CN102627783B - Crosslinked polyethylene pyrrolidone-base fluorescent composite thin film and preparation method thereof - Google Patents
Crosslinked polyethylene pyrrolidone-base fluorescent composite thin film and preparation method thereof Download PDFInfo
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- CN102627783B CN102627783B CN201210119277.7A CN201210119277A CN102627783B CN 102627783 B CN102627783 B CN 102627783B CN 201210119277 A CN201210119277 A CN 201210119277A CN 102627783 B CN102627783 B CN 102627783B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000010409 thin film Substances 0.000 title abstract 8
- 229920003020 cross-linked polyethylene Polymers 0.000 title abstract 3
- 239000004703 cross-linked polyethylene Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 33
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 33
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 7
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 7
- 229920004933 Terylene® Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 150000002790 naphthalenes Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- -1 polyethylene pyrrolidone Polymers 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000008961 swelling Effects 0.000 abstract description 5
- 239000003814 drug Substances 0.000 description 6
- 238000000053 physical method Methods 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- MURGITYSBWUQTI-UHFFFAOYSA-N fluorescin Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC=C(O)C=C2OC2=CC(O)=CC=C21 MURGITYSBWUQTI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004950 naphthalene Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a crosslinked polyethylene pyrrolidone-base fluorescent composite thin film and a preparation method thereof and belongs to the technical field of preparation of fluorescent polymeric membranes. By using the special structure of a side chain of polyethylene pyrrolidone, the polyethylene pyrrolidone is subjected to self-crosslinking under certain reaction conditions; and a polycyclic aromatic dye is simultaneously added into the reaction solution, and in a self-crosslinking process of the polyethylene pyrrolidone, the dye is dispersed and fixed in the polyethylene pyrrolidone to obtain the crosslinked polyethylene pyrrolidone-base fluorescent composite thin film. The fluorescent composite thin film prepared by the method has good swelling capacity and has high stability in a plurality of solvents; the thin film also has good water solubility and biocompatibility, so the thin film has wide application prospect in aspects, such as biomedicine, life sciences, and pharmacology; and furthermore, the thin film contains polycyclic aromatic fluorescent groups with excellent optical property, so that the optical property of the thin film is high in stability.
Description
Technical field
The invention belongs to fluorescence polymer membrane preparation technology field, particularly a kind of cross-linked polyvinylpyrrolidone base fluorescence laminated film and preparation method thereof.
Background technology
Therefore polymeric membrane has special three-dimensional net structure, is commonly used in the fixing matrix of fluorescent small molecule.The fixing means of fluorescent small molecule in polymeric membrane can be divided into two large classes: physical method and chemical process.
Physics fixing means is first fluorescent small molecule to be entrained in macromolecular solution by a certain percentage, then by whirl coating, is dried, and obtains the composite membrane of polymer embedding.And chemically fixedly time, be first fluorescent small molecule to be attached to chemical bond form on the macromolecular chain that is easy to film forming, then by spin coating or curtain coating, make polymer at solid substrate surface filming, thereby obtain fluorescence polymer film.This class fluorescence polymer film also can obtain via other approach, for example, first with chemical synthesis, obtain polymerizable fluorescent monomer, then by itself and non-fluorescent monomer copolymerization, finally with the fluorescent polymer obtaining, prepares fluorescence membrane.Certainly, also can be in the surface grafting fluorescent small molecule of existing polymeric membrane, thus obtain fluorescence polymer film.Although physical method is simple and cost is low, but the problem that the fluorescence polymer film of preparing with physical method all exists fluorescence molecule to leak, while therefore using in solution, resulting signal is the composite signal of combined and solubilised state, cause signal distortion, affect the quality of institute's obtaining information.In addition, the work-ing life of this class fluorescence membrane is also limited.On the contrary, the fluorescence polymer film chemically obtaining has overcome the defect that physical method causes substantially.But chemical process, due to shortcomings such as complicated operation, side reaction are many and cost is higher, does not also get the nod in large-scale commercial production.
Polyvinylpyrrolidone (PVP) is a kind of high molecular weight water soluble polymer with many special propertys.Due to its good water-soluble and complexing action, and harmless, can be used as finings.But water-soluble due to PVP, can not reuse part PVP, and then has improved use cost.Cross-linked pvp, when guaranteeing its complex ability, has improved recycle ability.
In preparing the method for cross-linked pvp, mainly comprise radiation crosslinking method, optical cross-linking method and chemical crosslink technique etc.Because cross-linked pvp is water insoluble, strong acid, highly basic and various organic solvent, only in solvent, have swelling in various degree.For cross-linked pvp different swelling ability and adsorptive power, can cross-linked pvp be divided into by the difference of mode of appearance: soft gel, white powder and porous granule.For different patterns and performance, can be applied to various fields.
Cross-linked pvp can be used as finings and the stablizer of beer and fruit juice in wine brewing, drink industry.Cross-linked pvp has good physiology inertia, biocompatibility and good complex performance, one is come out and just at field of medicaments, receive much attention, and cross-linked pvp is widely applied in the whole world at present.Its useful as drug disintegrating agent, slow releasing carrier of medication and hemodialysis membrane etc.Cross-linked pvp that can height swelling in water can be used as the disintegrating agent of tablet or capsule.The medicine that contains this type of cross-linked pvp runs into after water, because cross-linked pvp water swellability is very large, causes very large pressure in medicament, thereby makes the rapid disintegration of medicament, respond well.
In numerous fluorescent chemicalses, condensed-nuclei aromatics is the arene compound that a class has intense fluorescence, has large conjugated pi system.Derivative has excellent chemistry, light and heat chemical stability, light from visible region to infrared region is had to very strong absorption, be the special molectronics material of a class performance, aspect laserable material, biological fluorescent labeling molecule, liquid crystal display material, electroluminescent device, photoreceptor and solar cell, be widely used.Wherein, electron conjugated degree and molecule same flatness in Nai, perylene and terylene equimolecular are very big, therefore have very high fluorescence quantum yield.Because this compounds fluorescence is very strong, to their property research and application exploration, be therefore all the problem of Showed Very Brisk all the time.
Summary of the invention
The object of the invention is, in order to prepare the fluorescence membrane of high optical property, to be used for improving in conventional fluorescent film the shortcoming such as fluorophor easily runs off, quantum transformation efficiency is on the low side, technology energy consumption is large, throughput is low.The prepared fluorescence membrane of the present invention has stable fluorescence property, and that its preparation process has is simple to operate, production energy consumption is low, be easy to the advantages such as mass production.
The prepared fluorescence laminated film of the present invention utilizes the special construction of polyvinylpyrrolidone side chain, make its certain reaction conditions issue be conigenous crosslinked; In reaction soln, add condensed-nuclei aromatics dyestuff simultaneously, in polyvinylpyrrolidone self-crosslinking process, dyestuff disperseed and be fixed therein, obtain cross-linked polyvinylpyrrolidone base fluorescence laminated film.
The preparation method of described cross-linked polyvinylpyrrolidone base fluorescence laminated film, its concrete steps are:
(1) under ice-water bath churned mechanically condition, the polyvinylpyrrolidone of 0.03-1.5g is dissolved in the ethanol and acetone mixed solvent that 30-150ml volume ratio is 0.1-20, stirring velocity is 800-1000r/min, and churning time is 20-50min; Then at room temperature stir 20-50min; The last condensed-nuclei aromatics dyestuff that adds 5mg-0.5g under ultrasound condition, continues ultrasonic dispersion 20-50min;
(2) mixing solutions step (1) being made is transferred in autoclave, gets rid of oxygen, at 120-180 ℃ of temperature, reacts 1-40h;
(3) reaction is cooled to room temperature after finishing, and film is taken out and use second alcohol and water to clean, and then 20-60 ℃ of vacuum drying 1-24h, obtains cross-linked polyvinylpyrrolidone base fluorescence laminated film.
The molecular weight of described polyvinylpyrrolidone is 17k-90k.
Described condensed-nuclei aromatics dyestuff is Nai, perylene, terylene or the derivative of naphthalene derivatives, perylene, the derivative of terylene.
The cross-linked polyvinylpyrrolidone base fluorescence laminated film smooth surface that step (3) obtains, color even, fluorescence property is stable.
Compared with prior art, tool has the following advantages in the present invention:
1, PVP has the good water-soluble while in organic solvent, also to have good solvability, makes film under all kinds of SOLVENTS environment, have good consistency, has improved the Application Areas scope of film.And after crosslinking reaction occurs PVP, make the stability in the solvent of film also obtain improving significantly.Make work that film can be stable in liquid phase environment improve the application performance of film.
2, PVP has good biocompatibility, makes film, in living things system, biological rejection obtained to alleviation.The possibility of configuration aspects is provided for be applied to organism with rear film.The selected Shi of film fluorophor perylene class fluorescent chemicals.Because the wavelength of transmitted light of this compounds will be longer than the emission wavelength of the fluorescin that organism self has, so film when being applied to organism, has avoided coming from the impact of organism self.
3, prepared fluorescence laminated film, when retaining the simple advantage of traditional preparation method's technique, has overcome in conventional physical method the shortcomings such as fluorophor leakage; Meanwhile, the utilization ratio that has improved solvent has reduced production cost.
In sum, fluorescence laminated film prepared by the present invention has good swelling ability, shows satisfactory stability in multi-solvents; This film has good water-soluble and biocompatibility, so it has broad application prospects at aspects such as biomedicine, life science and pharmacology; Meanwhile, in film, contain the condensed-nuclei aromatics fluorophor of excellent optical performance, make the optical property of film there is satisfactory stability.
Accompanying drawing explanation:
The anhydride ester derivs structure iron of Fig. 1 condensed-nuclei aromatics dyestuff Nai, perylene and terylene.
The photo of the cross-linked polyvinylpyrrolidone base fluorescence laminated film that Fig. 2 embodiment 1 makes.
Ultraviolet-fluorescence spectrum figure of the cross-linked polyvinylpyrrolidone base fluorescence laminated film that Fig. 3 embodiment 1 makes.
The stereoscan photograph of the cross-linked polyvinylpyrrolidone base fluorescence laminated film that Fig. 4 embodiment 1 makes.
Fig. 5 is the reaction principle figure of embodiment 1.
Embodiment
Embodiment 1
1. it is that in 0.1 ethanol and acetone mixed solvent, stirring velocity is 800r/min that the polyvinylpyrrolidone that is 40k-50k by 0.03g molecular weight under ice-water bath churned mechanically condition is dissolved in 100ml volume ratio, and churning time is 30min; Then at room temperature stir 30min; The last 0.01g perylene acid anhydride that adds under ultrasound condition, continues ultrasonic dispersion 30min;
2. mixing solutions step 1 being made is transferred in autoclave, gets rid of oxygen, at 165 ℃ of temperature, reacts 30h;
3. reaction is cooled to room temperature after finishing, and film is taken out and use second alcohol and water to clean 3 times, and then 45 ℃ of vacuum drying 24h, obtain cross-linked polyvinylpyrrolidone base fluorescence laminated film.
The cross-linked polyvinylpyrrolidone base fluorescence laminated film smooth surface that step (3) obtains, color even, fluorescence property is stable, and emission wavelength is 620nm.
Embodiment 2
1. it is that in 0.1 ethanol and acetone mixed solvent, stirring velocity is 800r/min that the polyvinylpyrrolidone that is 17k by 0.03g molecular weight under ice-water bath churned mechanically condition is dissolved in 100ml volume ratio, and churning time is 30min; Then at room temperature stir 30min; The last 0.01g perylene acid anhydride that adds under ultrasound condition, continues ultrasonic dispersion 30min;
2. mixing solutions step 1 being made is transferred in autoclave, gets rid of oxygen, at 165 ℃ of temperature, reacts 30h;
3. reaction is cooled to room temperature after finishing, and film is taken out and use second alcohol and water to clean 3 times, and then 45 ℃ of vacuum drying 24h, obtain cross-linked polyvinylpyrrolidone base fluorescence laminated film.
The cross-linked polyvinylpyrrolidone base fluorescence laminated film smooth surface that step (3) obtains, color even, fluorescence property is stable.
Embodiment 3
1. it is that in 0.1 ethanol and acetone mixed solvent, stirring velocity is 800r/min that the polyvinylpyrrolidone that is 30k by 0.03g molecular weight under ice-water bath churned mechanically condition is dissolved in 100ml volume ratio, and churning time is 30min; Then at room temperature stir 30min; The last 4Cl-perylene acid anhydride that adds 0.01g under ultrasound condition, continues ultrasonic dispersion 30min;
2. mixing solutions step 1 being made is transferred in autoclave, gets rid of oxygen, at 165 ℃ of temperature, reacts 30h;
3. reaction is cooled to room temperature after finishing, and film is taken out and use second alcohol and water to clean 3 times, and then 45 ℃ of vacuum drying 24h, obtain cross-linked polyvinylpyrrolidone base fluorescence laminated film.
The cross-linked polyvinylpyrrolidone base fluorescence laminated film smooth surface that step (3) obtains, color even, fluorescence property is stable.
The structural formula of described 4Cl-perylene acid anhydride is:
Claims (1)
1. a preparation method for cross-linked polyvinylpyrrolidone base fluorescence laminated film, is characterized in that, its concrete steps are:
(1) under ice-water bath churned mechanically condition, the polyvinylpyrrolidone of 0.03-1.5g is dissolved in the ethanol and acetone mixed solvent that 30-150ml volume ratio is 0.1-20, stirring velocity is 800-1000r/min, and churning time is 20-50min; Then at room temperature stir 20-50min; The last condensed-nuclei aromatics dyestuff that adds 5mg-0.5g under ultrasound condition, continues ultrasonic dispersion 20-50min;
(2) mixing solutions step (1) being made is transferred in autoclave, gets rid of oxygen, at 120-180 ℃ of temperature, reacts 1-40h;
(3) reaction is cooled to room temperature after finishing, and film is taken out and use second alcohol and water to clean, and then 20-60 ℃ of vacuum drying 1-24h, obtains cross-linked polyvinylpyrrolidone base fluorescence laminated film;
The molecular weight of described polyvinylpyrrolidone is 17k-90k;
Described condensed-nuclei aromatics dyestuff is Nai, perylene, terylene or the derivative of naphthalene derivatives, perylene, the derivative of terylene.
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| DE102012019495A1 (en) | 2012-10-02 | 2014-04-17 | Heinz Langhals | New substituted imidazolo-perylene bisanhydride compounds useful e.g. as reference materials for fluorescence measurements, as pigments and dyes for dyeing purposes, and as pigments in lacquers, preferably synthetic resin lacquers |
| CN103524969B (en) * | 2013-10-22 | 2016-03-30 | 北京化工大学 | A kind of preparation method of oxide-doped polyvinylpyrrolidone fluorescence composite material |
| CN111560122B (en) * | 2020-04-14 | 2022-11-22 | 华南师范大学 | Method for enhancing PVP photosensitivity and crosslinking method |
| CN113279254B (en) * | 2021-06-30 | 2022-05-06 | 大连工业大学 | Polyvinylpyrrolidone coating fluorescent yarn and preparation method thereof |
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| CN101456677B (en) * | 2008-12-30 | 2011-08-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of light storage nano compound film and read-write method |
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