times of volumes that flow out solution, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample P (BMA-co-SPMA)-Br, for subsequent use after vacuum-drying 24h at 45 ℃,
2) 0.50g initiator P (BMA-co-SPMA)-Br is joined in two dry neck bottles, the applying argon gas of bleeding circulation three times, measure 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 add 18 μ l part PMDETA and 8.4mg CuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, initiator P (BMA-co-SPMA)-Br, the molar ratio of CuCl and part PMDETA remains on 1:1:1, the mol ratio of initiator P (BMA-co-SPMA)-Br and monomer DMAEMA is between 1000:1～1:1000, two neck bottles are placed in to 40～120 ℃ of oil baths reaction, 0.5～24h to be placed in 90 ℃ of oil baths by two neck bottles and to react, after reaction finishes, open two neck bottles, cooling stopped reaction in liquid nitrogen, add dilution with toluene product solution, separate and remove catalyzer by alkali alumina post, collect and flow out solution, and precipitate in-5 ℃ of methyl alcohol of 10 times of volumes that flow out solution, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample, obtain poly-(n-BMA-co-spiro-pyrans base ethyl-methyl acrylate)-b-polymethyl acrylic acid dimethylamino ethyl ester (its English is abbreviated as P (BMA-co-SPMA)-b-PDMAEMA) of di-block copolymer containing spiropyran groups, for subsequent use after vacuum-drying 24h at 45 ℃,
3) by step 2) segmented copolymer P (BMA-co-SPMA)-b-PDMAEMA of making is dissolved in THF, the ultrasonic polymkeric substance that makes dissolves completely, then deionized water is added drop-wise in polymkeric substance THF solution, stir simultaneously, after deionized water adds, continue to stir, it is in 3500 dialysis tubing that the mixing solutions obtaining is transferred to molecular weight cut-off, in deionized water, dialyses, change during this time fresh deionized water, after 2 days, obtain stable micella dispersion soln; Concrete reaction formula 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, after water at normal temperature solvent volatilizees completely, again evenly drips and is coated with, and repeats aforesaid operations, obtains applying the film of 11.5mg micella; UV-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 beneficial effect that the present invention has is:
1) polymeric film has the photochromic and adjustable performance of fluorescence simultaneously, is a kind of anti-fake material with dual recognition feature.
2) control the isomerization of spiro-pyrans a kind of component, just can regulate and control two kinds of stimuli responsive features such as photochromic and fluorescence intensity of micella simultaneously.
3) regulate micella colour-change and fluorescent switch by irradiating or closing UV-light, easy to operate, can repeatedly use, stability is higher, and the speed of response is very fast.
4) the synthetic polymkeric substance of the present invention obtains micella dispersion soln through self-assembly, to the less pollution of environment, is a kind of coated material of environmental protection.
Accompanying drawing explanation
Fig. 1 is reaction formula of the present invention and micelle formation schematic diagram.
Fig. 2 is the hydrogen-nuclear magnetic spectrogram of polymer P (BMA-co-SPMA)-Br in chloroformic solution of deuteration that the present invention makes.
Fig. 3 is the hydrogen-nuclear magnetic spectrogram of block polymer P (BMA-co-SPMA)-b-PDMAEMA in chloroformic solution of deuteration that the present invention makes.
Fig. 4 is the transmission electron microscope photo of block polymer P (BMA-co-SPMA)-b-PDMAEMA self-assembled micelle of making of the present invention.
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 ultra-violet lamp sees through hollow out " NANO " printed words irradiates the scraps of paper surface that applies micella, and scraps of paper surface demonstrates blueness " NANO " printed words, and " NANO " printed words part demonstrates pink colour fluorescence (B) under UV-light.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, person skilled in art can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
1. block polymer is synthetic
The CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate (SPMA) and 0.14g is joined in two dry neck bottles, measure the 2-isobutyl ethyl bromide of 0.12ml with syringe, 0.21ml part PMDETA, the monomers B MA of 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 freezing, two neck bottles are placed in after 90 ℃ of oil bath reaction 10h, open two neck bottles, and in liquid nitrogen cooling stopped reaction, add a small amount of dilution with toluene product solution, after separating by neutral alumina chromatography column, collect and flow out solution, and precipitate in the methyl alcohol (5 ℃) of 10 times of volumes, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample P (BMA-co-SPMA)-Br, for subsequent use after vacuum-drying 24h at 45 ℃, structure as shown in Figure 2.
0.50g macromole evocating agent P (BMA-co-SPMA)-Br polymkeric substance is joined in two dry neck bottles, the applying argon gas of bleeding circulation three times, measure 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 fast 18 μ l part PMDETA and 8.4mg CuCl, sealing, in liquid nitrogen, the freezing thaw cycles three times of bleeding, is placed in 90 ℃ of oil baths by two neck bottles and reacts.After reaction finishes, open two neck bottles, cooling stopped reaction in liquid nitrogen, add a small amount of dilution with toluene product solution, separate and remove catalyzer by alkali alumina post, collect and flow out solution, precipitation in the methyl alcohol (5 ℃) of 10 times of volumes, 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 di-block copolymer P (the BMA-co-SPMA)-b-PDMAEMA containing spiropyran groups, for subsequent use after vacuum-drying 24h at 45 ℃, structure as shown in Figure 3.
2. the preparation of block polymer micelle
34mg segmented copolymer P (BMA-co-SPMA)-b-PDMAEMA is dissolved in the THF of 0.6ml, the ultrasonic polymkeric substance that makes dissolves completely, then 15ml deionized water is slowly added drop-wise in the THF solution of polymkeric substance, vigorous stirring simultaneously, after adding, continues deionized water to stir 12h, the mixing solutions obtaining is transferred to (molecular weight cut-off 3500) in dialysis tubing, in deionized water, dialyse 2 days, change during this time fresh deionized water, after 2 days, obtain stable micella dispersion soln.
As shown in Figure 4, be the transmission electron microscope photo of block polymer P (BMA-co-SPMA)-b-PDMAEMA self-assembled micelle of making of the present invention.
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 on the scraps of paper, after water at normal temperature solvent volatilizees completely, again evenly drips and is coated with, and repeats aforesaid operations, obtains applying the film of 11.5mg micella; UV-light sees through the surface of the mould irradiation scraps of paper that are carved with " NANO " printed words, the scraps of paper that apply micella demonstrate the printed words of blueness " NANO ", as shown in Fig. 5 it (II), under UV-light, blue 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 step of the method is as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate and 0.14g is joined in two dry neck bottles, get the initiator 2-isobutyl ethyl bromide of 0.12ml, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml toluene, join in two neck bottles, initiator 2-isobutyl ethyl bromide, the molar ratio of CuBr and part PMDETA remains on 1:1:1, the molar ratio of monomers B MA and spiro-pyrans base ethyl-methyl acrylate is between 1:1000～1000:1, initiator and BMA, the mol ratio of two kinds of monomer total amounts of SPMA is between 1000:1～1:1000, sealing, then bleed thaw cycles three times of liquid nitrogen freezing, two neck bottles are placed in to 90
oafter C oil bath reaction 10h, open two neck bottles, and in liquid nitrogen cooling stopped reaction, add dilution with toluene product solution, after separating by neutral alumina chromatography column, collect and flow out solution, and flow out solution 10 times of volumes-5
oin C methyl alcohol, precipitate, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitating, this operation repeats twice, and suction filtration is collected solid sample P (BMA-
co-SPMA)-Br, 45
ofor subsequent use after vacuum-drying 24h under C,
2) by 0.50g initiator P (BMA-
co-SPMA)-Br joins in two dry neck bottles, and the applying argon gas of bleeding circulation three times, measures 1.0ml monomer DMAEMA and 2.8ml toluene with syringe, and joins and fill P (BMA-
co-SPMA) in the two neck bottles of-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 18 μ l part PMDETA and 8.4mg CuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, initiator P (BMA-
co-SPMA) molar ratio of-Br, CuCl and part PMDETA remains on 1:1:1, initiator P (BMA-
co-SPMA) mol ratio of-Br and monomer DMAEMA between 1000:1～1:1000, two neck bottles are placed in to 40～120
oc oil bath reaction 0.5～24h is placed in 90 by two neck bottles
oin C oil bath, react; After reaction finishes, open two neck bottles, cooling stopped reaction in liquid nitrogen, adds dilution with toluene product solution, is separated and is removed catalyzer by alkali alumina post, collect and flow out solution, and flow out solution 10 times of volumes-5
oin C methyl alcohol, precipitate, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample, obtains poly-(n-BMA-co-spiro-pyrans base ethyl-methyl acrylate)-b-polymethyl acrylic acid dimethylamino ethyl ester of di-block copolymer containing spiropyran groups, 45
ofor subsequent use after vacuum-drying 24h under C;
3) by step 2) the segmented copolymer P (BMA-that makes
co-SPMA)-
b-PDMAEMA is dissolved in THF, the ultrasonic polymkeric substance that makes dissolves completely, then deionized water is added drop-wise in polymkeric substance THF solution, stir simultaneously, after deionized water adds, continue to stir, it is in 3500 dialysis tubing that the mixing solutions obtaining is transferred to molecular weight cut-off, in deionized water, dialyses, change during this time fresh deionized water, after 2 days, obtain stable micella dispersion soln;
Concrete reaction formula as shown in Figure 1.
2. the purposes of a kind of di-block copolymer containing spiropyran groups according to claim 1, it is characterized in that: the micella dispersion soln that is 2.3mg/ml by the concentration of 5ml evenly drips and is coated on the scraps of paper, after water at normal temperature solvent volatilizees completely, again evenly drip and be coated with, repeat aforesaid operations, obtain applying the film of 11.5mg micella; UV-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.
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| 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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Cited By (6)
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| CN106835319A (en) * | 2016-12-14 | 2017-06-13 | 天津工业大学 | A kind of preparation method of photochromic block copolymer |
| CN106835319B (en) * | 2016-12-14 | 2019-08-20 | 天津工业大学 | A kind of preparation method of photochromic block copolymer |
| CN113416287A (en) * | 2021-06-17 | 2021-09-21 | 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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