CN107936172B - Preparation method of coumarin polymer semiconductor laser material - Google Patents
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229960000956 coumarin Drugs 0.000 title claims abstract description 41
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 39
- IVJMJRRORVMRJJ-UHFFFAOYSA-N 7-hydroxy-4-phenylchromen-2-one Chemical compound C=1C(=O)OC2=CC(O)=CC=C2C=1C1=CC=CC=C1 IVJMJRRORVMRJJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 acrylic acid-4-phenyl-7-hydroxycoumarin ester Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 claims description 11
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- JXHZRQHZVYDRGX-UHFFFAOYSA-M sodium;hydrogen sulfate;hydrate Chemical compound [OH-].[Na+].OS(O)(=O)=O JXHZRQHZVYDRGX-UHFFFAOYSA-M 0.000 claims description 11
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 11
- 235000021286 stilbenes Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005086 pumping Methods 0.000 abstract description 4
- 230000005669 field effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010035148 Plague Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/36—Structure or shape of the active region; Materials used for the active region comprising organic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention provides a preparation method of a coumarin polymer semiconductor laser material, which comprises the steps of preparation of 4-phenyl-7-hydroxycoumarin, preparation of acrylic acid-4-phenyl-7-hydroxycoumarin ester, preparation of coumarin polymer and the like. The invention also provides application of the coumarin polymer semiconductor laser material in a laser. The material has the advantages of low preparation cost, simple and controllable synthesis, high yield, good solubility and better thermal stability. The material has excellent thermal stability, film forming stability, low threshold characteristic, low water oxygen sensitivity and high luminous intensity in the application of an organic laser device. The high luminous efficiency and mobility of the organic light-emitting diode lead the organic light-emitting diode to have potential application value in the aspects of electrically pumping organic semiconductor laser, organic electroluminescence and organic field effect transistors.
Description
Technical Field
The invention belongs to the field of laser materials, and particularly relates to a coumarin polymer semiconductor laser material.
Background
The traditional laser has a plurality of problems, such as difficult crystal growth, high technical requirement, high price and the like for the solid laser; the laser glass is generally required to be melted under high temperature, OH groups and gas protection are also required to be removed for different matrix materials and different laser working wave bands, the process conditions are severe, and the production cost is high. At present, more carbon dioxide gas lasers are used, and the device is heavy and huge although the power is high, so that a plurality of inconveniences are brought to occasions needing a miniaturized laser. In recent years, inorganic semiconductor lasers have been rapidly developed and widely used, but have a problem of high production cost. In view of these limitations in laser performance, scientists have long been striving to develop new laser materials in an effort to achieve a more perfect laser. The exploration and development of novel laser working substances and materials are not only the precondition and basis for developing novel high-efficiency lasers and laser systems in the future, but also have great potential application value.
Organic semiconductor materials have been widely used in the fields of Organic Light Emitting Diodes (OLEDs), organic Field Effect Transistors (OFETs), organic solar cells (OPVs), organic lasers (organic lasers) and the like because of their good optical and electrical properties, simple preparation processes and structural and performance modulatability, and have become an important content for research on organic electronics. In recent years, research and development of organic lasers which are compact in structure and low in price (even can be abandoned) are very rapid. Compared with dye lasers, the organic semiconductor material has the advantages of organic laser dyes (high luminous efficiency, wide adjustable spectrum range, four-energy-level system and the like), high solid state luminous efficiency, good carrier transmission, good film forming property and the like, and is widely focused on laser application. However, the high laser threshold of the organic laser under the electric pumping makes the electric pumping of the organic laser difficult to realize, which is also a bottleneck problem which plagues the development of the organic laser. In order to reduce the laser threshold, organic semiconductor materials including small molecular materials, polymer materials, high molecular materials and the like are synthesized by optimizing molecular structure design. The polymer has a multidimensional space topological structure, is monodisperse and can be purified by using conventional silica gel column chromatography like small molecules, and has good film forming performance similar to polymers. In addition, because of the space multidimensional structure, the interaction among molecules is weakened, so that the materials have better solubility in polar solvents to form a film with regular and uniform surface morphology, and meanwhile, the materials have isotropic photoelectric properties.
Disclosure of Invention
Technical problems: in order to solve the defects in the prior art, the invention provides a coumarin polymer semiconductor laser material.
The technical scheme is as follows: the invention provides a coumarin polymer semiconductor laser material, which has the structural formula:
m and n respectively represent the number of monomers.
The melting point of the coumarin polymer semiconductor laser material is above 220.8.
The PL emission peak of the coumarin polymer semiconductor laser material is between 482 and 548 nm.
The full width at half maximum of PL emission peak of the coumarin polymer semiconductor laser material is below 4.9 nm.
The gain coefficient of the coumarin polymer semiconductor laser material is 91-98cm -1 Between them.
The invention also provides a preparation method of the coumarin polymer semiconductor laser material, which is characterized in that: the method comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin;
the reaction formula is:
(2) Preparation of 4-phenyl-7-hydroxycoumarin acrylate: in the presence of hydroquinone, 10mL of acrylic acid and dichloromaple react to obtain acrylic chloride; reacting 4-phenyl-7-hydroxycoumarin with acryloyl chloride in the presence of triethylamine to obtain acrylic acid-4-phenyl-7-hydroxycoumarin ester; the reaction formula is:
(3) Preparation of coumarin polymer: in the nitrogen atmosphere, in the presence of an initiator, reacting acrylic acid-4-phenyl-7-hydroxy coumarin ester with 4-nitro-4 '-acetamido-3' -methyl ester stilbene to obtain the catalyst; the reaction formula is:
in the step (1), the molar ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is (0.10-0.20): 1: (1-2), the reaction time is 10-20min.
In the step (2), the dosage ratio of the acrylic acid to the dichlorophenone in the preparation reaction of the acryloyl chloride is (40-60) mmol:10mL, the reaction temperature is 30-50 ℃ and the reaction time is 1-3h; in the preparation reaction of the acrylic acid-4-phenyl-7-hydroxycoumarin ester, the mole ratio of the acrylic acid chloride to the 4-phenyl-7-hydroxycoumarin to the triethylamine is as follows: (4-6): 2: (3-4), the reaction temperature is room temperature, and the reaction time is 3-5h.
In the step (3), the molar ratio of the acrylic acid-4-phenyl-7-hydroxy coumarin ester to the 4-nitro-4 '-acetamido-3' -methyl ester stilbene is 1:1; the initiator is AIBN; the reaction temperature is 70-80 ℃ and the reaction time is 20-30h.
The invention also provides application of the coumarin polymer semiconductor laser material in a laser.
The beneficial effects are that: the coumarin polymer semiconductor laser material provided by the invention has the advantages of low preparation cost, simple and controllable synthesis, high yield, good solubility and better thermal stability. The material has excellent thermal stability, film forming stability, low threshold characteristic, low water oxygen sensitivity and high luminous intensity in the application of an organic laser device. The high luminous efficiency and mobility of the organic light-emitting diode lead the organic light-emitting diode to have potential application value in the aspects of electrically pumping organic semiconductor laser, organic electroluminescence and organic field effect transistors.
Detailed Description
The present invention will be further described below.
Example 1
The preparation of the coumarin polymer semiconductor laser material comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: 40.0mmol of resorcinol, 60.0mmol of ethyl benzoylacetate and 4.0mmol of sodium bisulfate monohydrate are added into a round-bottomed flask, uniformly mixed, placed into a microwave chemical reactor, provided with a reflux device, intermittently heated under the condition of 400W of power, monitored by TLC for reaction progress, after heating for 8min, resorcinol disappears, and microwave heating is stopped. After cooling, 80mL of ice water was added to the reaction flask, stirred, dispersed with ultrasonic waves, a large amount of bulk solid was precipitated, filtered off with suction to remove water, and then recrystallized with 95% ethanol to give 7.08g of dark green solid with a yield of 70.9%.
MS(m/z):238.2(M+，92.1％)，210.1(100％)，181.2(34.2％)，152.1(26.3％)，76.1(9.2％)。R f (0.55, ethyl acetate: petroleum ether=2:1)
The reaction formula is:
(2) Preparation of 4-phenyl-7-hydroxycoumarin acrylate: in a dry three-necked flask, 50mmol of acrylic acid, 10mL of dichloromaple and a small amount of hydroquinone were added, the reaction was magnetically stirred at 40 ℃ for 2 hours, and after the reaction was completed, the excess dichloroalum was removed in vacuo. 20mmol of 4-phenyl-7-hydroxycoumarin and 30mmol of anhydrous triethylamine are dissolved in 30mL of dichloromethane (subjected to anhydrous treatment), the dichloromethane solution is dropwise added into a three-necked flask filled with acryloyl chloride through a dropping funnel under the cooling of an ice bath, the reaction phenomenon is very severe, a large amount of white smoke is generated, and after the dichloromethane solution of coumarin is dropwise added, the whole reaction system is yellow. After removing the ice bath and continuing the reaction at room temperature for 4 hours, TLC showed that the starting material point did not continue to diminish and the reaction stopped. After the reaction solution was concentrated, column chromatography was performed using silica gel, and ethyl acetate was used as an eluent: the petroleum ether 1:4 solvent was collected as a pale yellow solid, 2.95g, and the yield was 50.1%.
The reaction formula is:
(3) Preparation of coumarin polymer: in a dry round bottom flask was added magneton, 2mmol of 4-phenyl-7-hydroxycoumarin acrylate, 2mmol of 4-nitro-4 '-acetamido-3' -methyl ester stilbene, initiator AIBN0.0078g. After 3 times aeration with nitrogen, 10mL of anhydrous THF was injected into the flask with a rubber stopper, followed by reaction at 70 ℃ for 25 hours under nitrogen protection. After the reaction is finished, pouring the polymer solution into 200mL of methanol, precipitating a large amount of white solid, and airing the solid obtained after filtration at room temperature to obtain the polymer; the yield thereof was found to be 100%.
GPC：Mn＝4328，Mw＝5618，PDI＝1.29；
The reaction formula is:
example 2
The preparation of the coumarin polymer semiconductor laser material comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin; wherein, the mole ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is 0.15:1:1.5, the reaction time is 15min;
(2) Preparation of 4-phenyl-7-hydroxycoumarin acrylate: in the presence of hydroquinone, 10mL of acrylic acid and dichloromaple react to obtain acrylic chloride; reacting 4-phenyl-7-hydroxycoumarin with acryloyl chloride in the presence of triethylamine to obtain acrylic acid-4-phenyl-7-hydroxycoumarin ester; wherein, in the preparation reaction of the acrylic acid chloride, the dosage ratio of the acrylic acid to the dichlorophenone is 50mmol:10mL, the reaction temperature is 40 ℃, and the reaction time is 2h; in the preparation reaction of the acrylic acid-4-phenyl-7-hydroxycoumarin ester, the molar ratio of the acrylic acid chloride to the 4-phenyl-7-hydroxycoumarin to the triethylamine is 5:2: the temperature of 3.5 ℃ is room temperature, and the reaction time is 4;
(3) Preparation of coumarin polymer: in the nitrogen atmosphere, in the presence of an initiator, reacting acrylic acid-4-phenyl-7-hydroxy coumarin ester with 4-nitro-4 '-acetamido-3' -methyl ester stilbene to obtain the catalyst; wherein, the mol ratio of the acrylic acid-4-phenyl-7-hydroxy coumarin ester to the 4-nitro-4 '-acetamido-3' -methyl ester stilbene is 1:1; the initiator is AIBN; the reaction temperature was 75 and the reaction time was 25.
GPC：Mn＝4218，Mw＝5624，PDI＝1.36。
Example 3
The preparation of the coumarin polymer semiconductor laser material comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin; wherein, the mole ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is 0.10:1:2, the reaction time is 20min;
(2) Preparation of 4-phenyl-7-hydroxycoumarin acrylate: in the presence of hydroquinone, 10mL of acrylic acid and dichloromaple react to obtain acrylic chloride; reacting 4-phenyl-7-hydroxycoumarin with acryloyl chloride in the presence of triethylamine to obtain acrylic acid-4-phenyl-7-hydroxycoumarin ester; wherein, in the preparation reaction of the acrylic acid chloride, the dosage ratio of the acrylic acid to the dichlorophenone is 40mmol:10mL, the reaction temperature is 50 ℃, and the reaction time is 1h; in the preparation reaction of the acrylic acid-4-phenyl-7-hydroxycoumarin ester, the molar ratio of the acrylic acid chloride to the 4-phenyl-7-hydroxycoumarin to the triethylamine is 4:2:3, the reaction temperature is room temperature, and the reaction time is 3h;
(3) Preparation of coumarin polymer: in the nitrogen atmosphere, in the presence of an initiator, reacting acrylic acid-4-phenyl-7-hydroxy coumarin ester with 4-nitro-4 '-acetamido-3' -methyl ester stilbene to obtain the catalyst; wherein, the mol ratio of the acrylic acid-4-phenyl-7-hydroxy coumarin ester to the 4-nitro-4 '-acetamido-3' -methyl ester stilbene is 1:1; the initiator is AIBN; the reaction temperature was 70℃and the reaction time was 30 hours.
GPC：Mn＝4167，Mw＝5824，PDI＝1.39。
Example 4
The preparation of the coumarin polymer semiconductor laser material comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin; wherein, the mole ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is 0.20:1:1, the reaction time is 10min;
(2) Preparation of 4-phenyl-7-hydroxycoumarin acrylate: in the presence of hydroquinone, 10mL of acrylic acid and dichloromaple react to obtain acrylic chloride; reacting 4-phenyl-7-hydroxycoumarin with acryloyl chloride in the presence of triethylamine to obtain acrylic acid-4-phenyl-7-hydroxycoumarin ester; wherein, in the preparation reaction of the acrylic acid chloride, the dosage ratio of the acrylic acid to the dichlorophenone is 60mmol:10mL, the reaction temperature is 30 ℃, and the reaction time is 3h; in the preparation reaction of the acrylic acid-4-phenyl-7-hydroxycoumarin ester, the molar ratio of the acrylic acid chloride to the 4-phenyl-7-hydroxycoumarin to the triethylamine is 6:2:4, the reaction temperature is room temperature, and the reaction time is 5 hours;
(3) Preparation of coumarin polymer: in the nitrogen atmosphere, in the presence of an initiator, reacting acrylic acid-4-phenyl-7-hydroxy coumarin ester with 4-nitro-4 '-acetamido-3' -methyl ester stilbene to obtain the catalyst; wherein, the mol ratio of the acrylic acid-4-phenyl-7-hydroxy coumarin ester to the 4-nitro-4 '-acetamido-3' -methyl ester stilbene is 1:1; the initiator is AIBN; the reaction temperature was 80℃and the reaction time was 20h.
GPC：Mn＝4249，Mw＝5901，PDI＝1.38。
Example 5
The coumarin polymer semiconductor laser materials of examples 1 to 4 were tested for solubility, and the results are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Melting point DEG C | 222.6-223.2 | 220.8-222.3 | 228.6-229.8 | 227.1-228.4 |
The coumarin polymer semiconductor laser materials of examples 1 to 4 were tested for solubility, and the results are shown in table 2.
TABLE 2
And (2) the following steps: completely dissolving; delta: partially dissolving; x, insoluble.
THF is used as a solvent, and the coumarin polymer semiconductor laser materials of examples 1 to 4 are adopted as a luminous main body to prepare 20mg/mL solutions respectively. The quartz plate is cleaned by ultrasonic wave, and the organic laser device is prepared by adopting a spin coating mode, wherein the spin coating condition is 2000rpm, and the film thickness is about 100 nm. The properties were measured and the results are shown in Table 3.
TABLE 3 Table 3
Claims (8)
1. A preparation method of coumarin polymer semiconductor laser material is characterized in that: the method comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin;
the reaction formula is:
(2) Preparation of 4-phenyl-7-hydroxycoumarin acrylate: in the presence of hydroquinone, 10mL of acrylic acid and dichloromaple react to obtain acrylic chloride; reacting 4-phenyl-7-hydroxycoumarin with acryloyl chloride in the presence of triethylamine to obtain acrylic acid-4-phenyl-7-hydroxycoumarin ester; the reaction formula is:
(3) Preparation of coumarin polymer: in the nitrogen atmosphere, in the presence of an initiator, reacting acrylic acid-4-phenyl-7-hydroxy coumarin ester with 4-nitro-4 '-acetamido-3' -methyl ester stilbene to obtain the catalyst; wherein, the mol ratio of the acrylic acid-4-phenyl-7-hydroxy coumarin ester to the 4-nitro-4 '-acetamido-3' -methyl ester stilbene is 1:1;
the reaction formula is:
2. the method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: in the step (1), the molar ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is (0.10-0.20): 1: (1-2), the reaction time is 10-20min.
3. The method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: in the step (2), the dosage ratio of the acrylic acid to the dichlorophenone in the preparation reaction of the acryloyl chloride is (40-60) mmol:10mL, the reaction temperature is 30-50 ℃ and the reaction time is 1-3h; in the preparation reaction of the acrylic acid-4-phenyl-7-hydroxycoumarin ester, the mole ratio of the acrylic acid chloride to the 4-phenyl-7-hydroxycoumarin to the triethylamine is as follows: (4-6): 2:
(3-4), the reaction temperature is room temperature, and the reaction time is 3-5h.
4. The method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: in the step (3), the initiator is AIBN; the reaction temperature is 70-80 ℃ and the reaction time is 20-30h.
5. The method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: the melting point of the coumarin polymer semiconductor laser material is above 220.8.
6. The method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: the PL emission peak of the coumarin polymer semiconductor laser material is between 482 and 548 nm.
7. The method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: the full width at half maximum of PL emission peak of the coumarin polymer semiconductor laser material is below 4.9 nm.
8. The method for preparing the coumarin polymer semiconductor laser material according to claim 1, which is characterized in that: the gain coefficient of the coumarin polymer semiconductor laser material is 91-98cm -1 Between them.
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| US5231329A (en) * | 1990-07-16 | 1993-07-27 | Nippon Oil Co., Ltd. | Organic thin film electroluminescent device |
| US5360815A (en) * | 1993-06-23 | 1994-11-01 | Merck Frosst Canada, Inc. | Heteroaryl cinnamic acids as inhibitors of leukotriene biosynthesis |
| CN104892556A (en) * | 2015-05-29 | 2015-09-09 | 合肥工业大学 | Stilbene coumarin derivative as well as preparation method and application thereof |
| CN107003576A (en) * | 2014-12-08 | 2017-08-01 | 夏普株式会社 | Liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5231329A (en) * | 1990-07-16 | 1993-07-27 | Nippon Oil Co., Ltd. | Organic thin film electroluminescent device |
| US5360815A (en) * | 1993-06-23 | 1994-11-01 | Merck Frosst Canada, Inc. | Heteroaryl cinnamic acids as inhibitors of leukotriene biosynthesis |
| CN107003576A (en) * | 2014-12-08 | 2017-08-01 | 夏普株式会社 | Liquid crystal display device |
| CN104892556A (en) * | 2015-05-29 | 2015-09-09 | 合肥工业大学 | Stilbene coumarin derivative as well as preparation method and application thereof |
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