CN103881038B - Containing the Preparation method and use of the triblock copolymer of spiropyran groups - Google Patents
Containing the Preparation method and use of the triblock copolymer of spiropyran groups Download PDFInfo
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- CN103881038B CN103881038B CN201410039064.2A CN201410039064A CN103881038B CN 103881038 B CN103881038 B CN 103881038B CN 201410039064 A CN201410039064 A CN 201410039064A CN 103881038 B CN103881038 B CN 103881038B
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Abstract
The invention discloses a kind of Preparation method and use of the triblock copolymer containing spiropyran groups.The step of the method is as follows: step 1) prepares solid sample Br-P (BMA-<i>co</iGrea tT.GreaT.GT-SPMA)-Br; Step 2) obtain triblock copolymer PDMAEMA-<i>b</iG reatT.GreaT.GT-P (BMA-<i>co</iGrea the tT.GreaT.GT-SPMA)-<i>b</iGreatT.Gr eaT.GT-PDMAEMA containing spiropyran groups; 10mg polymer P DMAEMA-<i>b</iGr eatT.GreaT.GT-P (BMA-<i>co</iGrea tT.GreaT.GT-SPMA)-<i>b</iGreatT.Gr eaT.GT-PDMAEMA is dissolved in DMF and obtains stable micella dispersion soln by step 3).Being dripped by polyacrylic acid dispersion soln containing micella is coated on quartz plate, obtains the polyacrylic film sample containing micella.The present invention, to the less pollution of environment, is a kind of security coating material of environmental protection.
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 triblock copolymer containing spiropyran groups.
Background technology
Controlled the isomerization of photosensitive group by photoinduction, 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.Introduced by spiro-pyrans in hydrophobic cavity, the fluorescence of the merocyanine type isomer of spiro-pyrans significantly strengthens, and is controlled the isomerization reaction of spiropyran groups, with regard to the change of controllable adjustment color and the switching over of fluorescence by photoinduction.There is zwitter-ion and neutral quinoid structure in the merocyanine type body structure of spiro-pyrans in addition in nonpolar environment, along with the change of temperature, merocyanine type body transforms between multiple isomer, color also changes along with temperature, and these features can be applicable to the anti-fake material field of Multiple recognition feature.[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.ShiraishiY, MiyamotoR, HiraiT.Org.Lett., 2009,11 (7): 1571-1574.]
Summary of the invention
In order to develop the anti-fake material with triple recognition feature, the object of the present invention is to provide a kind of Preparation method and use of the triblock copolymer containing spiropyran groups, prepare a kind of water-soluble polymers micelle emulsion, by photosensitive group spiro-pyrans being introduced the hydrophobic inner core of micella, significantly improve the fluorescence intensity of micella, by irradiating and closing the isomerization that UV-light controls spiro-pyrans, regulate the performances such as the photochromic and fluorescent switch of micella.Selection polyacrylic acid is filmogen, water-soluble micella is dispersed in the polyacrylic acid aqueous solution, improve the concentration of micella, polyacrylic acid solution containing micella is coated on quartz plate, form polyacrylic film after drying, film, except having photochromic performance, can also send stronger pink colour fluorescence, controlled the isomerization of spiro-pyrans by UV-light and visible ray, the switching over of film fluorescence can be regulated.
The technical solution used in the present invention is:
One, containing a preparation method for the triblock copolymer of spiropyran groups, the step of the method is as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethylmethyl acrylate and 0.14g is joined in two dry neck bottles, get the initiator B MB of 0.20g, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml methyl-phenoxide, join in two neck bottles, initiator B MB, the molar ratio of CuBr and part PMDETA remains on 1:1:1, the molar ratio of monomers B MA and SPMA is between 1:1000 ~ 1000:1, initiator and BMA, the mol ratio of SPMA two kinds of monomer total amounts is between 1000:1 ~ 1:1000, sealing, then liquid nitrogen freezing is bled thaw cycles three times, after two neck bottles being placed in 90 DEG C of oil bath reaction 40min, open two neck bottles, and stopped reaction is cooled in liquid nitrogen, add dilution with toluene reaction mixture, after being separated by neutral alumina chromatography column, collect and flow out solution, and precipitate in-5 DEG C of methyl alcohol of 10 times of volumes, collected by suction deposit sample, and be again dissolved in toluene, precipitate in methyl alcohol, this operation repetition twice, collected by suction solid sample Br-P (BMA-co-SPMA)-Br, for subsequent use after vacuum-drying 24h at 45 DEG C,
2) 0.55g polymer B r-P (BMA-co-SPMA)-Br is joined in two dry neck bottles, applying argon gas of bleeding circulates three times, 2.4ml monomer DMAEMA and 1.8ml toluene is measured with syringe, and join and fill in the two neck bottles of Br-P (BMA-co-SPMA)-Br, sealing, after thing to be polymerized dissolves, the freezing thaw cycles three times of bleeding in liquid nitrogen, initiator B r-P (BMA-co-SPMA)-Br, the molar ratio of CuCl and part PMDETA remains on 1:1:1, the mol ratio of macromole evocating agent P (BMA-co-SPMA)-Br and monomer DMAEMA is between 1000:1 ~ 1:1000, then open two neck bottles and pass into argon gas, now add 76 μ l part PMDETA and 37mgCuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, two neck bottles are placed in 70 DEG C of oil baths and react 20h, after reaction terminates, open two neck bottles, stopped reaction is cooled in liquid nitrogen, add dilution with toluene reaction mixture, removing catalyzer is separated by alkali alumina post, collect and flow out solution, precipitate in-5 DEG C of methyl alcohol of 10 times of volumes, collected by suction deposit sample, and be again dissolved in toluene, precipitate in methyl alcohol, this operation repetition twice, collected by suction solid sample, obtain poly-(n-BMA-co-spiro-pyrans base the ethylmethyl acrylate)-b-polymethyl acrylic acid dimethylamino ethyl ester (its English is abbreviated as PDMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA) of triblock copolymer polymethyl acrylic acid dimethylamino ethyl ester-b-containing spiropyran groups, for subsequent use after vacuum-drying 24h at 45 DEG C,
3) 10mg polymer P DMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA is dissolved in the DMF of 1ml, ultrasonic 15min makes it dissolve completely, then 9ml deionized water is slowly added drop-wise in the DMF solution of polymkeric substance, stir simultaneously, continue after deionized water adds to stir 12h, then by the dialysis tubing of maximum molecular weight cut-off 3500 that obtains, dialyse 2 days in deionized water, period changes fresh deionized water, obtains stable micella dispersion soln after 2 days;
Concrete reaction formula and micelle formation schematic diagram are as shown in Figure 1.
Two, a kind of purposes of the triblock copolymer containing spiropyran groups
After micellar solution lyophilize, obtain white powder sample, join in deionized water, stir simultaneously, be made into micella Aqueous dispersions solution, by the polyacrylic acid aqueous solution of mass percent concentration 25%, polyacrylic acid weight-average molecular weight 2.4 × 10
5slowly be added drop-wise in micellar solution, constantly stir makes micellar solution and polyacrylic acid solution mix simultaneously, dropwise rear continuation and stir 30min, then being dripped by the polyacrylic acid dispersion soln containing micella is coated on quartz plate, after the complete volatile dry of solvent, obtain the polyacrylic film sample containing micella.
The beneficial effect that the present invention has is:
1) polymeric film have simultaneously photochromic, fluorescence is adjustable and the performance of thermochromism, is a kind of anti-fake material with triple recognition feature.
2) control the isomerization of spiro-pyrans a kind of component, just can regulate and control three kinds of stimuli responsive features such as photochromic, the fluorescence intensity of micella and thermochromism 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) polymkeric substance of the present invention's synthesis obtains micella 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 B r-P (BMA-co-SPMA)-Br in chloroformic solution of deuteration that the present invention obtains.
Fig. 3 is the hydrogen-nuclear magnetic spectrogram of block polymer PDMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA in chloroformic solution of deuteration that the present invention obtains.
Fig. 4 is the transmission electron microscope photo of block polymer PDMAEMA-b-P (the BMA-co-SPMA)-b-PDMAEMA self-assembled micelle that the present invention obtains.
Fig. 5 is the photo that the polyacrylic film comprising polymer micelle that the present invention obtains is subject to before and after UV-irradiation.The overcover irradiate surface of UV light permeability hollow out, the position be irradiated to becomes blueness from colourless, and under ultraviolet lamp, variable color position sends strong pink colour fluorescence.
Fig. 6 is the polyacrylic film the comprising polymer micelle photo at different temperatures that obtains of the present invention and the mechanism of thermochromism thereof.When 35 DEG C, film is aobvious red, and when 45, a DEG C film shows pink colour, and when 55 DEG C, film shows lightpink.
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 according to the content of foregoing invention to the present invention.
1. the synthesis of block polymer
The CuBr of 0.26g monomer spiro-pyrans base ethylmethyl acrylate (SPMA) and 0.14g is joined in two dry neck bottles, the initiator B MB of 0.20g is measured with syringe, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml methyl-phenoxide, join and fill in the two neck bottles of CuBr, sealing, then liquid nitrogen freezing is bled thaw cycles three times, after two neck bottles being placed in 90 DEG C of oil bath reaction 40min, open two neck bottles, and stopped reaction is cooled in liquid nitrogen, add a small amount of dilution with toluene reaction mixture, after being separated by neutral alumina chromatography column, collect and flow out solution, and precipitate in the methyl alcohol (-5 DEG C) of 10 times of volumes, collected by suction deposit sample, and be again dissolved in toluene, precipitate in methyl alcohol, this operation repetition twice, collected by suction solid sample Br-P (BMA-co-SPMA)-Br, for subsequent use after vacuum-drying 24h at 45 DEG C, structure as shown in Figure 2.
0.55g polymer B r-P (BMA-co-SPMA)-Br is joined in two dry neck bottles, applying argon gas of bleeding circulates three times, 2.4ml monomer DMAEMA and 1.8ml toluene is measured with syringe, and join and fill in the two neck bottles of Br-P (BMA-co-SPMA)-Br, sealing, after thing to be polymerized dissolves, the freezing thaw cycles three times of bleeding in liquid nitrogen.Then open two neck bottles and pass into argon gas, now adding 76 μ l part PMDETA and 37mgCuCl fast, sealing, in liquid nitrogen, two neck bottles are placed in 70 DEG C of oil baths and react 20h by the freezing thaw cycles three times of bleeding.After reaction terminates, open two neck bottles, stopped reaction is cooled in liquid nitrogen, add a small amount of dilution with toluene reaction mixture, removing catalyzer is separated by alkali alumina post, collect and flow out solution, precipitation in the methyl alcohol (-5 DEG C) of 10 times of volumes, collected by suction deposit sample, and be again dissolved in toluene, precipitate in methyl alcohol, this operates repetition twice, collected by suction solid sample, obtains di-block copolymer PDMAEMA-b-P (the BMA-co-SPMA)-b-PDMAEMA containing spiropyran groups, for subsequent use after vacuum-drying 24h at 45 DEG C, structure as shown in Figure 3.
2. the preparation of block polymer micelle
10mg polymer P DMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA is dissolved in the DMF of 1ml, ultrasonic 15min makes it dissolve completely, then 9ml deionized water is slowly added drop-wise in the DMF solution of polymkeric substance, vigorous stirring simultaneously, continue after deionized water adds to stir 12h, then the mixing solutions obtained is transferred to (maximum molecular weight cut-off 3500) in dialysis tubing, dialyse 2 days in deionized water, period changes fresh deionized water at set intervals, obtains stable micella dispersion soln after 2 days.
As shown in Figure 4, be the transmission electron microscope photo of block polymer PDMAEMA-b-P (the BMA-co-SPMA)-b-PDMAEMA self-assembled micelle that the present invention obtains.
3. the preparation of the polyacrylic film containing polymer micelle
After micellar solution lyophilize, obtain white powder sample, the powdered sample taking 16.7mg joins in 8.5ml deionized water, and vigorous stirring, is made into certain density micella Aqueous dispersions solution simultaneously.By the polyacrylic acid aqueous solution (the polyacrylic acid weight-average molecular weight 2.4 × 10 of 0.10g mass percent concentration 25%
5), be slowly added drop-wise in the micellar solution of 0.5ml, constantly stir simultaneously and micellar solution and polyacrylic acid solution are mixed, dropwise rear continuation and stir 30min.Then being dripped by the polyacrylic acid dispersion soln containing micella is coated on quartz plate, after the complete volatile dry of solvent, obtains the polyacrylic film sample containing micella.
Fig. 5 is the photo that the polyacrylic film comprising polymer micelle that the present invention obtains is subject to before and after UV-irradiation.The overcover irradiate surface of UV light permeability hollow out, the position be irradiated to becomes blueness from colourless, and under ultraviolet lamp, variable color position sends strong pink colour fluorescence.
Fig. 6 is the polyacrylic film the comprising polymer micelle photo at different temperatures that obtains of the present invention and the mechanism of thermochromism thereof.When 35 DEG C, film is aobvious red, and when 45 DEG C, film shows pink colour, and during 55oC, film shows lightpink.
Claims (2)
1., containing a preparation method for the triblock copolymer of spiropyran groups, it is characterized in that, the step of the method is as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethylmethyl acrylate and 0.14g is joined in two dry neck bottles, get the initiator B MPB of 0.20g, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml methyl-phenoxide, join in two neck bottles, initiator B MPB, the molar ratio of CuBr and part PMDETA remains on 1:1:1, the molar ratio of monomers B MA and SPMA is between 1:1000 ~ 1000:1, initiator and BMA, the mol ratio of SPMA two kinds of monomer total amounts is between 1000:1 ~ 1:1000, sealing, then liquid nitrogen freezing is bled thaw cycles three times, two neck bottles are placed in 90
oafter C oil bath reaction 40min, open two neck bottles, and cool stopped reaction in liquid nitrogen, add dilution with toluene reaction mixture, after being separated by neutral alumina chromatography column, collecting and flow out solution, and at-5 of 10 times of volumes
oprecipitate in C methyl alcohol, collected by suction deposit sample, and be again dissolved in toluene, precipitate in methyl alcohol, this operates repetition twice, collected by suction solid sample Br-P (BMA-
co-SPMA)-Br, 45
ofor subsequent use after vacuum-drying 24h under C,
2) by 0.55g polymer B r-P (BMA-
co-SPMA)-Br joins in two dry neck bottles, and applying argon gas of bleeding circulates three times, measures 2.4ml monomer DMAEMA and 1.8ml toluene with syringe, and joins and fill Br-P (BMA-
co-SPMA)-Br two neck bottles in, sealing, after thing to be polymerized dissolves, the freezing thaw cycles three times of bleeding in liquid nitrogen, initiator B r-P (BMA-
co-SPMA) molar ratio of-Br, CuCl and part PMDETA remains on 1:1:1, macromole evocating agent P (BMA-
co-SPMA) mol ratio of-Br and monomer DMAEMA is between 1000:1 ~ 1:1000, and then open two neck bottles and pass into argon gas, now adding 76 μ l part PMDETA and 37mgCuCl, sealing, in liquid nitrogen, two neck bottles are placed in 70 by the freezing thaw cycles three times of bleeding
o20h is reacted in C oil bath; After reaction terminates, open two neck bottles, in liquid nitrogen, cool stopped reaction, add dilution with toluene reaction mixture, be separated removing catalyzer by alkali alumina post, collect and flow out solution, at-5 of 10 times of volumes
oprecipitate in C methyl alcohol, collected by suction deposit sample, and be again dissolved in toluene, precipitate in methyl alcohol, this operation repetition twice, collected by suction solid sample, obtains poly-(n-BMA-co-spiro-pyrans base the ethylmethyl acrylate)-b-polymethyl acrylic acid dimethylamino ethyl ester of triblock copolymer polymethyl acrylic acid dimethylamino ethyl ester-b-containing spiropyran groups, 45
ofor subsequent use after vacuum-drying 24h under C;
3) by 10mg polymer P DMAEMA-
b-P (BMA-
co-SPMA)-
b-PDMAEMA is dissolved in the DMF of 1ml, ultrasonic 15min makes it dissolve completely, then 9ml deionized water is slowly added drop-wise in the DMF solution of polymkeric substance, stir simultaneously, continue after deionized water adds to stir 12h, then by the dialysis tubing of maximum molecular weight cut-off 3500 that obtains, dialyse 2 days in deionized water, period changes fresh deionized water, obtains stable micella dispersion soln after 2 days;
Described initiator B MPB is Isosorbide-5-Nitrae-(2-bromo-2-isobutyl acyl-oxygen) benzene, and English is the abbreviation of Isosorbide-5-Nitrae-(2-bromo-2-methylpropionato) benzene.
2. the purposes of a kind of triblock copolymer containing spiropyran groups according to claim 1, it is characterized in that: after micellar solution lyophilize, obtain white powder sample, join in deionized water, stir simultaneously, be made into micella Aqueous dispersions solution, by the polyacrylic acid aqueous solution of mass percent concentration 25%, polyacrylic acid weight-average molecular weight 2.4 × 10
5slowly be added drop-wise in micellar solution, constantly stir makes micellar solution and polyacrylic acid solution mix simultaneously, dropwise rear continuation and stir 30min, then being dripped by the polyacrylic acid dispersion soln containing micella is coated on quartz plate, after the complete volatile dry of solvent, obtain the polyacrylic film sample containing micella.
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Non-Patent Citations (2)
| Title |
|---|
| Multiresponsive spiropyran-based copolymers synthesized by atom transfer radical polymerization;Demetra S.Achilleos et al;《Macromolecules》;20100812;第43卷;p7073-7081 * |
| 含螺吡喃嵌段聚合物的合成及其光敏性能研究;张磊等;《2013年全国高分子学术论文报告会论文摘要集——主题F：功能高分子》;20131012;p366 * |
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