CN104845052A - Poly phenylenevinylene conjugated polymer fluorescent nanoparticles with controllable emission wavelength and preparation method - Google Patents
Poly phenylenevinylene conjugated polymer fluorescent nanoparticles with controllable emission wavelength and preparation method Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 68
- 229920000553 poly(phenylenevinylene) Polymers 0.000 title claims abstract description 47
- -1 Poly phenylenevinylene Polymers 0.000 title claims abstract description 35
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- 239000010408 film Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 5
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001338 self-assembly Methods 0.000 abstract description 4
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- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
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Abstract
The invention discloses poly phenylenevinylene conjugated polymer fluorescent nanoparticles with a controllable emission wavelength and a preparation method. The method comprises the following steps of preparing PPV (Poly-Phenylene Vinylene) precursor solution according to a Wessling polymer sulfonium salt precursor method, taking methanol as a substitution reaction agent, replacing tetrahydrothiophene groups of the PPV precursor partly by methoxyl under the anaerobic and high temperature condition, after removing the methanol by vacuum distillation, eliminating residual tetrahydrothiophene groups of the PPV precursor selectively, converting the PPV precursor to PPV light emitting polymer; and obtaining PPV nanoparticles through self-assembly of polymer chains in the process of elimination simultaneously. According to the method provided by the invention, the reaction time of the PPV precursor and the methanol is controlled to obtain PPV nanoparticles with different emission wavelengths. The prepared PPV conjugated polymer fluorescent nanoparticles have the advantages of being narrow in particle size distribution, controllable in emission wavelength, simple in preparation technology, convenient in operation, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of fluorescent nano material, sub-ethene fluorescent nano particles of the polyparaphenylene that particularly a kind of emission wavelength is controlled and preparation method thereof, belongs to high-molecular luminous material technical field.
Background technology
In recent years, semiconductive polymer nano-particle receives great concern because it possesses the excellent specific property needed for fluorescent probe.This polymer nano-particle is mainly made up of pi-conjugated polymkeric substance, is also referred to as polymerization object point.Their particle diameter is minimum, can between a few nanometer to hundreds of nanometer, there is very bright fluorescence, and luminous speed is fast, the various fields such as the advantage on these sizes and fluorescence property makes that polymer nano-particle is followed the trail of at photovoltaic device, cell marking, in-vivo imaging, single-particle, bio-sensing and drug release have good actual application prospect.
Since the electroluminescent properties of the sub-ethene (PPV) of people's reported first polyparaphenylenes such as nineteen ninety Cambridge University Burroughes, PPV class conjugated polymers is one of polymer luminescent material of most study always.The method of common adjustment conjugated polymers emission wavelength has physical blending process, copolymerization method, control conjugate length method and side base to modify method.For PPV class conjugated polymers, more research still concentrates in control PPV conjugate length (see document: J. Am. Chem. Soc. 1993,115,10117-10124 and J. Appl. Phys. 1993,73,5177-5180), this method is the syntheti c route based on Wessling sulfonium salt presoma, carry out part by selecting more stable group and replace the tetramethylene sulfide group of easily leaving away, the method eliminated by selectivity again makes the tetramethylene sulfide group cancellation remained, thus obtains the PPV with different conjugate length segment.In general, compare the method for physical blending, regulate emission wavelength to have better stability by the method for chemical modification.And the method that the method for selectivity elimination leavings group compares other chemical modifications is more easy to operate, and the Be very effective that emission wavelength regulates.
At present, the preparation method of the conjugated polymers nanoparticle reported can be divided into direct polymerization method and post polymerization method (see document: Chem. Rev. 2010,110,6260-6279 and Angew. Chem. Int. Ed. 2013,52,3086-3109).Direct polymerization method forms nano particle structure by small molecule monomer direct polymerization, and what usually adopt is the method for transition metal-catalyzed coupling in nonhomogeneous system.Post polymerization method is divided into again microemulsion method and reprecipitation method, is all first to dissolve conjugated polymers in organic solvent as starting soln, therefore needs first to obtain stable polymers soln.Microemulsion method is joined by polymers soln in the water containing tensio-active agent, utilizes the self-assembly between molecular chain to obtain nanoparticle.Reprecipitation method is expelled in large water gaging rapidly by the organic solvent being dissolved with polymkeric substance of trace, stirring or utilizing the self-assembly of polymer chain to form nanoparticle under ultrasonication.
The method of direct polymerization require polymer precursor or monomer not with solvent generation side reaction, but PPV sulfonium salt presoma at high temperature easily and polar solvent occur further to replace side reaction.Secondly, due to the PPV structure adaptability performance extreme difference of non-modified, be difficult to dissolve in common solvent, therefore, existing PPV polymkeric substance cannot meet the stable polymers soln adopting and obtain required by post polymerization method.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, provide a kind of aqueous phase dispersibility good, and the polyparaphenylene that preparation technology is simple, emission wavelength is controlled sub-ethene conjugated polymer fluorescent nano particles and preparation method thereof.
The technical scheme realizing the object of the invention is to provide the controlled polyparaphenylene of a kind of emission wavelength sub-ethene conjugated polymer fluorescent nano particles, and its structural formula is:
，
Wherein, n and x is positive integer, and x is the number of the effective conjugate unit of polymkeric substance, and n is the number of repeat unit of polymkeric substance, and 1≤x≤n, n≤70.
The scope of the maximum emission wavelength of described fluorescent nano particles is 467 ~ 491nm.
Technical solution of the present invention also comprises the preparation method of the controlled polyparaphenylene of emission wavelength as above sub-ethene conjugated polymer fluorescent nano particles, and step is as follows:
1, adopt Wessling sulfonium salt precursor process to obtain the sub-ethene precursor solution of polyparaphenylene, be denoted as pre-PPV solution;
2, in pre-PPV solution, methyl alcohol is added, the volume ratio of methyl alcohol and pre-PPV solution is 2 ﹕ 1 ~ 7 ﹕ 1, temperature be 40 ~ 60 DEG C, under oxygen free condition, reaction 10 ~ 72 h, again through underpressure distillation removing methyl alcohol, obtain polyparaphenylene sub-ethene conjugated polymer polymers soln, be denoted as pre-PPV-N polymers soln;
3, in pre-PPV-N polymers soln, tensio-active agent is added, the mass ratio of tensio-active agent and pre-PPV-N polymkeric substance is 3 ﹕ 1 ~ 10 ﹕ 1, described tensio-active agent is Krafft point lower than the ionogenic surfactant of 90 DEG C, and cloud point is higher than the nonionic surface active agent of 70 DEG C; Be react 1 ~ 6 h under the condition of 70 ~ 90 DEG C in temperature, obtain the aqueous dispersion liquid of a kind of polyparaphenylene sub-ethene conjugated polymer fluorescent nano particles.
Ionogenic surfactant described in technical solution of the present invention is containing the alkyl-sulphate of 12 ~ 18 carbonatomss, sulfonate, soap or quaternary ammonium salt; Concrete can be sodium lauryl sulphate or sodium laurylsulfonate.Described nonionic surface active agent is glycerin fatty acid ester, polyoxyethylene-type or EPE polyol EPE.
Technical solution of the present invention by changing the reaction times of the sub-ethene presoma of polyparaphenylene in step 2 and methyl alcohol, can also obtain the polyparaphenylene sub-ethene conjugated polymer fluorescent nano particles of different emission.
The Aqueous dispersions drop of polyparaphenylene step 3 of the present invention obtained sub-ethene conjugated polymer fluorescent nano particles is coated with or is spun on thin-film carrier surface, obtains a kind of polyparaphenylene sub-ethene fluorescent nano particles film after drying.
Mechanism of the present invention is: add methyl alcohol in sub-ethene presoma (pre-PPV) solution of polyparaphenylene, tetramethylene sulfide group on pre-PPV chain is replaced by methoxy moieties, by controlling the reaction times, the replacement degree of the pre-PPV obtained is different, the substitution reaction time is longer, replaces degree larger; Solution after substitution reaction is again through underpressure distillation removing methyl alcohol, under tensio-active agent participation role, while PPV conjugated polymer in aqueous phase is converted into luminous PPV, the self-assembly of polymer chain in eliminative reaction process is utilized to obtain PPV nanoparticle, its maximum emission wavelength is in 467 ~ 491 nm scopes, and emission wavelength regulates by controlling the substitution reaction time.
Compared with prior art, beneficial effect of the present invention is:
1. the emission wavelength of PPV nanoparticle that prepared by the present invention regulates by controlling intermediate reaction condition, and technique is simple, and convenient operation, is suitable for suitability for industrialized production.
2. compare with post polymerization method with prior art microemulsion polymerization method, the preparation method of PPV class fluorescent nano particles provided by the invention does not need the problem considering that PPV base polymer is poorly soluble, therefore need not carry out side chain modification to PPV, it also avoid that the PPV presoma that obtained by sulfonium salt precursor process brought when high temperature is eliminated easily and the problem of methyl alcohol polar solvent generation side reaction.
3. fluorescent nano particles emission wavelength provided by the invention is controlled, narrow diameter distribution, and its aqueous dispersion liquid can be applicable to the field such as biological detection, medical diagnosis, also makes film by spin coating or a mode be coated with and is applied to luminescent material and photovoltaic device.
Accompanying drawing explanation
Fig. 1 is the syntheti c route schematic diagram of the PPV fluorescent nano particles that the embodiment of the present invention provides;
Fig. 2 is the transmission electron microscope photo of the PPV fluorescent nano particles that the embodiment of the present invention provides;
Fig. 3 is the fluorescence spectrum figure of PPV fluorescent nano particles in water that the embodiment of the present invention provides;
Fig. 4 is the Tyndall effect figure of PPV-0, PPV-1, PPV-2, PPV-3 and PPV-4 nanoparticle aqueous dispersion liquid under laser pen irradiates that the embodiment of the present invention 1 ~ 5 provides;
Fig. 5 is the grain size distribution of PPV fluorescent nano particles in water that the embodiment of the present invention provides.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1
See accompanying drawing 1, it is the syntheti c route schematic diagram of the polyparaphenylene sub-ethene conjugated polymer nanoparticle that the present embodiment provides, and concrete steps are as follows:
1. reference literature (J. Am. Chem. Soc.1993,115,10117-10124) synthesis is containing the PPV monomer without substituted benzene ring, gets PPV monomer 0.6895 g (1.965 mmol), under anhydrous and oxygen-free condition, obtained PPV monomer is dissolved in 12 mL H
2in O; Again the NaOH aqueous solution of 1 M of 1.7 mL is slowly dripped wherein, to put in ice-water bath after stirring reaction 1 h, add the HCl solution termination reaction of 2 M of 3 mL, then to dialyse 24 h (removing 12 hours of spending the night with the dialysis tubing that molecular weight is 3500, section changes water once every 2 h At All Other Times, add 500 mL deionized waters at every turn), obtain PPV presoma (being denoted as pre-PPV) solution 20 mL.
2. to get in step 1 in gained PPV precursor water solution 5 ml 250 mL, two mouthfuls of flasks under oxygen free condition, after the dilution of 15ml deionized water, add 0.2000 g sodium laurylsulfonate SDS (0.0007 mol) wherein, first be warming up to 50 DEG C and treat that sodium laurylsulfonate is dissolved in the water, add 0.2 ml triethylamine (0.0014 mol) again as eliminative reaction catalyzer, continue to be warming up to 80 DEG C, react 3 h and obtain PPV(and be denoted as PPV-0) nanoparticle dispersion liquid.See accompanying drawing 2, it is the transmission electron microscope photo of the PPV-0 nanoparticle that the present embodiment provides.Can see that the size of PPV-0 nanoparticle is more homogeneous by Fig. 2, in irregular spherical.The maximum emission wavelength of nanoparticle dispersion liquid, see accompanying drawing 3, is 491 nm, and has acromion at 523 nm wavelength places.
3. take the infrared tabletting machine of 0.1 g graphene powder and carry out compressing tablet under the pressure of 24 MPa.Get 100 μ L PPV-0 nanoparticle dispersion liquids, add after 900 μ L deionized waters dilute, therefrom get 100 μ L and be coated on Graphene wafer surface, obtained PPV film.
PPV fluorescent nano particles aqueous dispersion liquid prepared by the present embodiment can be applicable to the fields such as biological chemistry detection and medical diagnosis.PPV fluorescent nano particles dispersion liquid is formed PPV light-emitting film by the mode of dripping painting or spin coating at Graphene wafer surface, can be used as luminescent material or photovoltaic material.
Embodiment 2
1. that synthesizes with reference to document (J. Am. Chem. Soc.1993,115,10117-10124) under anhydrous and oxygen-free condition is dissolved in 12 mL H containing PPV monomer 0.6895 g (1.965 mmol) without substituted benzene ring
2in O, then the NaOH aqueous solution of 1 M of 1.7 mL is slowly dripped wherein, to put in ice-water bath after stirring reaction 1 h, add the HCl solution termination reaction of 2 M of 3 mL, to dialyse 24 h (removing 12 hours of spending the night with the dialysis tubing that molecular weight is 3500 afterwards, section changes water once every 2 h At All Other Times, adds 500 mL deionized waters at every turn), obtain PPV precursor solution 20 mL.In 250 mL, two mouthfuls of flasks of anaerobic, add 5 ml gained solution, after add 15 ml deionized waters and dilute, then add 60 ml methyl alcohol and fully mix, be warming up to 50 DEG C, react 16 h.After reaction terminates at reduced pressure conditions, controlling bath temperature is 35 DEG C, revolves steaming 30 min and is removed by methyl alcohol, obtain the pre-PPV-1 aqueous solution 20 mL.
2. to get in step 1 in the gained pre-PPV-1 aqueous solution 5 ml 250 mL, two mouthfuls of flasks under oxygen free condition, after the dilution of 15ml deionized water, add 0.2000 g sodium laurylsulfonate SDS (0.0007 mol) wherein, first be warming up to 50 DEG C and treat that sodium laurylsulfonate is dissolved in the water, add 0.2 ml triethylamine (0.0014 mol) again as eliminative reaction catalyzer, continue to be warming up to 80 DEG C, react 3 h and obtain PPV-1 nanoparticle dispersion liquid.The particle diameter of obtained PPV-1 nanoparticle is in 61 ~ 110 nm and 130 ~ 1000 nm, two intervals, and the maximum emission wavelength of nanoparticle dispersion liquid is 484 nm, and has acromion at 511 nm wavelength places.
Embodiment 3
1. that synthesizes with reference to document (J. Am. Chem. Soc.1993,115,10117-10124) under anhydrous and oxygen-free condition is dissolved in 12 mL H containing PPV monomer 0.6895 g (1.965 mmol) without substituted benzene ring
2in O, then the NaOH aqueous solution of 1 M of 1.7 mL is slowly dripped wherein, to put in ice-water bath after stirring reaction 1 h, add the HCl solution termination reaction of 2 M of 3 mL, to dialyse 24 h (removing 12 hours of spending the night with the dialysis tubing that molecular weight is 3500 afterwards, section changes water once every 2 h At All Other Times, adds 500 mL deionized waters at every turn), obtain PPV precursor solution 20 mL.In 250 mL, two mouthfuls of flasks of anaerobic, add 5 ml gained solution, after add 15 ml deionized waters and dilute, then add 60 ml methyl alcohol and fully mix, be warming up to 50 DEG C, react 24 h.After reaction terminates at reduced pressure conditions, controlling bath temperature is 35 DEG C, revolves steaming 30 min and is removed by methyl alcohol, obtain the pre-PPV-2 aqueous solution 20 mL.
2. to get in step 1 in the gained pre-PPV-2 aqueous solution 5 ml 250 mL, two mouthfuls of flasks under oxygen free condition, after the dilution of 15ml deionized water, add 0.2000 g sodium laurylsulfonate SDS (0.0007 mol) wherein, first be warming up to 50 DEG C and treat that sodium laurylsulfonate is dissolved in the water, add 0.2 ml triethylamine (0.0014 mol) again as eliminative reaction catalyzer, continue to be warming up to 80 DEG C, react 3 h and obtain PPV-2 nanoparticle dispersion liquid.The particle diameter of obtained PPV-2 nanoparticle is at 5 ~ 8 nm, and the maximum emission wavelength of nanoparticle dispersion liquid is 467 nm, and has acromion at 495 nm wavelength places.
Embodiment 4
1. that synthesizes with reference to document (J. Am. Chem. Soc.1993,115,10117-10124) under anhydrous and oxygen-free condition is dissolved in 12 mL H containing PPV monomer 0.6895 g (1.965 mmol) without substituted benzene ring
2in O, then the NaOH aqueous solution of 1 M of 1.7 mL is slowly dripped wherein, to put in ice-water bath after stirring reaction 1 h, add the HCl solution termination reaction of 2 M of 3 mL, to dialyse 24 h (removing 12 hours of spending the night with the dialysis tubing that molecular weight is 3500 afterwards, section changes water once every 2 h At All Other Times, adds 500 mL deionized waters at every turn), obtain PPV precursor solution 20 mL.In 250 mL, two mouthfuls of flasks of anaerobic, add 5 ml gained solution, after add 15 ml deionized waters and dilute, then add 60 ml methyl alcohol and fully mix, be warming up to 50 DEG C, react 48 h.After reaction terminates at reduced pressure conditions, controlling bath temperature is 35 DEG C, revolves steaming 30 min and is removed by methyl alcohol, obtain the pre-PPV-3 aqueous solution 20 mL.
2. to get in step 1 in the gained pre-PPV-3 aqueous solution 5 ml 250 mL, two mouthfuls of flasks under oxygen free condition, after the dilution of 15ml deionized water, add 0.2000 g sodium laurylsulfonate SDS (0.0007 mol) wherein, first be warming up to 50 DEG C and treat that sodium laurylsulfonate is dissolved in the water, add 0.2 ml triethylamine (0.0014 mol) again as eliminative reaction catalyzer, continue to be warming up to 80 DEG C, react 3 h and obtain PPV-3 nanoparticle dispersion liquid.The particle diameter of obtained PPV-3 nanoparticle is at 29 ~ 49 nm, and the maximum emission wavelength of nanoparticle dispersion liquid is 467 nm, and has acromion at 443 nm wavelength places.
Embodiment 5
1. that synthesizes with reference to document (J. Am. Chem. Soc.1993,115,10117-10124) under anhydrous and oxygen-free condition is dissolved in 12 mL H containing PPV monomer 0.6895 g (1.965 mmol) without substituted benzene ring
2in O, then the NaOH aqueous solution of 1 M of 1.7 mL is slowly dripped wherein, to put in ice-water bath after stirring reaction 1 h, add the HCl solution termination reaction of 2 M of 3 mL, to dialyse 24 h (removing 12 hours of spending the night with the dialysis tubing that molecular weight is 3500 afterwards, section changes water once every 2 h At All Other Times, adds 500 mL deionized waters at every turn), obtain PPV precursor solution 20 mL.In 250 mL, two mouthfuls of flasks of anaerobic, add 5 ml gained solution, after add 15 ml deionized waters and dilute, then add 60 ml methyl alcohol and fully mix, be warming up to 50 DEG C, react 72 h.After reaction terminates at reduced pressure conditions, controlling bath temperature is 35 DEG C, revolves steaming 30 min and is removed by methyl alcohol, obtain the pre-PPV-4 aqueous solution 20 mL.
2. to get in step 1 in the gained pre-PPV-4 aqueous solution 5 ml 250 mL, two mouthfuls of flasks under oxygen free condition, after the dilution of 15ml deionized water, add 0.2000 g sodium laurylsulfonate SDS (0.0007 mol) wherein, first be warming up to 50 DEG C and treat that sodium laurylsulfonate is dissolved in the water, add 0.2 ml triethylamine (0.0014 mol) again as eliminative reaction catalyzer, continue to be warming up to 80 DEG C, react 3 h and obtain PPV-4 nanoparticle dispersion liquid.The particle diameter of obtained PPV-4 nanoparticle is at 95 ~ 127 nm, and the maximum emission wavelength of nanoparticle dispersion liquid is 467 nm, and has acromion at 441 nm wavelength places.
See accompanying drawing 3, it is the fluorescence spectrum figure of PPV-0, PPV-1, PPV-2, PPV-3 and PPV-4 nanoparticle in water that the embodiment of the present invention 1 ~ 5 provides; As seen from Figure 3, obtained PPV nanoparticle has different transmittings, launch blue shift gradually, and emmission spectrum all has fine structure from PPV-0 to PPV-4.
See accompanying drawing 4, it is the Tyndall effect figure of PPV-0, PPV-1, PPV-2, PPV-3 and PPV-4 nanoparticle aqueous dispersion liquid under laser pen irradiates that the embodiment of the present invention 1 ~ 5 provides; As seen from Figure 4, obtained PPV polymer dispersion liquid has obvious Tyndall effect, and the PPV-N polymer nano-particle that is scattered here and there equably is described in aqueous phase.
See accompanying drawing 5, it is the grain size distribution of PPV-0, PPV-1, PPV-2, PPV-3 and PPV-4 nanoparticle in water that the embodiment of the present invention 1 ~ 5 provides; As seen from Figure 4, the particle diameter of PPV-0 is at 34 ~ 46 nm; The size distribution of PPV-1, in two intervals, is 61 ~ 110 nm and 130 ~ 1000 nm respectively; The particle diameter of PPV-2 is at 5 ~ 8 nm; The particle diameter of PPV-3 is at 29 ~ 49 nm; The particle diameter of PPV-4 is at 95 ~ 127 nm.
Claims (8)
1. the polyparaphenylene that emission wavelength is a controlled sub-ethene conjugated polymer fluorescent nano particles, is characterized in that its structural formula is:
，
Wherein, n and x is positive integer, and x is the number of the effective conjugate unit of polymkeric substance, and n is the number of repeat unit of polymkeric substance, and 1≤x≤n, n≤70.
2. the polyparaphenylene that a kind of emission wavelength according to claim 1 is controlled sub-ethene conjugated polymer fluorescent nano particles, is characterized in that: the scope of its maximum emission wavelength is 467 ~ 491nm.
3. a preparation method for the polyparaphenylene that emission wavelength as claimed in claim 1 is controlled sub-ethene conjugated polymer fluorescent nano particles, is characterized in that comprising the steps:
(1) adopt Wessling sulfonium salt precursor process to obtain the sub-ethene precursor solution of polyparaphenylene, be denoted as pre-PPV solution;
(2) in pre-PPV solution, methyl alcohol is added, the volume ratio of methyl alcohol and pre-PPV solution is 2 ﹕ 1 ~ 7 ﹕ 1, temperature be 40 ~ 60 DEG C, under oxygen free condition, reaction 10 ~ 72 h, again through underpressure distillation removing methyl alcohol, obtain polyparaphenylene sub-ethene conjugated polymer polymers soln, be denoted as pre-PPV-N polymers soln;
(3) in pre-PPV-N polymers soln, tensio-active agent is added, the mass ratio of tensio-active agent and pre-PPV-N polymkeric substance is 3 ﹕ 1 ~ 10 ﹕ 1, described tensio-active agent is Krafft point lower than the ionogenic surfactant of 90 DEG C, and cloud point is higher than the nonionic surface active agent of 70 DEG C; Be react 1 ~ 6 h under the condition of 70 ~ 90 DEG C in temperature, obtain the aqueous dispersion liquid of a kind of polyparaphenylene sub-ethene conjugated polymer fluorescent nano particles.
4. the preparation method of a kind of emission wavelength according to claim 3 is controlled polyparaphenylene sub-ethene conjugated polymer fluorescent nano particles, is characterized in that: described ionogenic surfactant is containing the alkyl-sulphate of 12 ~ 18 carbonatomss, sulfonate, soap or quaternary ammonium salt.
5. the preparation method of the polyparaphenylene sub-ethene conjugated polymer fluorescent nano particles that a kind of emission wavelength according to claim 3 or 4 is controlled, is characterized in that: described ionogenic surfactant is sodium lauryl sulphate or sodium laurylsulfonate.
6. the preparation method of the polyparaphenylene that a kind of emission wavelength according to claim 3 is controlled sub-ethene conjugated polymer fluorescent nano particles, is characterized in that: described nonionic surface active agent is glycerin fatty acid ester, polyoxyethylene-type or EPE polyol EPE.
7. the preparation method of the polyparaphenylene that a kind of emission wavelength according to claim 3 is controlled sub-ethene conjugated polymer fluorescent nano particles, it is characterized in that: by changing the reaction times of the sub-ethene presoma of polyparaphenylene in step (2) and methyl alcohol, obtaining the polyparaphenylene sub-ethene conjugated polymer fluorescent nano particles of different emission.
8. the preparation method of the polyparaphenylene that a kind of emission wavelength according to claim 3 is controlled sub-ethene conjugated polymer fluorescent nano particles, it is characterized in that: the Aqueous dispersions drop of the polyparaphenylene obtained sub-ethene conjugated polymer fluorescent nano particles is coated with or is spun on thin-film carrier surface, after drying, obtain a kind of polyparaphenylene sub-ethene fluorescent nano particles film.
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