CN101338192B - Nanometer modified high molecular fluorescent material and method for preparing same - Google Patents
Nanometer modified high molecular fluorescent material and method for preparing same Download PDFInfo
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- CN101338192B CN101338192B CN2008100221193A CN200810022119A CN101338192B CN 101338192 B CN101338192 B CN 101338192B CN 2008100221193 A CN2008100221193 A CN 2008100221193A CN 200810022119 A CN200810022119 A CN 200810022119A CN 101338192 B CN101338192 B CN 101338192B
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Abstract
The invention discloses a nano-modified polymer fluorescence material which is made from emthylation polystyrene modified by nano-sulfide. The nano-sulfide is selected from one of nano-cadmium sulfide, nano-copper sulfide, nano-zinc sulfide and nano-manganese sulfide. In the preparation method, the polymerization reaction is implemented on 4-vinyl benzyl chlorine and styrene to prepare chloromethyl polystyrene; the hydrosulfuryl methylation is implemented to obtain the emthylation polystyrene; finally, the in-situ synthesis is implemented to obtain the required nano-modified polymer material. The obtained material of the invention has the characteristics of multi-end modification, controllable content of nano-particles, strengthened fluorescence after the polymer modification and fluorescence displacement and is provided with certain application potential in iron detection and photoelectric energy transformation.
Description
Technical field
The present invention relates to a kind of nano-modified macromolecule material, be suitable for application at aspects such as light, electricity, catalysis with fluorescence property.
Background technology
Nano material demonstrates the not available conductive characteristic of body material, photoelectric characteristic, photo-catalysis capability owing to the size quantum effect and with the absorption or the emmission spectrum of change of size, and causes numerous scholars' concern.The body material of composite nano materials employing at present mainly contains unorganic glass, molecular sieve, polymkeric substance etc.Polymkeric substance is compared the stability that can improve nanoparticle widely with other base materials, make nanoparticle controlled in very big size range simultaneously; Finishing coat structure that can the stabilized nanoscale particulate, and then realize microcosmic regulation and control to the nanoparticle special property; The optical property of polymer materials excellence provides good condition for developing novel composite non-linear optical material.
The following two kinds of methods of the general employing of the preparation of nano-modified macromolecule:
(1) adopt ion exchange method that metal ion is introduced polymkeric substance, again by with other reagent react original position synthesizing inorganic nanoparticles, as the preparation of Nano cadmium sulphide modified high molecular:
(2) utilize the monomer of organometallics, carry out random copolymerization or alternating copolymerization, metal ion is introduced polymkeric substance with another kind of free radical as Raolical polymerizable, and then by forming the nanoparticle of metallic sulfide with the reaction of other reagent.As:
New nano-modified macromolecule material and preparation method thereof is provided, realizes control, have special meaning for the application of nonlinear optical material etc. to nanoparticle content in the macromolecular material.
Summary of the invention
The object of the invention provides a kind of nanometer sulfide modified high molecular fluorescent material and preparation method thereof, to obtain the specific polymers structure, is applicable to aspects such as light, electricity, catalysis.
For achieving the above object, the technical solution used in the present invention is: a kind of nanometer modified high molecular fluorescent material, it is modified the thiopurine methyltransferase polystyrene by nanometer sulfide and forms, and described nanometer sulfide is selected from a kind of in Nano cadmium sulphide, nano-copper sulfide, nano-zinc sulfide, the nanometer manganese sulfide.
The preparation method of above-mentioned nanometer modified high molecular fluorescent material may further comprise the steps:
(1) according to mol ratio 1: 10~40 4-vinyl benzyl chloride and vinylbenzene are added in the reaction vessel, add the dibenzoyl peroxide initiator, initiator and monomeric mol ratio are 1: 100~150, under nitrogen protection, stir, carry out polyreaction, the preparation chloromethylated polystyrene, polymeric reaction temperature is at 75~95 ℃;
(2) be 1: 1.2~1.5 to take by weighing chloromethylated polystyrene, the thiocarbamide of step (1) gained respectively according to mol ratio, add N, dinethylformamide is as solvent, and nitrogen protection is stirred down, in oil bath in 100~110 ℃ of insulation reaction 24~30 hours, the back adds soda-lye, continues 110~120 ℃ of following insulation reaction 24~28 hours, after reaction finishes again, neutralize with concentrated sulfuric acid solution, methanol extraction, drying obtains the thiopurine methyltransferase polystyrene;
(3) be to take by weighing thiopurine methyltransferase polystyrene, metal chloride in 5: 1~20: 1 according to the mol ratio of thiopurine methyltransferase and metal chloride, add the DMF dissolving, stirred under the room temperature 4~6 hours, add and the equimolar nine water cure sodium of metal chloride then, stirred under the room temperature 1~2 hour, after reaction finishes, methanol extraction goes out product, washing, ultrasonic concussion washing, remove the inorganics of attachment removal, obtain required nano-modified macromolecule material, described metal chloride is selected from Cadmium chloride fine powder, cupric chloride, zinc chloride or Manganous chloride tetrahydrate.
In the technique scheme, the concentration of described sodium hydroxide solution is 2~3mol/L, and sodium hydroxide solution and reactant solution volume ratio are 1: 100.
The preferred way of realization of technique scheme can be expressed as follows:
The first step adds 4-vinyl benzyl chloride and vinylbenzene in the polymerizing pipe according to certain molar ratio, then adds the dibenzoyl peroxide initiator of monomer molar several 1%, adds and stirs magneton.Vacuumize, charge into nitrogen, repeatedly 3 rear enclosed polymerizing pipes.Start stirring, in oil bath, be heated to 95 ℃, insulation pre-polymerization 1 hour, after cool to 75 ℃, insulation polymerization 48 hours.Reaction finishes the back and add an amount of N in polymerizing pipe, and the dinethylformamide cut back precipitates product in industrial methanol, and drying obtains white chloromethylated polystyrene (PS (CH
2Cl)
x).
Second step was to take by weighing known molecular amount and chloromethyl (CH at 1: 1.2 according to mol ratio
2Cl) chloromethylated polystyrene of content, thiocarbamide add in 100 milliliters of there-necked flasks.Add an amount of N, dinethylformamide solvent and stir magneton, under the nitrogen protection in oil bath in 100 ℃ of insulation reaction 24 hours, the back adds an amount of soda-lye, continues 120 ℃ of following insulation reaction 24 hours again.Reaction neutralizes with concentrated sulfuric acid solution after finishing.Methanol extraction, drying obtains thiopurine methyltransferase polystyrene (PS (CH
2SH)
x).
The 3rd step, according to mol ratio be take by weighing the thiopurine methyltransferase polystyrene at 1: 1, Cadmium chloride fine powder (cupric chloride, zinc chloride, Manganous chloride tetrahydrate) adds in 100 milliliters of there-necked flasks, adds an amount of DMF dissolving, stirred 4 hours under the room temperature.Add and the equimolar nine water cure sodium of Cadmium chloride fine powder then, stirred 2 hours under the room temperature.After reaction finished, methanol extraction went out product, washing, and ultrasonic concussion washing removes the inorganics of attachment removal, obtains pure nano Cadmium Sulfide (cupric sulfide, zinc sulphide, manganese sulfide) and modifies the thiopurine methyltransferase polystyrene.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the material of the present invention's acquisition excites down at xenon source, has fluorescence to produce, than strengthening 4~5 times without nano-modified high molecular fluorescent.
2. in the preparation of nano-modified macromolecule of the present invention,, can control the chloromethylation content in the polymer, and then control the content of nano-modified middle nanoparticle by control 4-vinyl benzyl chloride and cinnamic mol ratio.
3. the material of the present invention's acquisition has the advantages that the multiterminal base is modified, nanoparticle content is controlled, the modified back of polymer fluorescence strengthens and exist the fluorescence displacement, has certain application potential at ion detection, photoelectric energy conversion aspect.
Description of drawings
Fig. 1 is a nano-modified thiopurine methyltransferase polystyrene preparation technology schema among the embodiment one.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: shown in accompanying drawing 1, according to mol ratio 1: 40 0.0005 mole of 4-vinyl benzyl chloride and 0.02 mole of vinylbenzene are added in the polymerizing pipe, then add 0.0002 mole dibenzoyl peroxide initiator, add and stir magneton.Vacuumize, charge into nitrogen, repeatedly 3 rear enclosed polymerizing pipes.Start stirring, in oil bath, be heated to 95 ℃, insulation pre-polymerization 1 hour, after cool to 75 ℃, insulation polymerization 48 hours.Reaction finishes the back and add 5 milliliters of N in polymerizing pipe, dinethylformamide, and cut back precipitates product in 250 milliliters of industrial methanols, and drying obtains white chloromethylated polystyrene (PS (CH
2Cl)
x), yield is 95%.
Then, be to take by weighing that the known molecular amount is 6000, chloromethyl (CH at 1: 1.2 according to mol ratio
2Cl) molar content is 20% chloromethylated polystyrene 1 gram and thiocarbamide 0.2 gram, adds in 100 milliliters of there-necked flasks.Add 30 milliliters of N, dinethylformamide and stir magneton, under the nitrogen protection in oil bath in 110 ℃ of insulation reaction 24 hours, the back adds the strong solution that 0.2g sodium hydroxide and 0.2 ml deionized water are made into, and continues 120 ℃ of following insulation reaction 24 hours again.Reaction neutralizes with concentrated sulfuric acid solution after finishing.Methanol extraction, drying obtains thiopurine methyltransferase polystyrene (PS (CH
2SH)
x), yield is 92% (in chloromethylated polystyrene).
Then, take by weighing Cadmium chloride fine powder 0.1 gram of thiopurine methyltransferase polystyrene 0.2 gram, 2.5 crystal water, add in 100 milliliters of there-necked flasks, add 20 milliliters of N, dinethylformamide, 25 ℃ were stirred 4 hours down.Add 0.18 gram sodium sulphite then, 25 ℃ were stirred 12 hours down.Reaction goes out product with methanol extraction after finishing, washing, and ultrasonic concussion washing removes the inorganics of attachment removal, obtains pure nano CdS and modifies thiopurine methyltransferase polystyrene ((PS (CH
2SH)
xCdS)), yield is 87% (in the thiopurine methyltransferase polystyrene).
Embodiment two: according to mol ratio 1: 40 0.0010 mole of 4-vinyl benzyl chloride and 0.04 mole of vinylbenzene are added in the polymerizing pipe, then add 0.0004 mole dibenzoyl peroxide initiator, add and stir magneton.Vacuumize, charge into nitrogen, repeatedly 3 rear enclosed polymerizing pipes.Start stirring, in oil bath, be heated to 95 ℃, insulation pre-polymerization 1 hour, after cool to 75 ℃, insulation polymerization 48 hours.Reaction finishes the back and add 5 milliliters of N in polymerizing pipe, dinethylformamide, and cut back precipitates product in 250 milliliters of industrial methanols, and drying obtains white chloromethylated polystyrene (PS (CH
2Cl)
x), yield is 94%.
Then, be to take by weighing that the known molecular amount is 7000, chloromethyl (CH at 1: 1.2 according to mol ratio
2Cl) molar content is 18% chloromethylated polystyrene 1 gram and thiocarbamide 0.2 gram, adds in 100 milliliters of there-necked flasks.Add 30 milliliters of N, dinethylformamide and stir magneton, under the nitrogen protection in oil bath in 110 ℃ of insulation reaction 24 hours, the back adds the strong solution that 0.2g sodium hydroxide and 0.2 ml deionized water are made into, and continues 120 ℃ of following insulation reaction 24 hours again.Reaction neutralizes with concentrated sulfuric acid solution after finishing.Methanol extraction, drying obtains thiopurine methyltransferase polystyrene (PS (CH
2SH)
x), yield is 91% (in chloromethylated polystyrene).
Then, take by weighing Cadmium chloride fine powder 0.2 gram of thiopurine methyltransferase polystyrene 0.3 gram, 2.5 crystal water, add in 100 milliliters of there-necked flasks, add 30 milliliters of N, dinethylformamide, 25 ℃ were stirred 4 hours down.Add 0.20 gram sodium sulphite then, 25 ℃ were stirred 12 hours down.Reaction goes out product with methanol extraction after finishing, washing, and ultrasonic concussion washing removes the inorganics of attachment removal, obtains pure nano CdS and modifies thiopurine methyltransferase polystyrene ((PS (CH
2SH)
xCdS)), yield is 83% (in the thiopurine methyltransferase polystyrene).
Claims (3)
1. nanometer modified high molecular fluorescent material is characterized in that: it is modified the thiopurine methyltransferase polystyrene by nanometer sulfide and forms, and described nanometer sulfide is selected from a kind of in Nano cadmium sulphide, nano-copper sulfide, nano-zinc sulfide, the nanometer manganese sulfide; Described modifying method is, according to the mol ratio of thiopurine methyltransferase and metal chloride is to take by weighing thiopurine methyltransferase polystyrene, metal chloride in 5: 1~20: 1, add the DMF dissolving, stirred under the room temperature 4~6 hours, add and the equimolar nine water cure sodium of metal chloride then, stirred under the room temperature 1~2 hour, after reaction finishes, methanol extraction goes out product, washing, ultrasonic concussion washing removes the inorganics of attachment removal, obtain required nano-modified macromolecule material, described metal chloride is selected from Cadmium chloride fine powder, cupric chloride, zinc chloride or Manganous chloride tetrahydrate.
2. the preparation method of a nanometer modified high molecular fluorescent material is characterized in that, may further comprise the steps:
(1) according to mol ratio 1: 10~40 4-vinyl benzyl chloride and vinylbenzene are added in the reaction vessel, add the dibenzoyl peroxide initiator, initiator and monomeric mol ratio are 1: 100~150, under nitrogen protection, stir, carry out polyreaction, the preparation chloromethylated polystyrene, polymeric reaction temperature is at 75~95 ℃;
(2) be 1: 1.2~1.5 to take by weighing chloromethylated polystyrene, the thiocarbamide of step (1) gained respectively according to mol ratio, add N, dinethylformamide is as solvent, and nitrogen protection is stirred down, in oil bath in 100~110 ℃ of insulation reaction 24~30 hours, the back adds soda-lye, continues 110~120 ℃ of following insulation reaction 24~28 hours, after reaction finishes again, neutralize with concentrated sulfuric acid solution, methanol extraction, drying obtains the thiopurine methyltransferase polystyrene;
(3) be to take by weighing thiopurine methyltransferase polystyrene, metal chloride in 5: 1~20: 1 according to the mol ratio of thiopurine methyltransferase and metal chloride, add the DMF dissolving, stirred under the room temperature 4~6 hours, add and the equimolar nine water cure sodium of metal chloride then, stirred under the room temperature 1~2 hour, after reaction finishes, methanol extraction goes out product, washing, ultrasonic concussion washing, remove the inorganics of attachment removal, obtain required nano-modified macromolecule material, described metal chloride is selected from Cadmium chloride fine powder, cupric chloride, zinc chloride or Manganous chloride tetrahydrate.
3. the preparation method of nanometer modified high molecular fluorescent material according to claim 2, it is characterized in that: in the described step (2), the concentration of sodium hydroxide solution is 2~3mol/L, sodium hydroxide solution and reactant solution volume ratio are 1: 100.
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CN103159876A (en) * | 2013-01-30 | 2013-06-19 | 中国科学技术大学 | Preparation method of macromolecule solid acid catalyst based on chlorine ball modification |
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Citations (3)
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US6093236A (en) * | 1998-05-30 | 2000-07-25 | Kansas State University Research Foundation | Porous pellet adsorbents fabricated from nanocrystals |
CN1772837A (en) * | 2005-11-02 | 2006-05-17 | 苏州大学 | Functional luminescent material and its prepn |
CN1944519A (en) * | 2006-06-21 | 2007-04-11 | 华东师范大学 | Nano zinc oxide/poly styrene composite material and its preparing method |
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US6093236A (en) * | 1998-05-30 | 2000-07-25 | Kansas State University Research Foundation | Porous pellet adsorbents fabricated from nanocrystals |
CN1772837A (en) * | 2005-11-02 | 2006-05-17 | 苏州大学 | Functional luminescent material and its prepn |
CN1944519A (en) * | 2006-06-21 | 2007-04-11 | 华东师范大学 | Nano zinc oxide/poly styrene composite material and its preparing method |
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CN103159876A (en) * | 2013-01-30 | 2013-06-19 | 中国科学技术大学 | Preparation method of macromolecule solid acid catalyst based on chlorine ball modification |
CN103159876B (en) * | 2013-01-30 | 2015-12-09 | 中国科学技术大学 | A kind of preparation method of the macromolecule solid acid catalyst based on the modification of chlorine ball |
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