CN108017521B - Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene - Google Patents
Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene Download PDFInfo
- Publication number
- CN108017521B CN108017521B CN201711029609.1A CN201711029609A CN108017521B CN 108017521 B CN108017521 B CN 108017521B CN 201711029609 A CN201711029609 A CN 201711029609A CN 108017521 B CN108017521 B CN 108017521B
- Authority
- CN
- China
- Prior art keywords
- fluorene
- bis
- naphthyl
- degrees
- hydroxyethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention uses polar aprotic solvents of N, N-dimethylacetamide and N, N-dimethylacetamideMethyl formamide, N-methyl pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, polyethylene glycol dimethyl (or ethylene) ether and the like are used as reaction promoters, and 9, 9-bis (2-hydroxy naphthyl) fluorene and ethylene carbonate are condensed under alkaline conditions to prepare high-purity and high-bulk-density 9, 9-bis [6- (2-hydroxy ethoxy) naphthyl ] fluorene]Fluorene. Purity (HPLC) greater than 99.0%; bulk density greater than 0.4 g/cubic centimeter, loss on drying<0.5% (120 ℃, 30 min); melting absorption peak 213-222oC. An X-ray powder diffraction (XRPD) spectrum having a morphology as shown in figure 3 and having a 2 theta value of 7.7 + -0.20,8.8±0.20,12.5±0.20,14.3±0.20,15.5±0.20,17.7±0.20,18.7±0.20,19.5±0.20,20.4±0.20,20.9±0.20,21.2±0.20,22.2±0.20,22.7±0.20,23.1±0.20,24.8±0.20,25.4±0.20,25.9±0.20,26.7±0.20Characteristic diffraction peaks.
Description
Technical Field
A preparation method of a high-purity high-bulk density photoelectric material intermediate 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene.
Background
The 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene is an important intermediate of photoelectric materials, and epoxy resin, polyester resin, polyacrylic resin and polyimide which are derived and synthesized from the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene have excellent properties of high refractive index, high thermal stability, good transparency and the like, and have important application in the aspects of light-emitting diode packaging materials, light guide devices, brightness enhancement films, polarizing films, reflective films, optical lenses, electronic photoetching materials and the like.
Japanese patents JP5513825, JP2011068624, JP2016069643 and JP2016079405 report on the preparation of 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene, and the synthetic procedures and results of these patents are the same. The synthesis method comprises the steps of taking concentrated sulfuric acid as a catalyst and 3-mercaptopropionic acid as a cocatalyst, carrying out stirring reaction on 9-fluorenone and 2- (naphthyloxy) ethanol in a xylene solution at 60 ℃ for 5 hours, washing the reaction product with 48% sodium hydroxide solution and washing the reaction product with water for multiple times after the reaction is finished, wherein the purity (HPLC analysis) of the obtained product is 98.3%, the yield is 67%, and Japanese patents do not report the melting point, crystal form and bulk density of the product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene. The process consumes a large amount of sulfuric acid (the amount of sulfuric acid is 4 times the molar amount of 9-fluorenone). And needs high-concentration sodium oxide for neutralization and washing, thereby causing environmental pollution of a large amount of waste acid and waste water. Meanwhile, a large excess of 2- (naphthyloxy) ethanol raw material (more than 4 times of the molar weight of 9-fluorenone) is needed, the recovery is difficult, and the production cost is high. And the obtained product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene has low yield and low purity (98%).
Japanese patents JP5330683, JP2009155253, JP2009173648, JP2011168721, JP2011168722 and JP2011168723 all use ethylene carbonate as hydroxyethylation reagent and methylimidazole as base in diethylene glycol solvent at 100 deg.C oCHydroxyethylation of 9, 9-bis (2-hydroxynaphthyl) fluorene. The synthetic procedures and results of these patents are the same. The crude reaction product was obtained by recrystallization from isopropanol and the synthesis from 1 mole of 9-fluorenone gave only 61 g of product in only 11.3% yield. The purity is 95.7%. The product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]The yield of fluorene is very low, and the purity is low. Also, these patents do not report the product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]Melting point, crystal form and bulk density of fluorene. In order to overcome the defects of the method, the invention adds a proper amount of polar aprotic solvent in the hydroxyethylation reaction of 9, 9-bis (2-hydroxynaphthyl) fluorene by using ethylene carbonate to promote the solubility of alkali in an organic solvent, promotes the hydroxyethylation reaction due to the solid-liquid phase transfer effect, shortens the reaction time, inhibits the formation of a byproduct polymer, simplifies the post-treatment steps, greatly reduces three wastes, greatly improves the yield, and obtains the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl with high purity and high stacking density]Fluorene.
Disclosure of Invention
Aiming at the defects, in the hydroxyethylation reaction of 9, 9-bis (2-hydroxynaphthyl) fluorene by ethylene carbonate, a proper amount of polar aprotic solvent is added, so that the reaction time is shortened, the formation of a byproduct polymer is inhibited, the post-treatment steps are simplified, the three wastes are greatly reduced, and the yield is greatly improved. The invention provides a preparation method of a high-purity high-bulk density photoelectric material intermediate 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene.
Technical solution of the invention
The synthesis process and the purification method of the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene with high purity and high bulk density are characterized by comprising the following steps:
1) adding 9, 9-bis (2-hydroxy naphthyl) fluorene, ethylene carbonate, alkali, reaction promoter and aromatic solvent into a reaction bottle, heating until the raw materials are completely dissolved, and adding the mixture into the reaction bottle at 90 DEGoC-130oC, stirring and reacting for 5-6 hours. Sampling HPLC analysis raw material 9, 9-bis (2-hydroxy naphthyl) fluorene content is less than 0.1%, stopping reaction.
2) After the step 1) is finished, washing the mixture to be neutral by water. Cooling to separate out solid, and obtaining the high-purity and high-bulk density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene.
3) The solid obtained in the step 2) is 80-100%oC, drying for 6-12 hours to obtain the product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]The melting endothermic peak of fluorene is 213-222oC。
4) The product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl) as in step 3)]The purity (HPLC) of fluorene was greater than 99%. The product 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]An X-powder diffraction (XRPD) spectrum of fluorene has morphology as shown in figure 3 and has 2 theta value of 7.7 +/-0.20, 8.8±0.20, 12.5±0.20, 14.3±0.20, 15.5±0.20,17.7±0.20, 18.7±0.20, 19.5±0.20, 20.4±0.20, 20.9±0.20, 21.2±0.20, 22.2±0.20, 22.7±0.20, 23.1±0.20, 24.8±0.20, 25.4±0.20, 25.9±0.20, 26.7±0.20Characteristic diffraction peaks. 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]The fluorene has the structure
。
The invention has the beneficial effects that: polar aprotic solvent is used as a reaction promoter, so that the reaction time is shortened from 10 hours to about 6 hours, and the production efficiency is greatly improved. Meanwhile, the formation of a byproduct polymer is inhibited, the post-treatment steps are simplified, the three wastes are greatly reduced, and the yield is greatly improved. The invention provides a preparation method of a high-purity high-bulk density photoelectric material intermediate 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene.
Drawings
FIG. 1 shows a thermal analysis DSC spectrum of 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene prepared by the present invention.
FIG. 2 is a TGA spectrum of 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene prepared by the present invention.
FIG. 3 is an X-powder diffraction (XRPD) spectrum of 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene prepared in accordance with the present invention.
Detailed Description
Purity determination method (HPLC): the instrument comprises the following steps: LC-15C (Shimadzu); column type: kromasil 100-5C 18150X 4.6 mm; mobile phase: acetonitrile/water; flow rate: 1 mL/min; detection wavelength: 260 nm; sample introduction amount: 2 ul; pump mode: a binary high pressure gradient.
The thermal analysis method comprises the following steps: pyris1 thermal analyzer (Perkin Elemer Co.) with DSC heating range of 50-300oC，10 oCPer minute; TGA heating range is 25-300 oC，10 oCIn terms of a/minute.
X-powder diffraction (XRPD) spectrum: x' TRAX-ray diffractometer (ARL Switzerland Co.) determination, copper target, continuous scanning mode, scanning step size of 0.02 deg. (2 theta), and scanning speed of 2.5 deg./min.
Nuclear magnetic resonance spectroscopy: bruker AM 500 MHz (Germany) Nuclear magnetic resonance apparatus assay (CD)3SO CD3As solvent, TMS as internal standard).
Example 1
In a 500mL reaction flask, add45.6g (0.1 mol) of 9, 9-bis (2-hydroxynaphthyl) fluorene, 200 mL of toluene, 20 g of DMAC, 1.0 g of potassium carbonate and 22g (0.25 mol) of ethylene carbonate. At 110-oC, refluxing and reacting for 5-6 h, and stopping the reaction when the content of the 9, 9-bis (2-hydroxynaphthyl) fluorene is less than 0.1 percent by HPLC analysis. Washing with water to neutrality, separating out organic phase, cooling to separate out solid, and purifying at 80-100 deg.coVacuum drying for 12 hr to obtain 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]45.8 g of fluorene, a yield of 85.2%, a purity of 99.2% by High Performance Liquid Chromatography (HPLC) analysis, and a melting endothermic peak range of 213-222 oC(figure 1), the loss on drying is 0.10% under the condition of 120 ℃, and the loss on weight is 0.2% at 200 ℃ by TGA thermal analysis (figure 2); the bulk density was 0.45 g/cc,1HNMR（CD3SOCD3) δ: 3.76 (t, 4H), 4.05 (t, 4H), 4.87 (s, 2H, plus D)2O disappearance), 7.01 to 7.10 (d, 2H), 7.26 to 7.70 (m, 16H), 7.96 (d, 2H). An X-ray powder diffraction (XRPD) spectrum having a morphology as shown in figure 3 and having a 2 theta value of 7.7 + -0.20, 8.8±0.20, 12.5±0.20, 14.3±0.20, 15.5±0.20,17.7±0.20, 18.7±0.20, 19.5±0.20, 20.4±0.20, 20.9±0.20, 21.2±0.20, 22.2±0.20, 22.7±0.20, 23.1±0.20, 24.8±0.20, 25.4±0.20, 25.9±0.20, 26.7±0.20Characteristic diffraction peaks.
Example 2 in a 500mL reaction flask, 45.6g (0.1 mol) of 9, 9-bis (2-hydroxynaphthyl) fluorene, 200 mL of toluene, 20 g of DMF, 1.0 g of potassium carbonate and 22g (0.25 mol) of ethylene carbonate were added. At 110-oC, refluxing and reacting for 5-6 h, and stopping the reaction when the content of the 9, 9-bis (2-hydroxynaphthyl) fluorene is less than 0.1 percent by HPLC analysis. Washing with water to neutrality, separating out organic phase, cooling to separate out solid, and purifying at 80-100 deg.coVacuum drying for 12 hr to obtain 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]45.8 g of fluorene, a yield of 82.7%, a purity of 99.1% by High Performance Liquid Chromatography (HPLC) analysis, and a melting endothermic peak range of 213-222 oCThe weight loss on drying at 120 ℃ is 0.2%, and the bulk density is 0.48 g/cubic centimeter.
Example 3 in a 500mL reaction flask, 45.6g (0.1 mol) of 9, 9-bis (2-hydroxynaphthyl) fluorene, 200 mL of toluene, 20 g of diethylene glycol dimethyl ether, 1.0 g of potassium carbonate and 22g (0.25 mol) of ethylene carbonate were charged. At 110-oC, refluxing and reacting for 5-6 h, and stopping the reaction when the content of the 9, 9-bis (2-hydroxynaphthyl) fluorene is less than 0.1 percent by HPLC analysis. Washing with water to neutrality, separating out organic phase, cooling to separate out solid, and purifying at 80-100 deg.coVacuum drying for 12 hr to obtain 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]Fluorene 46.3 g, yield 86.0%, purity 99.3% by High Performance Liquid Chromatography (HPLC) analysis, and melting endothermic peak range 213-222 oCThe weight loss on drying at 120 ℃ is 0.2%, and the bulk density is 0.48 g/cubic centimeter.
Example 4 in a 500mL reaction flask, 45.6g (0.1 mol) of 9, 9-bis (2-hydroxynaphthyl) fluorene, 200 mL of toluene, 20 g of triethylene glycol dimethyl ether, 1.0 g of potassium carbonate and 22g (0.25 mol) of ethylene carbonate were charged. At 110-oC, refluxing and reacting for 5-6 h, and stopping the reaction when the content of the 9, 9-bis (2-hydroxynaphthyl) fluorene is less than 0.1 percent by HPLC analysis. Washing with water to neutrality, separating out organic phase, cooling to separate out solid, and purifying at 80-100 deg.coVacuum drying for 12 hr to obtain 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]45.7 g of fluorene, a yield of 85.0%, a purity of 99.3% by High Performance Liquid Chromatography (HPLC) analysis, and a melting endothermic peak range of 213-222 oCThe drying weight loss under the condition of 120 ℃ is 0.2 percent, and the bulk density is 0.5 g/cubic centimeter.
Comparative example 1 in a 500mL four-necked flask, 45.6g (0.1 mol) of 9, 9-bis (2-hydroxynaphthyl) fluorene, 200 mL of toluene, 1.0 g of potassium carbonate, and 22g (0.25 mol) of ethylene carbonate were charged. At 110-oC, refluxing and reacting for 12-13 hours, and stopping the reaction when the content of the 9, 9-bis (2-hydroxynaphthyl) fluorene is less than 0.1 percent by HPLC analysis. Washing with water to neutrality, separating out organic phase, cooling to separate out solid, and purifying at 80-100 deg.coVacuum drying for 12 hr to obtain 9, 9-bis [6- (2-hydroxyethoxy) naphthyl]41.8 g of fluorene, a yield of 78.0%, a purity of 98.5% by High Performance Liquid Chromatography (HPLC) analysis, and a melting endothermic peak range of 213-222 oCAnd the bulk density is 0.35 g/cubic centimeter.
Claims (6)
- A method for producing 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene, characterized in that: taking a polar aprotic solvent as a reaction promoter, carrying out condensation reaction on 9, 9-bis (2-hydroxynaphthyl) fluorene and ethylene carbonate under an alkaline condition to prepare 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene;the reaction accelerator is one or more of N, N-dimethylacetamide, N-dimethylformamide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether; the solvent is one or more of toluene, benzene, xylene, ethylbenzene, diethylbenzene and cumene.
- 2. A process for producing 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene according to claim 1, wherein: the temperature of the reaction is 90-130 ℃.
- 3. A process for producing 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene according to claim 1, wherein: the purity of the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene is more than 99%, and the loss on drying is less than 0.5%.
- 4. A process for producing 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene according to claim 1, wherein: the bulk density of the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene is more than 0.4g/cm 3.
- 5. A process for producing 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene according to claim 1, wherein: the X-powder diffraction spectrum of the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene has characteristic diffraction peaks with 2 theta values of 7.7 +/-0.2 degrees, 8.8 +/-0.2 degrees, 12.5 +/-0.2 degrees, 14.3 +/-0.2 degrees, 15.5 +/-0.2 degrees, 17.7 +/-0.2 degrees, 18.7 +/-0.2 degrees, 19.5 +/-0.2 degrees, 20.4 +/-0.2 degrees, 20.9 +/-0.2 degrees, 21.2 +/-0.2 degrees, 22.2 +/-0.2 degrees, 22.7 +/-0.2 degrees, 23.1 +/-0.2 degrees, 24.8 +/-0.2 degrees, 25.4 +/-0.2 degrees, 25.9 +/-0.2 degrees and 26.7 +/-0.2 degrees.
- 6. A process for producing 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene according to claim 1, wherein: the structure of the 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene is as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711029609.1A CN108017521B (en) | 2017-10-30 | 2017-10-30 | Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711029609.1A CN108017521B (en) | 2017-10-30 | 2017-10-30 | Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108017521A CN108017521A (en) | 2018-05-11 |
| CN108017521B true CN108017521B (en) | 2022-04-01 |
Family
ID=62080394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711029609.1A Active CN108017521B (en) | 2017-10-30 | 2017-10-30 | Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108017521B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7128581B2 (en) * | 2017-06-15 | 2022-08-31 | 田岡化学工業株式会社 | Method for producing alcohol having fluorene skeleton |
| CN114394887A (en) * | 2022-01-28 | 2022-04-26 | 江苏锐鸣材料科技有限公司 | Phenyloxyethanol compound and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155256A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Epoxy compound having fluorene skeleton |
-
2017
- 2017-10-30 CN CN201711029609.1A patent/CN108017521B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155256A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Epoxy compound having fluorene skeleton |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108017521A (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3051350B1 (en) | Alcoholic compound and method for producing alcoholic compound | |
| TWI732808B (en) | Methods for the preparation of 1,3-benzodioxole heterocyclic compounds | |
| CN108017521B (en) | Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene | |
| CN110741005B (en) | Process for preparing 1, 3-benzodioxole heterocyclic compounds | |
| CN106349030A (en) | Preparation of high stacking density 9,9-bi[3-phenyl-4-(2-hydroxy oxethyl)phenyl]fluorine crystal | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN102329298A (en) | Optical resin monomer with high refractive index and preparation method thereof | |
| CN110922597B (en) | Synthesis method of bisphenol S derivative type polysulfate | |
| CN107176905B (en) | Preparation method of high-purity (+/-) -2,2 '-di- (2-hydroxyethoxy) -1,1' -binaphthyl | |
| CN108395363B (en) | Preparation method of 2, 2-bis (3, 4-xylyl) hexafluoropropane | |
| JP2018115129A (en) | Method for producing fluorenylidene diallyl phenols and fluorenylidene diallyl phenols | |
| CN110963938B (en) | Preparation method of C15 side chain substituted fluorine-containing diamine monomer | |
| CN108586205B (en) | Preparation of 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal free from residual solvent in complex form | |
| CN117088746A (en) | Preparation method of parylene series products and parylene series products | |
| WO2022138178A1 (en) | Crystal of 1,1,1-tris(4-hydroxy-3,5-dimethylphenyl)ethane and production method therefor | |
| CN108129654A (en) | A kind of readily soluble flame retardant type fluorinated poly arylene ether nitrile resin of high temperature resistant and preparation method thereof | |
| CN104910113B (en) | Preparation method of hydroxy benzene anhydride | |
| CN111018737B (en) | Preparation method of C12 side chain substituted fluorine-containing diamine monomer | |
| CN115583929B (en) | Preparation method of bisphenol A diether dianhydride | |
| CN111484412A (en) | Method for synthesizing compound containing indan structure | |
| CN101973855B (en) | Novel 4,4'-di(alkoxy/aryloxy methyl) biphenyl and preparation thereof | |
| CN115536666B (en) | Dianhydride monomer containing benzobisnorbornene cyclobutane structure and preparation method and application thereof | |
| CN117164440A (en) | Fluorenyl diol compound and preparation method thereof | |
| CN114195697B (en) | Dichloro diphthalimide intermediate and synthetic method and application thereof | |
| CN106831357B (en) | Preparation method of 9, 9-bis [ (4-hydroxyethoxy) phenyl ] fluorene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |