CN101906249A - Method for preparing quantum dot/polyurethane nano crystal composite - Google Patents
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- CN101906249A CN101906249A CN 201010235499 CN201010235499A CN101906249A CN 101906249 A CN101906249 A CN 101906249A CN 201010235499 CN201010235499 CN 201010235499 CN 201010235499 A CN201010235499 A CN 201010235499A CN 101906249 A CN101906249 A CN 101906249A
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Abstract
The invention discloses a method for preparing a quantum dot/polyurethane nano crystal composite, which comprises the following steps of: (1) mixing 1 mol of dibromoneopentyl glycol, 2 mol of imidazoles compound and a tetrahydrofuran solvent, and reacting at 70 DEG C to obtain imidazole glycol; (2) mixing 1-10 mol of imidazole glycol, 1-10 mol of long-chain glycol with weight-average molecular weight of 100-2000, 1.8-20 mol of diisocyanate, a tetrahydrofuran solvent and 2-3 drops of catalyst, and reacting in the nitrogen at 40-60 DEG C to obtain cationic polyurethane; (3) mixing 10-20 ml of cationic polyurethane and 10-20 ml of quantum dot nano crystal solution, stirring for 30 min, removing the tetrahydrofuran solvent by distillation and obtaining the quantum dot/polyurethane nano crystal composite. In the invention, in the combination of the optical property of the quantum dot and the chemical resistance, low temperature resistance and easy processing and molding property of the polyurethane, the transparent and easily processed quantum dot/polyurethane nano crystal composite is prepared. The quantum dot/polyurethane nano crystal composite is expected to be used for the manufacturing of LEDs, sensors, fluorescent probes, optical switches and the like.
Description
Technical field
The present invention relates to a kind of preparation method of quantum dot/polyurethane nano crystal composite.
Background technology
Quantum dot (QDs) refer generally to radius less than or near the semiconductor nano particle (about 1～100nm) of Bohr's exciton radius.When particle size enters nanometer scale, the size confinement will cause quantum effects such as quantum size effect, quantum confined effect, macro quanta tunnel effect and surface effects.Quantum dot-based in the low-dimensional rerum natura different with conventional system and microsystem, show many physicochemical property that are different from macroscopic material, have very wide application prospect at aspects such as nonlinear optics, magneticmedium, catalysis, medicine and functional materialss, will produce deep effect to the sustainable development of life science and information technology and the fundamental research of material sphere simultaneously.
Yet small size and surface effects make the quantum dot surface atom have high activity, extremely unstable, be easy to combine with other atom, promptly quantum dot surface energy height is easy to reunite.In order to bring into play the photoelectric characteristic of quantum dot better, they need be dispersed in the well behaved matrix, and increase the interaction of quantum dot and matrix.For this reason, need modify processing to the quantum dot surface.
Because density polymer is little, be easy to machine-shaping, mechanical mechanics property is good, energy consumption is low and has good dielectricity and biocompatibility, research at present concentrates on polymkeric substance processing is modified on the quantum dot surface.The preparation method of these quantum dot mixtures is simple and temperature required lower, can make the minimum that influences that the optical property of semiconductor nano quantum dot is subjected in preparation process, and material is transparent at visible light near infrared range again.In addition, the adding of semi-conductor nano particles can also effectively remedy carrier mobility in the polymkeric substance, exciton radiant ratio and the lower deficiency of fluorescence quantum efficiency, inorganic nanoparticles and polymkeric substance is had complementary advantages obtain more effectively and economical utilization.
That urethane is that a class has is expandable, elasticity, cohesiveness, wear resistance, lower temperature resistance, solvent resistance, resistance to biodeterioration, be difficult for the high-performance polymer of degraded.By regulating isocyanic ester, long chain diol, the character of the contained functional group of short-chain diol, ratio can be produced the thermoplastic resin of line style or the thermosetting resin of build, its good processing characteristics makes its goods that can make the various performances from plastics to rubber, from soft to hard, thereby is widely used in hard or various fields such as flex foam, elastomer material, coating, binding agent, synthetic leather and fiber.
At present, the polymkeric substance that is used for stablizing quantum dot of bibliographical information mainly is charged long chain alkane and acrylic polymer.The invention is characterized in cation type polyurethane the quantum dot surface is modified, the optical characteristics of quantum dot and the high-performance of urethane are combined, obtain having optical characteristics and stable quantum dot/polyurethane nano crystal composite.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of quantum dot/polyurethane nano crystal composite is provided.
A kind of preparation method of quantum dot/polyurethane nano crystal composite comprises the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol imidazole salts glycol, 1～10mol weight-average molecular weight is 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix are under nitrogen atmosphere, 40～60 ℃ of reaction 18～24h obtain cation type polyurethane;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1Tetrahydrofuran solution and 10～20mL concentration of cation type polyurethane be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Quantum dot nano crystal aqueous solution, stir 30min, revolve to steam and remove solvents tetrahydrofurane, obtain quantum dot/polyurethane nano crystal composite.
A kind of preparation method of quantum dot/polyurethane nano crystal composite comprises the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol imidazole salts glycol, 1～10mol weight-average molecular weight is 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix are under nitrogen atmosphere, 40～60 ℃ of reaction 18～24h obtain cation type polyurethane;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1The tetrahydrofuran solution of cation type polyurethane, with 10～20mL concentration be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Na
2The S aqueous solution, adding 10～20mL concentration again is 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Cd (Ac)
22H
2O or Zn (Ac)
22H
2The aqueous solution of O, original position generates CdS or ZnS quantum dot nano crystal, revolves to steam to remove solvents tetrahydrofurane, obtains quantum dot/polyurethane nano crystal composite.
A kind of preparation method of quantum dot/polyurethane nano crystal composite comprises the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol weight-average molecular weight be 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix, under nitrogen atmosphere, 40～60 ℃ of pre-polymerization 2～3h with 1～10mol imidazole salts diol chain extender reaction, 18～24h, obtain cation type polyurethane again;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1Tetrahydrofuran solution and 10～20mL concentration of cation type polyurethane be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Quantum dot nano crystal aqueous solution, stir 30min, revolve to steam and remove solvents tetrahydrofurane, obtain quantum dot/polyurethane nano crystal composite.
A kind of preparation method of quantum dot/polyurethane nano crystal composite comprises the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol weight-average molecular weight be 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix, under nitrogen atmosphere, 40～60 ℃ of pre-polymerization 2～3h with 1～10mol imidazole salts diol chain extender reaction, 18～24h, obtain cation type polyurethane again;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1The tetrahydrofuran solution of cation type polyurethane, with 10～20mL concentration be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Na
2The S aqueous solution, adding 10～20mL concentration again is 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Cd (Ac)
22H
2O or Zn (Ac)
22H
2The aqueous solution of O, original position generates CdS or ZnS quantum dot nano crystal, revolves to steam to remove solvents tetrahydrofurane, obtains quantum dot/polyurethane nano crystal composite.
Described quantum dot is: a kind of by the stable nanoparticle with fluorescent characteristics of Thiovanic acid, thiohydracrylic acid or N-(2-sulfydryl propionyl) glycine among CdTe, CdSe, CdS, ZnS, CdTe/CdS, CdTe/ZnS, CdSe/CdS, CdSe/ZnS, CdS/ZnS, ZnS/CdS, ZnS/CdS/ZnS, CdSe/CdS or the CdSe/ZnS.
Described glyoxaline compound is: imidazoles, N-Methylimidazole, N-ethyl imidazol(e), N-butyl imidazole.Described long chain diol is: contain 5 and the glycol of above carbonatoms, as 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 2-methyl-2,4-pentanediol, triethylene glycol, dipropylene glycol, polyoxyethylene glycol, both-end hydroxyl polycaprolactone or both-end hydroxyl polylactide.Described vulcabond is: aliphatics and aromatic diisocyanate, as hexyl diisocyanate, octyl group vulcabond, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, ditane-4,4 '-vulcabond, hexamethylene diisocyanate, dicyclohexyl-4,4 '-vulcabond, cyclohexyl-1,4-vulcabond, isophorone diisocyanate.Described catalyzer is: amine compound: triethylenediamine, dimethylcyclohexylamine; Organometallic compound: dibutyl tin dilaurate, dibutyl tin maleate.
The present invention adopts a kind of new polymkeric substance---cation type polyurethane, the quantum dot surface is modified, combine the optical characteristics of quantum dot and urethane resistance to chemical attack, low temperature resistant, resistance to biodeterioration, be difficult for degraded, easy machine-shaping property, prepare transparent, the simple quantum dot/polyurethane nano crystal composite of machine-shaping.Be expected to be used to prepare photoelectric devices such as LED, transmitter, fluorescent probe, optical switch.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment 1CdTe/CdS/ polyurethane nano crystal composite;
Fig. 2 is the transmission electron microscope picture of embodiment 2CdTe/ polyurethane nano crystal composite.
Embodiment
Embodiment 1
Imidazole salts glycol preparation: the 20g dibromoneopentyl glycol is placed 250mL single port flask, add 100mL solvent THF successively, 27g N-ethyl imidazol(e), back flow reaction 15h in 70 ℃ of oil baths.Revolve to steam and remove the THF that desolvates, obtain ethyl imidazol(e) salt glycol.
Cation type polyurethane preparation: under nitrogen protection; be 600 polyoxyethylene glycol successively with the 5.6g weight-average molecular weight; 30mL solvent THF; 2.6mL Toluene-2,4-diisocyanate; the 6-vulcabond joins in the 100mL there-necked flask, drips two catalyzer dibutyl tin dilaurates, pre-polymerization 2h in 50 ℃ of oil baths; the ethyl imidazol(e) salt glycol that adds the 5.0g preparation again, reaction 22h.Methanol extraction obtains cation type polyurethane.
The preparation of CdTe/CdS/ polyurethane nano crystal composite: with 20mL concentration is 0.1mg mL
-1Urethane-THF solution and 10mL concentration be 1.80 * 10
-3Mol mL
-1Particle diameter be the stable CdTe/CdS aqueous solution of thiohydracrylic acid of 2.5nm, stir 30min, revolve to steam and remove the THF that desolvates, obtain the CdTe/CdS/ polyurethane nano crystal composite.Product is removed unreacted quantum dot CdTe/CdS through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdTe/CdS/ polyurethane nano crystal composite.
Embodiment 2
The preparation of imidazole salts glycol: the 30g dibromoneopentyl glycol is placed 250mL single port flask, add 100mL solvent THF successively, 18mL N-Methylimidazole places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain the methylimidazole salt glycol.
Cation type polyurethane preparation: under nitrogen protection; successively with 3.2g methylimidazole salt glycol; 12.7g weight-average molecular weight is 106 polyoxyethylene glycol; 30mL solvent THF; 1.8mL Toluene-2,4-diisocyanate; the 4-vulcabond joins in the 100mL there-necked flask, drips two catalyzer dibutyl tin dilaurates, places 40 ℃ of oil baths to react 24h.Methanol extraction obtains cation type polyurethane.
The preparation of CdTe/ polyurethane nano crystal composite: with 10mL concentration is 0.1mg mL
-1Urethane-THF solution and 10mL concentration be 1.25 * 10
-3Mol mL
-1Particle diameter be the stable CdTe aqueous solution of Thiovanic acid of 2.0nm, stir 30min, revolve to steam and remove the THF that desolvates, obtain the CdTe/ polyurethane nano crystal composite.Product is removed unreacted quantum dot CdTe through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdTe/ polyurethane nano crystal composite.
Embodiment 3
The preparation of imidazole salts glycol: the 15g dibromoneopentyl glycol is placed 250mL single port flask, add 100mL solvent THF successively, 9mL N-Methylimidazole places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain the methylimidazole salt glycol.
Cation type polyurethane preparation: under nitrogen protection; successively with the methylimidazole salt glycol of 1.4g preparation; 1.0g molecular weight is 1400 both-end hydroxyl polycaprolactone; 30mL solvent THF; 6.3mL hexyl diisocyanate joins in the 100mL there-necked flask; drip two catalyzer dibutyl tin maleates, place 50 ℃ of oil baths to react 24h.Methanol extraction obtains cation type polyurethane.
The preparation of CdTe/ZnS/ polyurethane nano crystal composite: with 10mL concentration is 0.1mg mL
-1Urethane-THF solution and 10mL concentration be 1.25 * 10
-3Mol mL
-1Particle diameter be the stable CdTe/ZnS aqueous solution of thiohydracrylic acid of 3.0nm, stir 30min, revolve to steam and remove the THF that desolvates, precipitation obtains the CdTe/ZnS/ polyurethane nano crystal composite.Product is removed unreacted quantum dot CdTe/ZnS through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdTe/ZnS/ polyurethane nano crystal composite.
Embodiment 4
The preparation of imidazole salts glycol: the 30g dibromoneopentyl glycol is placed 250mL single port flask, add 100mL solvent THF successively, 18mL N-Methylimidazole places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain the methylimidazole salt glycol.
Cation type polyurethane preparation: under nitrogen protection; successively with 3.2g methylimidazole salt glycol; 12.7g weight-average molecular weight is 106 polyoxyethylene glycol; 30mL solvent THF; 1.8mL Toluene-2,4-diisocyanate; the 4-vulcabond joins in the 100mL there-necked flask, drips two catalyzer triethylenediamines, places 40 ℃ of oil baths to react 24h.Methanol extraction obtains cation type polyurethane.
The preparation of ZnS/ polyurethane nano crystal composite: with 20mL concentration is 0.1mg mL
-1Urethane-THF solution and 10mL concentration be 1.25 * 10
-3Mol mL
-1Na
2The S aqueous solution stirs 30min, and then adding 10mL concentration is 1.25 * 10
-3Mol mL
-1Zn (Ac)
22H
2The O aqueous solution forms ZnS quantum dot nano crystal by the original position method of formation, revolves to steam to remove the THF that desolvates, and precipitation obtains quantum dot/polyurethane nano crystal composite.Product is removed unreacted reactant through washed several times with water, and vacuum is placed 72h, obtains exsiccant ZnS/ polyurethane nano crystal composite.
Embodiment 5
The preparation of imidazole salts glycol: the 26.2g dibromoneopentyl glycol is placed 250mL single port flask, add the 13.6g imidazoles successively, 100mL solvent THF places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain the imidazole salts glycol;
The cation type polyurethane preparation: with 1mol imidazole salts glycol, the 1mol weight-average molecular weight is 106 polyoxyethylene glycol, 1.8mol octyl group vulcabond, and 50mL solvent THF, 2 catalyzer dibutyl tin dilaurates mix, under nitrogen atmosphere, 40 ℃ of reaction 18h.Methanol extraction obtains cation type polyurethane;
The preparation of CdSe/CdS/ polyurethane nano crystal composite: with 10mL concentration is 0.1mg mL
-1Urethane-THF solution and 10mL concentration be 1.25 * 10
-3Mol mL
-1The stable CdSe/CdS aqueous solution of N-(2-sulfydryl propionyl) glycine, stir 30min, revolve to steam and remove the THF that desolvates, precipitation obtains the CdSe/CdS/ polyurethane nano crystal composite.Product is removed the unreacted quantum dot through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdSe/CdS/ polyurethane nano crystal composite.
Embodiment 6
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add 2mol N-butyl imidazole successively, 200mL solvent THF places 70 ℃ of oil bath back flow reaction 24h.Revolve to steam and remove the THF that desolvates, obtain butyl imidazole salt glycol;
Cation type polyurethane preparation: with 10mol butyl imidazole salt glycol, the 10mol weight-average molecular weight is 2000 both-end hydroxyl polylactide, 20mol cyclohexyl-1, the 4-vulcabond, 100mL solvent THF, 3 catalyzer dibutyl tin maleates mix, under nitrogen atmosphere, and 60 ℃ of reaction 24h.Methanol extraction obtains cation type polyurethane;
The preparation of CdSe/ polyurethane nano crystal composite: with 20mL concentration is 0.2mg mL
-1Urethane-THF solution and 20mL concentration be 2.5 * 10
-2Mol mL
-1The stable CdSe aqueous solution of thiohydracrylic acid, stir 30min, revolve to steam and remove the THF that desolvates, precipitation obtains the CdSe/ polyurethane nano crystal composite.Product is removed the unreacted quantum dot through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdSe/ polyurethane nano crystal composite.
Embodiment 7
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add 2mol N-ethyl imidazol(e) successively, 100mL solvent THF places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain ethyl imidazol(e) salt glycol;
Cation type polyurethane preparation: with 1mol ethyl imidazol(e) salt glycol, the 1mol weight-average molecular weight be 104 1, the 5-pentanediol, 1.8mol dicyclohexyl-4,4 '-vulcabond, 50mL solvent THF, 2 catalyzer dimethylcyclohexylamines mix, under nitrogen atmosphere, and 40 ℃ of reaction 18h.Methanol extraction obtains cation type polyurethane;
The preparation of CdS/ polyurethane nano crystal composite: with 10mL concentration is 0.1mg mL
-1Urethane-THF solution, with 10mL concentration be 1.25 * 10
-3Mol mL
-1Na
2The S aqueous solution, adding 10mL concentration again is 1.25 * 10
-3Mol mL
-1Cd (Ac)
22H
2The aqueous solution of O, original position generate CdS quantum dot nano crystal, revolve to steam to remove the THF that desolvates, and precipitation obtains the CdS/ polyurethane nano crystal composite.Product is removed unreacted reactant through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdS/ polyurethane nano crystal composite.
Embodiment 8
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add 2mol N-butyl imidazole successively, 200mL solvent THF places 70 ℃ of oil bath back flow reaction 24h.Revolve to steam and remove the THF that desolvates, obtain butyl imidazole salt glycol;
The cation type polyurethane preparation: with 10mol butyl imidazole salt glycol, the 10mol weight-average molecular weight is 2000 polyoxyethylene glycol, 20mol ditane-4,4 '-vulcabond, 100mL solvent THF, 3 catalyzer triethylenediamines mix, under nitrogen atmosphere, 60 ℃ of reaction 24h.Methanol extraction obtains cation type polyurethane;
The preparation of ZnS/ polyurethane nano crystal composite: with 20mL concentration is 0.2mg mL
-1Urethane-THF solution, with 20mL concentration be 2.5 * 10
-2Mol mL
-1Na
2The S aqueous solution, adding 20mL concentration again is 2.5 * 10
-2Mol mL
-1Zn (Ac)
22H
2The aqueous solution of O, original position generate ZnS quantum dot nano crystal, revolve to steam to remove the THF that desolvates, and precipitation obtains the ZnS/ polyurethane nano crystal composite.Product is removed unreacted reactant through washed several times with water, and vacuum is placed 72h, obtains exsiccant ZnS/ polyurethane nano crystal composite.
Embodiment 9
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add 2mol N-Methylimidazole successively, 100mL solvent THF places, back flow reaction 10h in 70 ℃ of oil baths.Revolve to steam and remove the THF that desolvates, obtain the methylimidazole salt glycol;
Cation type polyurethane preparation: with the 1mol weight-average molecular weight is 104 neopentyl glycol, 1.8mol isophorone diisocyanate, 50mL solvent THF, 2 catalyzer dimethylcyclohexylamines mix, under nitrogen atmosphere, 40 ℃ of pre-polymerization 2h are again with 1mol imidazole salts diol chain extender reaction 18h.Methanol extraction obtains cation type polyurethane;
The preparation of ZnS/CdS/ polyurethane nano crystal composite: with 10mL concentration is 0.1mg mL
-1Urethane-THF solution and 10mL concentration be 1.25 * 10
-3Mol mL
-1The stable ZnS/CdS aqueous solution of Thiovanic acid, stir 30min, revolve to steam and remove the THF that desolvates, precipitation obtains the ZnS/CdS/ polyurethane nano crystal composite.Product is removed the unreacted quantum dot through washed several times with water, and vacuum is placed 72h, obtains exsiccant ZnS/CdS/ polyurethane nano crystal composite.
Embodiment 10
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add 2mol N-ethyl imidazol(e) successively, 200mL solvent THF places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain ethyl imidazol(e) salt glycol;
Cation type polyurethane preparation: be 2000 both-end hydroxyl polylactide with the 10mol weight-average molecular weight, 20mol dicyclohexyl-4,4 '-vulcabond, 100mL solvent THF, 3 catalyzer dibutyl tin dilaurates mix, under nitrogen atmosphere, 60 ℃ of pre-polymerization 3h are again with 10mol ethyl imidazol(e) salt diol chain extender reaction 24h.Methanol extraction obtains cation type polyurethane;
The preparation of ZnS/CdS/ZnS/ polyurethane nano crystal composite: with 20mL concentration is 0.2mg mL
-1Urethane-THF solution and 20mL concentration be 2.5 * 10
-2Mol mL
-1The stable ZnS/CdS/ZnS aqueous solution of N-(2-sulfydryl propionyl) glycine, stir 30min, revolve to steam and remove the THF that desolvates, obtain the ZnS/CdS/ZnS/ polyurethane nano crystal composite.Product is removed the unreacted quantum dot through washed several times with water, and vacuum is placed 72h, obtains exsiccant ZnS/CdS/ZnS/ polyurethane nano crystal composite.
Embodiment 11
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add the 2mol imidazoles successively, 100mL solvent THF places 70 ℃ of oil bath back flow reaction 10h.Revolve to steam and remove the THF that desolvates, obtain the imidazole salts glycol;
Cation type polyurethane preparation: with the 1mol weight-average molecular weight be 118 1,6-hexylene glycol, 1.8mol hexamethylene diisocyanate, 50mL solvent THF, 2 catalyzer dibutyl tin dilaurates mix, under nitrogen atmosphere, 40 ℃ of pre-polymerization 2h are again with 1mol imidazole salts diol chain extender reaction 18h.Methanol extraction obtains cation type polyurethane;
The preparation of CdS/ polyurethane nano crystal composite: with 10mL concentration is 0.1mg mL
-1Urethane-THF solution, with 10mL concentration be 1.25 * 10
-3Mol mL
-1Na
2The S aqueous solution, adding 10mL concentration again is 1.25 * 10
-3Mol mL
-1Cd (Ac)
22H
2The aqueous solution of O, original position generate CdS quantum dot nano crystal, revolve to steam to remove the THF that desolvates, and obtain the CdS/ polyurethane nano crystal composite.Product is removed unreacted reactant through washed several times with water, and vacuum is placed 72h, obtains exsiccant CdS/ polyurethane nano crystal composite.
Embodiment 12
The preparation of imidazole salts glycol: the 1mol dibromoneopentyl glycol is placed 250mL single port flask, add 2mol N-butyl imidazole successively, 200mL solvent THF places, back flow reaction 24h in 70 ℃ of oil baths.Revolve to steam and remove the THF that desolvates, obtain butyl imidazole salt glycol;
Cation type polyurethane preparation: be 2000 both-end hydroxyl polylactide with the 10mol weight-average molecular weight, the 20mol Toluene-2,4-diisocyanate, the 4-vulcabond, 100mL solvent THF, 3 catalyzer dibutyl tin maleates mix, under nitrogen atmosphere, 60 ℃ of pre-polymerization 3h are again with 10mol imidazole salts diol chain extender reaction 24h.Methanol extraction obtains cation type polyurethane;
The preparation of ZnS/ polyurethane nano crystal composite: with 20mL concentration is 0.2mg mL
-1Urethane-THF solution, with 20mL concentration be 2.5 * 10
-2Mol mL
-1Na
2The S aqueous solution, adding 20mL concentration again is 2.5 * 10
-2Mol mL
-1Zn (Ac)
22H
2The aqueous solution of O, original position generate ZnS quantum dot nano crystal, revolve to steam to remove the THF that desolvates, and obtain the ZnS/ polyurethane nano crystal composite.Product is removed unreacted reactant through washed several times with water, and vacuum is placed 72h, obtains exsiccant ZnS/ polyurethane nano crystal composite.
The part experimental data
The burst of ultraviolel wavelength is 400nm, and the fluorescence efficiency object of reference is rhodamine 6B (fluorescence efficiency is 97%).
Example 1 product is yellow elastomerics, its emmission spectrum and CdTe/CdS aqueous solution basically identical, and a small amount of blue shift of peak position, emission 539nm yellow fluorescence under the 400nm ultraviolet excitation, the peak width at half height 3nm that narrows down slightly is 54nm.TEM shows quantum dot size homogeneous, is about 3nm, and is uniformly dispersed, and does not have and reunites.
Example 2 products are green powders, its emmission spectrum and CdTe aqueous solution basically identical, and a small amount of blue shift of peak position, emission 528nm green fluorescence under the 400nm ultraviolet excitation, peak width at half height is very close, is 47nm.TEM shows quantum dot size homogeneous, is about 2.5nm, and is uniformly dispersed, and does not have and reunites.
Claims (9)
1. the preparation method of a quantum dot/polyurethane nano crystal composite is characterized in that comprising the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol imidazole salts glycol, 1～10mol weight-average molecular weight is 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix are under nitrogen atmosphere, 40～60 ℃ of reaction 18～24h obtain cation type polyurethane;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1Tetrahydrofuran solution and 10～20mL concentration of cation type polyurethane be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Quantum dot nano crystal aqueous solution, stir 30min, revolve to steam and remove solvents tetrahydrofurane, obtain quantum dot/polyurethane nano crystal composite.
2. the preparation method of a quantum dot/polyurethane nano crystal composite is characterized in that comprising the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol imidazole salts glycol, 1～10mol weight-average molecular weight is 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix are under nitrogen atmosphere, 40～60 ℃ of reaction 18～24h obtain cation type polyurethane;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1The tetrahydrofuran solution of cation type polyurethane, with 10～20mL concentration be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Na
2The S aqueous solution, adding 10～20mL concentration again is 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Cd (Ac)
22H
2O or Zn (Ac)
22H
2The aqueous solution of O, original position generates CdS or ZnS quantum dot nano crystal, revolves to steam to remove solvents tetrahydrofurane, obtains quantum dot/polyurethane nano crystal composite.
3. the preparation method of a quantum dot/polyurethane nano crystal composite is characterized in that comprising the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol weight-average molecular weight be 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix, under nitrogen atmosphere, 40～60 ℃ of pre-polymerization 2～3h with 1～10mol imidazole salts diol chain extender reaction, 18～24h, obtain cation type polyurethane again;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1Tetrahydrofuran solution and 10～20mL concentration of cation type polyurethane be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Quantum dot nano crystal aqueous solution, stir 30min, revolve to steam and remove solvents tetrahydrofurane, obtain quantum dot/polyurethane nano crystal composite.
4. the preparation method of a quantum dot/polyurethane nano crystal composite is characterized in that comprising the steps:
1) with the 1mol dibromoneopentyl glycol, the 2mol glyoxaline compound, 100～200mL solvents tetrahydrofurane is mixed, and in 70 ℃ of reaction 10～24h, obtains the imidazole salts glycol;
2) with 1～10mol weight-average molecular weight be 100～2000 long chain diol, 1.8～20mol vulcabond, 50～100mL solvents tetrahydrofurane, 2～3 catalyst mix, under nitrogen atmosphere, 40～60 ℃ of pre-polymerization 2～3h with 1～10mol imidazole salts diol chain extender reaction, 18～24h, obtain cation type polyurethane again;
3) be 0.1～0.2mg mL with 10～20mL concentration
-1The tetrahydrofuran solution of cation type polyurethane, with 10～20mL concentration be 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Na
2The S aqueous solution, adding 10～20mL concentration again is 1.25 * 10
-3～2.5 * 10
-2Mol mL
-1Cd (Ac)
22H
2O or Zn (Ac)
22H
2The aqueous solution of O, original position generates CdS or ZnS quantum dot nano crystal, revolves to steam to remove solvents tetrahydrofurane, obtains quantum dot/polyurethane nano crystal composite.
5. according to the preparation method of claim 1 or 3 described a kind of quantum dot/polyurethane nano crystal composites, it is characterized in that described quantum dot is: a kind of among CdTe, CdSe, CdS, ZnS, CdTe/CdS, CdTe/ZnS, CdSe/CdS, CdSe/ZnS, CdS/ZnS, ZnS/CdS, ZnS/CdS/ZnS, CdSe/CdS or the CdSe/ZnS by the stable nanoparticle of Thiovanic acid, thiohydracrylic acid or N-(2-sulfydryl propionyl) glycine with fluorescent characteristics.
6. according to the preparation method of claim 1,2,3 or 4 described a kind of quantum dot/polyurethane nano crystal composites, it is characterized in that described glyoxaline compound is: imidazoles, N-Methylimidazole, N-ethyl imidazol(e), N-butyl imidazole.
7. according to the preparation method of claim 1,2,3 or 4 described a kind of quantum dot/polyurethane nano crystal composites, it is characterized in that described long chain diol is: contain 5 and the glycol of above carbonatoms, as 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 2-methyl-2,4-pentanediol, triethylene glycol, dipropylene glycol, polyoxyethylene glycol, both-end hydroxyl polycaprolactone or both-end hydroxyl polylactide.
8. according to the preparation method of claim 1,2,3 or 4 described a kind of quantum dot/polyurethane nano crystal composites, it is characterized in that described vulcabond is: aliphatics and aromatic diisocyanate, as hexyl diisocyanate, octyl group vulcabond, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, ditane-4,4 '-vulcabond, hexamethylene diisocyanate, dicyclohexyl-4,4 '-vulcabond, cyclohexyl-1,4-vulcabond, isophorone diisocyanate.
9. according to the preparation method of claim 1,2,3 or 4 described a kind of quantum dot/polyurethane nano crystal composites, it is characterized in that described catalyzer is: amine compound: triethylenediamine, dimethylcyclohexylamine; Organometallic compound: dibutyl tin dilaurate, dibutyl tin maleate.
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|---|---|---|---|---|
| CN103709731A (en) * | 2013-12-27 | 2014-04-09 | Tcl集团股份有限公司 | Quantum dot/polyurethane nano crystal complex and preparation method thereof as well as colorful conversion film |
| CN105446003A (en) * | 2015-12-01 | 2016-03-30 | 苏州星烁纳米科技有限公司 | Quantum dot dispersion, preparation method, backlight module and display device |
| CN109504368A (en) * | 2018-11-19 | 2019-03-22 | 太原科技大学 | A kind of CDs/TPU fluorescence nano composite material preparation method |
| CN111393985A (en) * | 2020-04-03 | 2020-07-10 | 佛山市新量子环保材料有限公司 | Modified polyurethane water-based paint and preparation method thereof |
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| US20070170418A1 (en) * | 2005-12-02 | 2007-07-26 | Bowers Michael J | Broad-emission nanocrystals and methods of making and using same |
| US20070249747A1 (en) * | 2004-07-07 | 2007-10-25 | Kaneka Corporation | Process for Producing Polymer-Modified Nanoparticle |
| CN101723311A (en) * | 2009-11-06 | 2010-06-09 | 武汉理工大学 | Magnetic flourescent nano material for magnetic-photo sensor and preparation method thereof |
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| US20070249747A1 (en) * | 2004-07-07 | 2007-10-25 | Kaneka Corporation | Process for Producing Polymer-Modified Nanoparticle |
| CN1687225A (en) * | 2005-03-26 | 2005-10-26 | 吉林大学 | Method for preparing transparent optical material of polymer in high nano phase |
| US20070170418A1 (en) * | 2005-12-02 | 2007-07-26 | Bowers Michael J | Broad-emission nanocrystals and methods of making and using same |
| CN101723311A (en) * | 2009-11-06 | 2010-06-09 | 武汉理工大学 | Magnetic flourescent nano material for magnetic-photo sensor and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709731A (en) * | 2013-12-27 | 2014-04-09 | Tcl集团股份有限公司 | Quantum dot/polyurethane nano crystal complex and preparation method thereof as well as colorful conversion film |
| CN105446003A (en) * | 2015-12-01 | 2016-03-30 | 苏州星烁纳米科技有限公司 | Quantum dot dispersion, preparation method, backlight module and display device |
| CN109504368A (en) * | 2018-11-19 | 2019-03-22 | 太原科技大学 | A kind of CDs/TPU fluorescence nano composite material preparation method |
| CN109504368B (en) * | 2018-11-19 | 2020-05-12 | 太原科技大学 | Preparation method of CDs/TPU fluorescent nano composite material |
| CN111393985A (en) * | 2020-04-03 | 2020-07-10 | 佛山市新量子环保材料有限公司 | Modified polyurethane water-based paint and preparation method thereof |
| CN111393985B (en) * | 2020-04-03 | 2021-12-14 | 佛山市新量子环保材料有限公司 | Modified polyurethane water-based paint and preparation method thereof |
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