CN102241809A - Process for preparing water-soluble red organic polymer luminescent material - Google Patents
Process for preparing water-soluble red organic polymer luminescent material Download PDFInfo
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Abstract
The invention provides a process for preparing a water-soluble red organic polymer luminescent material. The process has the following beneficial effects: 3-carboxyl polythiophene is taken as the main raw material; the water-soluble carboxyl is imported into the side chain of the polythiophene; the polymer has good film forming property, water solubility and stability; the pollution caused by the organic solvents in the process of processing the polymer is reduced; and the production cost of the polymer is effectively lowered. The common organic luminescent polymer compounds are oil-soluble, such as polythiophene compounds, and because such strongly polar organic solvents as trichloromethane, tetrahydrofuran and the like are used in the process of the processing the compounds, serious pollution is caused and the compounds have certain environmental loads; therefore the compounds are restricted from practical application.
Description
Technical field
The present invention relates to a kind of preparation technology of red illuminating material, be specifically related to a kind of preparation technology of water miscible red organic macromolecular LED material.
Background technology
The organic macromolecular LED material is the development trend of following luminescent material and display material.Polythiophene has a lot of advantages, for example: good film-forming properties, thermostability, high luminous efficiency, lower exciting voltage.So the compound of Polythiophene series has obtained practical application widely.Polythiophene has good solubility and film-forming properties in polar organic solvent (trichloromethane, methylene dichloride and tetrahydrofuran (THF)), but its drawback is apparent, is exactly that the environmental pollution that brings of the use of organic solvent is big, has improved production cost.
Summary of the invention
The objective of the invention is to solve the existing problem in the above-mentioned field, the preparation technology of a kind of water miscible red organic macromolecular LED material with low cost is provided.
For achieving the above object, the technical solution used in the present invention is:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes backflow 2 hours with the thionyl chloride of 1-1.2 mole, the ethanol, methyl alcohol or the propyl alcohol that add after the 1-1.2 mole is made with extra care reflux again, the reaction beginning added the pyridine of 2-5ml in back 1 hour, continue reaction 4-6 hour, after reaction finishes, the ether that adds 30-100ml, the water repetitive scrubbing is removed ethanol, methyl alcohol or propyl alcohol, pyridinium salt and thionyl chloride, and then Calcium Chloride Powder Anhydrous, anhydrous potassium sulfate or the anhydrous magnesium sulfate of adding 5-10 gram, dry 24-36 hour; After removing by filter calcium chloride, vitriolate of tartar or sal epsom, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
2) polymerization
The monomer of getting the step 1) preparation of 0.1-0.5mol is dissolved in the methyl-sulphoxide of 10-30ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.001-0.05mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 10-20ml tetrahydrofuran (THF), and then add sodium hydroxide or the potassium hydroxide of 0.1-0.5ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
The treating process of described ethanol, methyl alcohol or propyl alcohol is: ethanol, methyl alcohol or the propyl alcohol of getting 1000ml were to the iodine backflow that wherein adds 5-10 gram magnesium powder and 1-2 gram 48-36 hour, and distillation obtains purified ethanol, methyl alcohol or propyl alcohol.
The present invention has imported water miscible carboxyl on polyphosphazene polymer thiophene side chain, polymkeric substance has good film-forming properties, water-soluble and stable, has reduced the pollution that its work in-process organic solvent brings, and has effectively reduced its production cost.
Description of drawings
Fig. 1 is the illuminated diagram of the water miscible red organic macromolecular LED material for preparing of the present invention, and wherein X-coordinate is a photon absorbing intensity, and ordinate zou is a wavelength.
Embodiment
Embodiment 1:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes with 1 mole thionyl chloride and refluxed 2 hours, add 1 mole of alcohol reflux after refining again, the reaction beginning added the pyridine of 2ml in back 1 hour, continued reaction 4 hours, after reaction finishes, add the ether of 30ml, the water repetitive scrubbing is removed ethanol, pyridinium salt and thionyl chloride, and then add the Calcium Chloride Powder Anhydrouss of 5 grams, dry 24 hours; After removing by filter calcium chloride, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
Described alcoholic acid treating process is: the ethanol of getting 1000ml refluxed 36 hours to the iodine that wherein adds 5 gram magnesium powder and 1 gram, and distillation obtains purified ethanol.
2) polymerization
The monomer of getting the step 1) preparation of 0.1mol is dissolved in the methyl-sulphoxide of 10ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.001mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 10ml tetrahydrofuran (THF), and then add the sodium hydroxide of 0.1ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
Embodiment 2:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes with 1.1 moles thionyl chloride and refluxed 2 hours, add 1.1 moles of methanol eddies after refining again, the reaction beginning added the pyridine of 3.5ml in back 1 hour, continued reaction 5 hours, after reaction finishes, add the ether of 60ml, the water repetitive scrubbing is removed methyl alcohol, pyridinium salt and thionyl chloride, and then add the anhydrous potassium sulfates of 7 grams, dry 36 hours; After removing by filter vitriolate of tartar, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
The treating process of described methyl alcohol is: the methyl alcohol of getting 1000ml refluxed 48 hours to the iodine that wherein adds 7 gram magnesium powder and 1.5 grams, and distillation obtains purified methyl alcohol.
2) polymerization
The monomer of getting the step 1) preparation of 0.3mol is dissolved in the methyl-sulphoxide of 20ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.01mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 15ml tetrahydrofuran (THF), and then add the potassium hydroxide of 0.3ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
Embodiment 3:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes with 1.2 moles thionyl chloride and refluxed 2 hours, add 1.2 moles of propyl alcohol after refining again and reflux, the reaction beginning added the pyridine of 5ml in back 1 hour, continued reaction 6 hours, after reaction finishes, add the ether of 100ml, the water repetitive scrubbing is removed propyl alcohol, pyridinium salt and thionyl chloride, and then add the anhydrous magnesium sulfates of 10 grams, dry 28 hours; After removing by filter sal epsom, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
The treating process of described propyl alcohol is: the propyl alcohol of getting 1000ml refluxed 38 hours to the iodine that wherein adds 10 gram magnesium powder and 2 grams, and distillation obtains the purified propyl alcohol.
2) polymerization
The monomer of getting the step 1) preparation of 0.5mol is dissolved in the methyl-sulphoxide of 30ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.05mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 20ml tetrahydrofuran (THF), and then add the sodium hydroxide of 0.5ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
Embodiment 4:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes with 1.15 moles thionyl chloride and refluxed 2 hours, add 1.15 moles of alcohol refluxs after refining again, the reaction beginning added the pyridine of 4ml in back 1 hour, continued reaction 4.5 hours, after reaction finishes, add the ether of 80ml, the water repetitive scrubbing is removed ethanol, pyridinium salt and thionyl chloride, and then add the anhydrous magnesium sulfates of 9 grams, dry 30 hours; After removing by filter sal epsom, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
Described alcoholic acid treating process is: the ethanol of getting 1000ml refluxed 40 hours to the iodine that wherein adds 8 gram magnesium powder and 1.8 grams, and distillation obtains purified ethanol.
2) polymerization
The monomer of getting the step 1) preparation of 0.2mol is dissolved in the methyl-sulphoxide of 15ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.005mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 12ml tetrahydrofuran (THF), and then add the potassium hydroxide of 0.15ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
Embodiment 5:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes with 1.05 moles thionyl chloride and refluxed 2 hours, add 1.05 moles of methanol eddies after refining again, the reaction beginning added the pyridine of 3ml in back 1 hour, continued reaction 5.5 hours, after reaction finishes, add the ether of 45ml, the water repetitive scrubbing is removed methyl alcohol, pyridinium salt and thionyl chloride, and then add the Calcium Chloride Powder Anhydrouss of 6 grams, dry 32 hours; After removing by filter calcium chloride, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
The treating process of described methyl alcohol is: the methyl alcohol of getting 1000ml refluxed 45 hours to the iodine that wherein adds 6 gram magnesium powder and 1.3 grams, and distillation obtains purified methyl alcohol.
2) polymerization
The monomer of getting the step 1) preparation of 0.4mol is dissolved in the methyl-sulphoxide of 25ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.02mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 18ml tetrahydrofuran (THF), and then add the sodium hydroxide of 0.45ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
Embodiment 6:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes with 1.2 moles thionyl chloride and refluxed 2 hours, add 1.2 moles of propyl alcohol after refining again and reflux, the reaction beginning added the pyridine of 4.5ml in back 1 hour, continued reaction 6 hours, after reaction finishes, add the ether of 90ml, the water repetitive scrubbing is removed propyl alcohol, pyridinium salt and thionyl chloride, and then add the anhydrous potassium sulfates of 8 grams, dry 26 hours; After removing by filter vitriolate of tartar, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
The treating process of described propyl alcohol is: the propyl alcohol of getting 1000ml refluxed 42 hours to the iodine that wherein adds 9 gram magnesium powder and 1.6 grams, and distillation obtains the purified propyl alcohol.
2) polymerization
The monomer of getting the step 1) preparation of 0.1mol is dissolved in the methyl-sulphoxide of 10ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.04mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 16ml tetrahydrofuran (THF), and then add the potassium hydroxide of 0.4ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
As can be seen from Figure 1, synthetic luminescent material, its emission wavelength are about 660nm, and its wavelength region just within the red light scope, shows that it is a kind of red illuminating material.
Claims (2)
1. the preparation technology of a water miscible red organic macromolecular LED material is characterized in that:
1) monomeric preparation
Get 1 mole 2,5-two bromos-3-carboxylic acid group thiophene mixes backflow 2 hours with the thionyl chloride of 1-1.2 mole, the ethanol, methyl alcohol or the propyl alcohol that add after the 1-1.2 mole is made with extra care reflux again, the reaction beginning added the pyridine of 2-5ml in back 1 hour, continue reaction 4-6 hour, after reaction finishes, the ether that adds 30-100ml, the water repetitive scrubbing is removed ethanol, methyl alcohol or propyl alcohol, pyridinium salt and thionyl chloride, and then Calcium Chloride Powder Anhydrous, anhydrous potassium sulfate or the anhydrous magnesium sulfate of adding 5-10 gram, dry 24-36 hour; After removing by filter calcium chloride, vitriolate of tartar or sal epsom, ether is removed in distillation, and frozen drying obtained purified monomer in 48 hours;
2) polymerization
The monomer of getting the step 1) preparation of 0.1-0.5mol is dissolved in the methyl-sulphoxide of 10-30ml anhydrous and oxygen-free, and then Iron triperchlorate's catalyzer of adding 0.001-0.05mol, under argon shield, refluxed 196 hours, after reaction stops, remove monomer and catalyzer with hydrochloric acid and methanol wash, the product frozen drying is got polymkeric substance;
3) hydrolysis
Get the 0.1mol polymkeric substance and join in the 10-20ml tetrahydrofuran (THF), and then add sodium hydroxide or the potassium hydroxide of 0.1-0.5ml, refluxing in argon shield got water miscible red organic macromolecular LED material in 400 hours.
2. the preparation technology of water miscible red organic macromolecular LED material according to claim 1, it is characterized in that: the treating process of described ethanol, methyl alcohol or propyl alcohol is: ethanol, methyl alcohol or the propyl alcohol of getting 1000ml were to the iodine backflow that wherein adds 5-10 gram magnesium powder and 1-2 gram 48-36 hour, and distillation obtains purified ethanol, methyl alcohol or propyl alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732718A (en) * | 2020-06-15 | 2020-10-02 | 河北工业大学 | Water-soluble conjugated polymer with antibacterial and antiviral functions and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412802A (en) * | 2007-10-18 | 2009-04-22 | 北京化工大学 | Thiophen polymer and preparation process thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412802A (en) * | 2007-10-18 | 2009-04-22 | 北京化工大学 | Thiophen polymer and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Macromolecules》 19990520 ByoungSuhk Kim,et al "Titration Behavior and Spectral Transitions of Water-Soluble Polythiophene Carboxylic Acids" 第3964-3969页 1-2 第32卷, 第12期 * |
| 《胶体与聚合物》 20060930 周海骏等 "水溶性导电聚合物的合成与表征" 第16-17,21页 1-2 第24卷, 第3期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732718A (en) * | 2020-06-15 | 2020-10-02 | 河北工业大学 | Water-soluble conjugated polymer with antibacterial and antiviral functions and preparation and application thereof |
| CN111732718B (en) * | 2020-06-15 | 2021-06-18 | 河北凯尔威生物技术有限公司 | Water-soluble conjugated polymer with antibacterial and antiviral functions and preparation and application thereof |
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Application publication date: 20111116 |