CN103554806A - Fluorescent hyperbranched polymer-nano clay film composite material and preparation method thereof - Google Patents
Fluorescent hyperbranched polymer-nano clay film composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorescent hyperbranched polymer-nano clay film composite material and a preparation method thereof, wherein the film composite material is formed from a fluorescent hyperbranched polymer and nano clay which are alternatively assembled; the fluorescent hyperbranched polymer is selected from one or more of hyperbranched polyamide-amine, hyperbranched poly-amino-ester and hyperbranched polyether amide. The film composite material has a layered structure similar with a shell pearl layer, so that the tensile strength is increased by about 300% relative to that of an original polymer matrix, is about 20MPa and keeps very high toughness; the elongation at break is about 67%. The film composite material does not contain biological toxicity substances and has good biocompatibility. More importantly, the film composite material has the characteristics that under the irradiation of ultraviolet ray, the film composite material gives out bright and blue fluorescent light, the fluorescence intensity of the film composite material is obviously improved compared with that of an original fluorescent hyperbranched polymer, that other biomimetic composite materials do not have.
Description
One, technical field
The present invention relates to a kind of preparation method of composite organic-inorganic material, specifically a kind of fluorescence hyperbranched polymer-nanoclay film composite material and preparation method thereof.Film composite material of the present invention, when having the laminate structure and photoluminescent property of imitative shell pearl layer, also has good biocompatibility.
Two, background technology
Bionics techniques has been used to prepare diversified artificial material.Imitation for shell structure not only makes people can obtain the new structural material with excellent mechanical performances, and can also obtain the matrix material with specific function.Wherein, there is the function film matrix material of photoluminescent property and biocompatibility in biomedical research field, such as organizational project, biosensor aspect have broad application prospects.
At present, visible following about thering is the research report of the imitative shell structural composite material of photoluminescent property:
< < advanced material > > (Advanced Materials, calendar year 2001s 13 211 pages of volumes) reported to there is the conjugated polymers of photoluminescent property---poly-[2-methoxyl group-5-(2 '-ethyl-hexyloxy)-1,4-vinylbenzene support] and nanoclay be raw material, prepared can emitting fluorescence polymkeric substance-nanoclay film composite material.But because the biocompatibility of conjugated polymers is poor, the biocompatibility of this film composite material is not good.
< < applied chemistry > > (Angewandte Chemie International Edition, within 2010,49 volume is 2140 pages) reported that what take chitosan and have photoluminescent property is raw material containing the double-metal hydroxide of rare earth elements europium, prepared can emitting fluorescence film composite material.But due to the potential bio-toxicity of rare earth element, this matrix material biocompatibility is poor.
< < materials chemistry > > (Journal of Materials Chemistry, within 2012,22 volume is 13005 pages) reported that the CdSe nano-particle of take polyvinyl alcohol, silicon zeolite sheet and having photoluminescent property is raw material, prepared can emitting fluorescence nano composite material.But owing to containing heavy metal element cadmium in this film composite material, biocompatibility is poor.
There is as follows as seen at present the imitative shell structure function film composite material of biocompatibility:
< < advanced material > > (Advanced Materials, 24 volume was 3426 pages in 2012) has reported take the film composite material with conductivity and cell attachment energy for growth that polyvinyl alcohol and Graphene make as raw material.But this matrix material is without photoluminescent property.
< < materials chemistry > > (Journal of Materials Chemistry, 22 volume was 21667 pages in 2012) has reported take the film composite material with blood compatibility that heparin and double-metal hydroxide prepared as raw material.But this matrix material is without photoluminescent property.
In sum, the current known imitative shell structural membrane matrix material with photoluminescent property, in preparation process, all adopt the conjugated polymer material that there is the inorganic materials of photoluminescent property or there is photoluminescent property, and these materials self do not have good biocompatibility, so the biocompatibility of the imitative shell film composite material of these fluorescence is not good.
Secondly, the known imitative shell structure function film composite material with biocompatibility does not have photoluminescent property at present.
Three, summary of the invention
The present invention aims to provide a kind of fluorescence hyperbranched polymer-nanoclay film composite material and preparation method thereof, technical problem to be solved is to make the film composite material of imitative shell structure have photoluminescent property and biocompatibility simultaneously, enable to be applied to biomedical research field, as novel tissue engineering material or biosensor.
The present invention selects has the fluorescence hyperbranched polymer of biocompatibility and the nanoclay without bio-toxicity, by fluorescence hyperbranched polymer and alternately assembling of nanoclay, form the laminate structure of imitative shell pearl layer, obtain thering is biocompatibility, and can be at the film composite material of emitting fluorescence under uviolizing.
Fluorescence hyperbranched polymer-nanoclay film composite material of the present invention is alternately to be assembled and form by fluorescence hyperbranched polymer and nanoclay;
Described film composite material is the laminate structure of imitative shell pearl layer;
Described fluorescence hyperbranched polymer is selected from one or more in ultrabranching polyamide-amine, hyperbranched poly amino ester, hyperbranched polyether acid amides, and the number-average molecular weight of described fluorescence hyperbranched polymer is 8000-10000.
Described nanoclay is sodium-based montmorillonite, and radius-thickness ratio is 10-100:1, and thickness is 1 nanometer.
Described fluorescence hyperbranched polymer is according to the ratio of mol ratio 2:1～1:2, to be mixed through Michael addition polyreaction and obtain with monomer II by N-aminoethyl piperazine; Described monomer II comprises N, N '-methylene-bisacrylamide, N, one or more in N '-cystamine bisacrylamide, BDO double methacrylate.
The solvent of described polyaddition reaction is selected from one or more in water, methyl alcohol, dimethyl sulfoxide (DMSO), and temperature of reaction is 30-70 ℃, and the reaction times is 2-7 days.
Described fluorescence hyperbranched polymer is to be obtained through Michael addition polyreaction by hydroxyl and the polyfunctional monomer of two keys; The polyfunctional monomer of described hydroxyl and two keys comprises 2-acrylamido-2-methylol-propane-1,3-glycol, 2-acrylamido-2-methyl-propane-1,3-glycol, 2-methacryloyl amido-2-methylol-propane-1,3-glycol, 2-methacryloyl amido-2-methyl-propane-1, one or more in 3-glycol.
The solvent of described polyaddition reaction is selected from one or more in water, methyl alcohol, dimethyl sulfoxide (DMSO), and temperature of reaction is 30-70 ℃, and the reaction times is 2-7 days.
The preparation method of fluorescence hyperbranched polymer-nanoclay film composite material of the present invention operates according to the following steps:
1) nanoclay is added in deionized water, after being uniformly dispersed, obtain the nanoclay aqueous dispersions of massfraction 0.5%, by described nanoclay aqueous dispersions with the speed of 3000 revs/min centrifugal 10 minutes, leave and take supernatant liquid;
2) aqueous solution of the fluorescence hyperbranched polymer of massfraction 2-6% and supernatant liquid equal-volume prepared by step 1) are mixed, dispersed with stirring obtains mixed solution after evenly;
3) will after described mixed solution centrifugation, obtain jelly, the rotating speed of centrifugation is 9000 revs/min.
4) described jelly is scattered in the deionized water of 15-20 times of volume, after being uniformly dispersed, by vacuum aided, filters and obtain filter cake, described filter cake, at seasoning 1-3 days in air, is obtained to fluorescence hyperbranched polymer-nanoclay film composite material.
Film composite material of the present invention can send blue-fluorescence under uviolizing, and emission band scope is 400-500nm.
Film composite material of the present invention has good toughness, the transparency and biocompatibility, is expected to as bioengineered tissue material or biosensor.
The self-assembly layer by layer of film composite material of the present invention realizes by vacuum filtration, and the method for vacuum filtration self-assembly is simple to operation, can produce in a large number the film composite material of arbitrary dimension.
Through the nanoclay surface adsorption of lift-off processing a large amount of hyperbranched polymers, form hybrid systems, hybrid systems ordered arrangement under the effect of vacuum filtration, has formed the laminate structure of orderly fluorescence hyperbranched polymer and nanoclay alternative arrangement.
Film composite material of the present invention has the laminate structure that is similar to shell pearl layer, and this makes its tensile strength improve approximately 300% with respect to original polymer matrix, is about 20MPa, and has kept very high toughness, and elongation at break is about 67%.
Film composite material of the present invention does not contain bio-toxicity material, has good biocompatibility.Therefore, be expected to be applied to biologic medical research field, as organizational project and biosensor.The more important thing is, film composite material of the present invention has the advantages that other bionic composite materials do not possess: under ultraviolet irradiation, can send bright blue-fluorescence, and the more former fluorescence hyperbranched polymer of the fluorescence intensity of film composite material is significantly increased.Therefore, composite film material of the present invention can be opened up a new approach for preparing high-intensity biocompatibility fluorescent material in practical application.
The present invention adopts the thin film-forming method of vacuum filtration self-assembly, operating process is convenient, experimental installation is simple, and can be as required the composite film material of a large amount of manufacture arbitrary dimensions, the method can be applied to preparing the fluorescence hyperbranched polymer composite film material of various new.
Four, accompanying drawing explanation
Fig. 1 is the fluorescence spectrum of fluorescence hyperbranched polymer-nanoclay film composite material in embodiment 1.As can be seen from Figure 1, the fluorescent emission wavelength of film composite material and the fluorescent emission wavelength of the hyperbranched polymer aqueous solution are basically identical, fluorescent emission bands of a spectrum scope is at 400-500nm, maximum emission wavelength is in blue light region, maximum emission wavelength is 438nm, shows that this film composite material has the photoluminescent property similar to fluorescence hyperbranched polymer.In addition, the fluorescent emission intensity of film composite material will be higher than former fluorescence hyperbranched polymer.
Fig. 2 is the electron scanning micrograph of fluorescence hyperbranched polymer-nanoclay film composite material in embodiment 1.As can be seen from Figure 2, film composite material of the present invention present clearly, the laminate structure quite similar with the layered microstructure of shell.
Fig. 3 is the XRD spectra of film composite material of the present invention, sodium-based montmorillonite (MTM) and fluorescence hyperbranched polymer.As can be seen from Figure 3, between hyperbranched polymer and polynite, formed orderly arrangement architecture: pure hyperbranched polymer does not have diffraction peak in 2 θ angular ranges of test, shows in fluorescence hyperbranched polymer without ordered structure.And after hyperbranched polymer mixes with nano imvite, can see diffraction peak clearly, obviously this diffraction peak is because the rule of montmorillonite layer is piled up formation.The diffraction peak of film composite material has largely and moves to Small angle direction relative to the diffraction peak of polynite, illustrate that the spacing of polynite is along with adding of polymkeric substance of obvious increase, this has proved that polyalcohol intercalation has entered the interlayer of polynite, has pulled open the distance of its sheet interlayer.
Fig. 4 is the stress-strain curve of fluorescence hyperbranched polymer-nanoclay film composite material in embodiment 1.As can be seen from Figure 4, the ultimate strength of film composite material has had and has significantly improved with respect to fluorescence hyperbranched polymer, and increase rate is about 300%, is about 20MPa.Meanwhile, film composite material has also kept very high elongation at break, is about 67%.
Five, embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
1) 2.5g sodium-based montmorillonite is placed in to round-bottomed flask, adds 497.5mL deionized water, stir seven days; With the speed centrifugal treating of 3000 revs/min 10 minutes, centrifugal sediment is given up subsequently, left and taken supernatant liquid.
2) by 7.71g N, N '-methylene-bisacrylamide (50mmol) and 6.46g N-aminoethyl piperazine (50mmol) join in methanol/water (volume ratio the is 7/3) mixed solvent of 90mL, continue to react 5 days under agitation condition, 50 ℃ of temperature of reaction, reaction finishes to add in backward reaction solution the acetone precipitation of 10 times of volumes, obtains fluorescence hyperbranched polymer.
3) fluorescence hyperbranched polymer is scattered in deionized water, be mixed with the aqueous solution of the fluorescence hyperbranched polymer of massfraction 2%, the supernatant liquid 40mL that the aqueous solution 40mL of described fluorescence hyperbranched polymer is obtained with step 1) mixes, stir 24 hours, make fluorescence hyperbranched polymer be adsorbed onto better the surface of sodium-based montmorillonite, obtain mixed solution, the rotating speed centrifugation 10min by described mixed solution with 9000rpm, collects jelly.
4) with deionized water wash gained jelly, and jelly is scattered in 20mL deionized water, stirs 20min, more ultrasonic 10min, suspension obtained; Described suspension is poured in the Büchner funnel that cellulose mixture filter paper (aperture 0.22 μ m) is housed, carry out vacuum filtration self-assembly, by seasoning under suction filtration gained filter cake room temperature one day, with acetone, dissolve filter paper and obtain fluorescence hyperbranched polymer-nanoclay film composite material.
Adopt respectively fluorescence spectrophotometer, scanning electronic microscope, X-ray diffractometer and electronic universal tester to characterize film composite material sample.
The fluorescence emission spectrum of film composite material sample prepared by the present embodiment as shown in Figure 1, analysis shows, the fluorescent emission spectrogram of film composite material of the present invention and the fluorescent emission spectrogram of hyperbranched polymer solution are basically identical, show that this film composite material sample has photoluminescent property, this photoluminescent property comes from fluorescence hyperbranched polymer, and the more former fluorescence hyperbranched polymer of the fluorescence intensity of film composite material is significantly increased.
As shown in Figure 2, film composite material sample presents clearly the cross-section morphology sem observation result of film composite material prepared by the present embodiment, the laminate structure quite similar with the layered microstructure of shell.
As shown in Figure 3, in film composite material, there is ordered structure, and in fluorescence hyperbranched polymer, do not have ordered structure in the X-ray diffraction analysis result of film composite material prepared by the present embodiment.Move to Small angle direction compared with sodium-based montmorillonite the diffraction peak position of film composite material, shows that polymkeric substance and polynite have formed stratiform packing structure, and pulled open the distance between montmorillonite layer.
As shown in Figure 4, the more former fluorescence hyperbranched polymer of the ultimate tensile strength of film composite material has had and has significantly improved the mechanical experimental results of film composite material prepared by the present embodiment, and increase rate is about 300%.Meanwhile, film composite material has kept very high elongation at break, is about 67%.
By carry out cell cultures test on film sample surface, show, cell can be attached to sample surfaces growth effectively, has confirmed its biocompatibility.
Embodiment 2:
1) 2.5g sodium-based montmorillonite is placed in to round-bottomed flask, adds 497.5mL deionized water, stir seven days; With the speed centrifugal treating of 3000 revs/min 10 minutes, centrifugal sediment is given up subsequently, left and taken supernatant liquid.
2) 4.63g N, N '-methylene-bisacrylamide (30mmol), 3.911g N, N '-cystamine bisacrylamide (15mmol) and 5.82g N-aminoethyl piperazine (45mmol) join in methanol/water (volume ratio the is 8/2) mixed solvent of 100mL, continue to react 5 days under agitation condition, 50 ℃ of temperature of reaction, reaction finishes to add in backward reaction solution the acetone precipitation of 10 times of volumes, obtains fluorescence hyperbranched polymer.
3) fluorescence hyperbranched polymer is scattered in deionized water, be mixed with the aqueous solution of the fluorescence hyperbranched polymer of massfraction 4%, the supernatant liquid 40mL that the aqueous solution 40mL of described fluorescence hyperbranched polymer is obtained with step 1) mixes, stir 24 hours, make fluorescence hyperbranched polymer be adsorbed onto better the surface of sodium-based montmorillonite, obtain mixed solution, the rotating speed centrifugation 10min by described mixed solution with 9000rpm, collects jelly.
4) with deionized water wash gained jelly, and jelly is scattered in the deionized water of 15 times of volumes, stirs 20min, more ultrasonic 10min, suspension obtained; Described suspension is poured in the Büchner funnel that cellulose mixture filter paper (aperture 0.22 μ m) is housed, carry out vacuum filtration self-assembly, by seasoning under suction filtration gained filter cake room temperature 2 days, with acetone, dissolve filter paper and obtain fluorescence hyperbranched polymer-nanoclay film composite material.
Embodiment 3:
1) 2.5g sodium-based montmorillonite is placed in to round-bottomed flask, adds 497.5mL deionized water, stir seven days; With the speed centrifugal treating of 3000 revs/min 10 minutes, centrifugal sediment is given up subsequently, left and taken supernatant liquid.
2) 9.91g1,4-butyleneglycol double methacrylate (50mmol) and 6.46g N-aminoethyl piperazine (50mmol) join in the dimethyl sulfoxide (DMSO) of 120mL, continue to react 4 days under agitation condition, 70 ℃ of temperature of reaction, reaction finishes to add in backward reaction solution the acetone precipitation of 10 times of volumes, obtains fluorescence hyperbranched polymer.
3) fluorescence hyperbranched polymer is scattered in deionized water, be mixed with the aqueous solution of the fluorescence hyperbranched polymer of massfraction 6%, the supernatant liquid 30mL that the aqueous solution 30mL of described fluorescence hyperbranched polymer is obtained with step 1) mixes, stir 24 hours, make fluorescence hyperbranched polymer be adsorbed onto better the surface of sodium-based montmorillonite, obtain mixed solution, the rotating speed centrifugation 10min by described mixed solution with 9000rpm, collects jelly.
4) with deionized water wash gained jelly, and jelly is scattered in the deionized water of 20 times of volumes, stirs 20min, more ultrasonic 10min, suspension obtained; Described suspension is poured in the Büchner funnel that cellulose mixture filter paper (aperture 0.22 μ m) is housed, carry out vacuum filtration self-assembly, by seasoning under suction filtration gained filter cake room temperature 3 days, with acetone, dissolve filter paper and obtain fluorescence hyperbranched polymer-nanoclay film composite material.
In experimentation, find, the fluorescence hyperbranched polymer solution of high density decrease with the ultimate tensile strength that the sodium-based montmorillonite dispersion liquid of same concentrations mixes formed film composite material (this is because the mechanical property of fluorescence hyperbranched polymer self is weak), but elongation at break improves, when the fluorescence hyperbranched polymer solution that adopts massfraction 6% is during with massfraction 0.5% sodium-based montmorillonite dispersion liquid formation matrix material, ultimate tensile strength is only 6MPa left and right, but elongation at break can reach the level similar to original copolymer, approach 200%, meanwhile, the fluorescence intensity of film composite material improves with the ratio of fluorescence hyperbranched polymer and clay.
Embodiment 4:
1) 2.5g sodium-based montmorillonite is placed in to round-bottomed flask, adds 497.5mL deionized water, stir seven days; With the speed centrifugal treating of 3000 revs/min 10 minutes, centrifugal sediment is given up subsequently, left and taken supernatant liquid.
2) 3.96g1,4-butyleneglycol double methacrylate (20mmol), by 4.63g N, N '-methylene-bisacrylamide (30mmol) and 6.46g N-aminoethyl piperazine (50mmol) join in the dimethyl sulfoxide (DMSO) of 120mL, continue to react 4 days under agitation condition, 70 ℃ of temperature of reaction, reaction finishes to add in backward reaction solution the acetone precipitation of 10 times of volumes, obtains fluorescence hyperbranched polymer.
3) fluorescence hyperbranched polymer is scattered in deionized water, be mixed with the aqueous solution of the fluorescence hyperbranched polymer of massfraction 2%, the supernatant liquid 40mL that the aqueous solution 40mL of described fluorescence hyperbranched polymer is obtained with step 1) mixes, stir 24 hours, make fluorescence hyperbranched polymer be adsorbed onto better the surface of sodium-based montmorillonite, obtain mixed solution, the rotating speed centrifugation 10min by described mixed solution with 9000rpm, collects jelly.
4) with deionized water wash gained jelly, and jelly is scattered in the deionized water of 20 times of volumes, stirs 20min, more ultrasonic 10min, suspension obtained; Described suspension is poured in the Büchner funnel that cellulose mixture filter paper (aperture 0.22 μ m) is housed, carry out vacuum filtration self-assembly, by seasoning under suction filtration gained filter cake room temperature 2 days, with acetone, dissolve filter paper and obtain fluorescence hyperbranched polymer-nanoclay film composite material.
Embodiment 5:
1) 2.5g sodium-based montmorillonite is placed in to round-bottomed flask, adds 497.5mL deionized water, stir seven days; With the speed centrifugal treating of 3000 revs/min 10 minutes, centrifugal sediment is given up subsequently, left and taken supernatant liquid.
2) by 15.80g2-acrylamido-2-methyl-propane-1,3-glycol (100mmol) joins in the dimethyl sulfoxide (DMSO) of 50mL, continue to react 3 days under agitation condition, 60 ℃ of temperature of reaction, reaction finishes to add in backward reaction solution the acetone precipitation of 10 times of volumes, obtains fluorescence hyperbranched polymer.
3) fluorescence hyperbranched polymer is scattered in deionized water, be mixed with the aqueous solution of the fluorescence hyperbranched polymer of massfraction 2%, the supernatant liquid 50mL that the aqueous solution 50mL of described fluorescence hyperbranched polymer is obtained with step 1) mixes, stir 24 hours, make fluorescence hyperbranched polymer be adsorbed onto better the surface of sodium-based montmorillonite, obtain mixed solution, the rotating speed centrifugation 10min by described mixed solution with 9000rpm, collects jelly.
4) with deionized water wash gained jelly, and jelly is scattered in the deionized water of 20 times of volumes, stirs 20min, more ultrasonic 10min, suspension obtained; Described suspension is poured in the Büchner funnel that cellulose mixture filter paper (aperture 0.22 μ m) is housed, carry out vacuum filtration self-assembly, by seasoning under suction filtration gained filter cake room temperature 1 day, with acetone, dissolve filter paper and obtain fluorescence hyperbranched polymer-nanoclay film composite material.
Embodiment 6:
1) 2.5g sodium-based montmorillonite is placed in to round-bottomed flask, adds 497.5mL deionized water, stir seven days; With the speed centrifugal treating of 3000 revs/min 10 minutes, centrifugal sediment is given up subsequently, left and taken supernatant liquid.
2) by 7.90g2-acrylamido-2-methyl-propane-1,3-glycol (50mmol) and 9.40g2-methacryloyl amido-2-methylol-propane-1,3-glycol joins in the dimethyl sulfoxide (DMSO) of 50mL, continue to react 2 days under agitation condition, 60 ℃ of temperature of reaction, reaction finishes to add in backward reaction solution the acetone precipitation of 10 times of volumes, obtains fluorescence hyperbranched polymer.
3) fluorescence hyperbranched polymer is scattered in deionized water, be mixed with the aqueous solution of the fluorescence hyperbranched polymer of massfraction 2%, the supernatant liquid 50mL that the aqueous solution 50mL of described fluorescence hyperbranched polymer is obtained with step 1) mixes, stir 24 hours, make fluorescence hyperbranched polymer be adsorbed onto better the surface of sodium-based montmorillonite, obtain mixed solution, the rotating speed centrifugation 10min by described mixed solution with 9000rpm, collects jelly.
4) with deionized water wash gained jelly, and jelly is scattered in the deionized water of 15 times of volumes, stirs 20min, more ultrasonic 10min, suspension obtained; Described suspension is poured in the Büchner funnel that cellulose mixture filter paper (aperture 0.22 μ m) is housed, carry out vacuum filtration self-assembly, by seasoning under suction filtration gained filter cake room temperature 2 days, with acetone, dissolve filter paper and obtain fluorescence hyperbranched polymer-nanoclay film composite material.
Claims (8)
1. fluorescence hyperbranched polymer-nanoclay film composite material, is characterized in that: described film composite material is alternately to be assembled and form by fluorescence hyperbranched polymer and nanoclay;
Described film composite material is the laminate structure of imitative shell pearl layer;
Described fluorescence hyperbranched polymer is selected from one or more in ultrabranching polyamide-amine, hyperbranched poly amino ester, hyperbranched polyether acid amides.
2. fluorescence hyperbranched polymer-nanoclay film composite material according to claim 1, is characterized in that:
Described nanoclay is sodium-based montmorillonite, and radius-thickness ratio is 10-100:1, and thickness is 1 nanometer.
3. fluorescence hyperbranched polymer-nanoclay film composite material according to claim 1, is characterized in that:
Described fluorescence hyperbranched polymer is according to the ratio of mol ratio 2:1～1:2, to be mixed through Michael addition polyreaction and obtain with monomer II by N-aminoethyl piperazine; Described monomer II comprises N, N '-methylene-bisacrylamide, N, one or more in N '-cystamine bisacrylamide, BDO double methacrylate.
4. fluorescence hyperbranched polymer-nanoclay film composite material according to claim 3, is characterized in that:
The solvent of described polyaddition reaction is selected from one or more in water, methyl alcohol, dimethyl sulfoxide (DMSO), and temperature of reaction is 30-70 ℃, and the reaction times is 2-7 days.
5. fluorescence hyperbranched polymer-nanoclay film composite material according to claim 1, is characterized in that:
Described fluorescence hyperbranched polymer is to be obtained through Michael addition polyreaction by hydroxyl and the polyfunctional monomer of two keys; The polyfunctional monomer of described hydroxyl and two keys comprises 2-acrylamido-2-methylol-propane-1,3-glycol, 2-acrylamido-2-methyl-propane-1,3-glycol, 2-methacryloyl amido-2-methylol-propane-1,3-glycol, 2-methacryloyl amido-2-methyl-propane-1, one or more in 3-glycol.
6. fluorescence hyperbranched polymer-nanoclay film composite material according to claim 5, is characterized in that:
The solvent of described polyaddition reaction is selected from one or more in water, methyl alcohol, dimethyl sulfoxide (DMSO), and temperature of reaction is 30-70 ℃, and the reaction times is 2-7 days.
7. a preparation method for fluorescence hyperbranched polymer-nanoclay film composite material claimed in claim 1, is characterized in that operating according to the following steps:
1) nanoclay is added in deionized water, after being uniformly dispersed, obtain the nanoclay aqueous dispersions of massfraction 0.5%, by described nanoclay aqueous dispersions with the speed of 3000 revs/min centrifugal 10 minutes, leave and take supernatant liquid;
2) aqueous solution of the fluorescence hyperbranched polymer of massfraction 2-6% and supernatant liquid equal-volume prepared by step 1) are mixed, dispersed with stirring obtains mixed solution after evenly;
3) will after described mixed solution centrifugation, obtain jelly;
4) described jelly is scattered in the deionized water of 15-20 times of volume, after being uniformly dispersed, by vacuum aided, filters and obtain filter cake, described filter cake, at seasoning 1-3 days in air, is obtained to fluorescence hyperbranched polymer-nanoclay film composite material.
8. preparation method according to claim 7, is characterized in that:
In step 3), the rotating speed of centrifugation is 9000 revs/min.
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| CN111180732A (en) * | 2019-12-30 | 2020-05-19 | 深圳市研一新材料有限责任公司 | Hyperbranched water-soluble lithium ion battery binder for lithium ion battery and preparation method thereof |
| CN112940669A (en) * | 2021-02-04 | 2021-06-11 | 西安交通大学 | Fluorescent polyamide hot melt adhesive and preparation method thereof |
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