CN107935827A - Graininess 9,9 2 [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes and preparation method thereof - Google Patents

Graininess 9,9 2 [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes and preparation method thereof Download PDF

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Publication number
CN107935827A
CN107935827A CN201711256474.2A CN201711256474A CN107935827A CN 107935827 A CN107935827 A CN 107935827A CN 201711256474 A CN201711256474 A CN 201711256474A CN 107935827 A CN107935827 A CN 107935827A
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phenyl
fluorenes
hydroxyl
bis
oxethyls
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CN107935827B (en
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赵金龙
张强
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Jiangsu Yongxing Chemical Ltd By Share Ltd
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Priority to PCT/CN2017/114869 priority patent/WO2019109276A1/en
Priority to JP2020517247A priority patent/JP6905293B2/en
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    • 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
    • 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
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses graininess 9,9 two [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes and preparation method thereof, 100 microns to 2000 microns of its particle diameter distribution；Wherein, particle diameter is more than or equal to 180 microns of part, at least accounts for whole more than 90%.The angle of repose of graininess 9,9 2 [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes is 25 ~ 39 degree.The mobility of graininess 9,9 two [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes of the present invention is greatly improved, easy blowing and conveying, does not stick wall, blowing is clean, is more suitable for industrialized production.

Description

[3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes of graininess 9,9- bis- and its preparation Method
Technical field
Characteristic and its making side the present invention relates to graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes Method, belongs to chemical technology field.
Technical background
In recent years, 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] resin of the fluorenes as raw material, increasingly by joyous Meet.It is the resin that raw material is made with 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, there is heat resistance, the transparency, height The advantages that refractive index, shaping good fluidity.Such as epoxy resin, polyester resin, polycarbonate resin etc., for camera, hand The optical materials such as machine camera lens, vehicle-mounted camera, unmanned plane camera lens.
The shape of 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes is mainly powdered, and mobility is bad, It is unfavorable for being industrially used.For example, being not easy to discharge in hopper, storage bin etc., it is also easy to produce " bridging "；Can transporting it is poor, can hinder Fill in pipeline flowing；Powder may be attached to wall, and blowing is not clean；The shortcomings of.
Therefore, find and be conducive to industrial use, mobility and transportability good the graininess 9, [3- phenyl -4- of 9- bis- (2- hydroxyl-oxethyls) phenyl] fluorenes necessitates.
The content of the invention
The present invention in view of the above-mentioned problems, purpose provide a kind of mobility and it is transportability it is good, beneficial to of industrialized production Granular 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes.
To achieve the above object, the technology of the present invention solution is as follows：
Graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, 100 microns to 2000 microns of its particle diameter distribution； Wherein, particle diameter is more than or equal to 180 microns of part, at least accounts for more than 90% whole
The angle of repose of graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes is 25 ~ 39 degree.
Further, the graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes TGA thermogravimetric analysis, Loss on drying is less than 1%.
The graininess 9, the production method of 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, including following step Suddenly：
Step 1：9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes solution pass through aromatic hydrocarbon solvents crystallization, centrifugation Separation, the residual solvents amount in crystallization is 10%~30%.
Step 2：9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] the fluorenes crystalline solid obtained by step 1 crystallization leads to It is being granulated by comminutor for 1mm~2mm to cross aperture.
Step 3：9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes obtained by step 2, passes through vacuum drying oven It is dry, so that graininess 9 is obtained, 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes.
Further, the aromatic hydrocarbon solvents include benzene,toluene,xylene and mesitylene.It is preferred that toluene.
Further, the vacuum of the vacuum drying oven is 133~4000Pa, 60-120 DEG C of drying temperature, drying time When 18-40 is small.
Further, the comminutor is to wave comminutor.
Referring now to the prior art, the present invention has the advantages that：
Graininess 9 of the present invention, the mobility of 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes are greatly improved, and are held Easy blowing and conveying, do not stick wall, blowing is clean, is more suitable for industrialized production.
Embodiment
According to examples below, illustrate.But this patent is not only limited in examples below.
Embodiment 1
Prepare the reaction kettle of 3000L, built-in blender, cooling tube, dripping device.750 kilograms of toluene are added in reaction kettle, 150 kilograms of 9-Fluorenones, 540 kilograms of adjacent phenyl Phenoxyethanols, 10 kilograms of 3- mercaptopropionic acids.In 60 minutes, drip 280 kilograms 95% sulfuric acid.Reaction temperature is maintained at 50 DEG C, when reaction 5 is small.
After reaction, 1500L toluene is added in reaction solution, adds 500L water, is repeatedly washed to pH equal to 7, then - 5 DEG C are cooled to, centrifuge.Wet crystalline solid（Contain about 20% toluene）It is 1-2 millimeters by sieve mesh to wave Comminutor is granulated, and then, is dried with vacuum drying oven.Under the vacuum of 1300Pa, when 60-120 DEG C of drying 26 is small, graininess is obtained Product, angle of repose are 32.3 degree, and it is 0.23% that particle diameter distribution, which is shown in Table 1, TGA losss on drying,.(Particle size analysis methods:Sieve method, Granulometry sieves, normative reference GB/TT210.3-2004)
Table 1
Embodiment 2
Prepare the reaction kettle of 3000L, built-in blender, cooling tube, dripping device.750 kilograms of dimethylbenzene are added in reaction kettle, 150 kilograms of 9-Fluorenones, 540 kilograms of adjacent phenyl Phenoxyethanols, 10 kilograms of 3- mercaptopropionic acids.In 60 minutes, drip 280 kilograms 95% sulfuric acid.Reaction temperature is maintained at 50 DEG C, when reaction 5 is small.After reaction, 1500L dimethylbenzene is added in reaction solution, 500L water is added, is repeatedly washed to pH equal to 7, is then cooled to -5 DEG C, crystallization is taken out by centrifuge.Wet crystalline solid （Contain about 20% dimethylbenzene）It is granulated by the comminutor that waves that sieve mesh is 1-2 millimeters, then, is dried with vacuum drying oven. Under the vacuum of 1300Pa, when 60-120 DEG C of drying 32 is small, granular product is obtained, angle of repose is 34.8 degree, and particle diameter distribution is shown in Table 2.TGA losss on drying are 0.21%.(Particle size analysis methods:Sieve method, granulometry sieve, normative reference GB/TT210.3- 2004)
Table 2
Comparative example 1
Prepare the reaction kettle of 3000L, built-in blender, cooling tube, dripping device.750 kilograms of toluene are added in reaction kettle, 150 kilograms of 9-Fluorenones, 540 kilograms of adjacent phenyl Phenoxyethanols, 10 kilograms of 3- mercaptopropionic acids.In 60 minutes, drip 280 kilograms 95% sulfuric acid.Reaction temperature is maintained at 50 DEG C, when reaction 5 is small.
After reaction, 1500L toluene is added in reaction solution, adds 500L water, is repeatedly washed to pH equal to 7, then - 5 DEG C are cooled to, crystallization is taken out by centrifuge.Wet crystalline solid（Contain about 20% toluene）, not by comminutor, directly put Enter dry in vacuum drying oven.Under the vacuum of 1300Pa, when 60-80 DEG C of drying 10 is small, powdery product is obtained, cannot get particle Shape product.Angle of repose is 41 degree, and particle diameter distribution is shown in Table 3, and loss on drying is 2.5%.(Particle size analysis methods:Malvern 2000 swashs Light particle size analyzer, normative reference GB/T 19077-2016)
Table 3
Comparative example 2
Prepare the reaction kettle of 3000L, built-in blender, cooling tube, dripping device.750 kilograms of toluene are added in reaction kettle, 150 kilograms of 9-Fluorenones, 540 kilograms of adjacent phenyl Phenoxyethanols, 10 kilograms of 3- mercaptopropionic acids.In 60 minutes, drip 280 kilograms 95% sulfuric acid.Reaction temperature is maintained at 50 DEG C, when reaction 5 is small.
After reaction, 1500L toluene is added in reaction solution, when stirring 1 is small.Then 500L water is added, repeatedly washing Be equal to 7 to pH, add 1000L methanol be warming up to 70 degree of stirrings 2 it is small when, be then cooled to -5 DEG C, crystallization passes through centrifuge taking-up. Wet crystalline solid（Contain about 25% residual solvent）, then, dried with vacuum drying oven.Under the vacuum of 1300Pa, 60-70 DEG C When drying 10 is small, powdery product is obtained.Angle of repose is 45 degree, and particle diameter distribution is shown in Table 4.Loss on drying is 0.6%.(granularmetric analysis Method:2000 laser particle analyzer of Malvern, normative reference GB/T 19077-2016)
Table 4
The present invention key property be：
1）The graininess 9 that this patent obtains, 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, angle of repose is 25 ~ 39 Degree.
When angle of repose is 50 degree, lack mobility.It can be not easy to discharge in hopper, storage bin etc.（Powder among only Down discharge, form duck eye/" bridging "）.Therefore, hopper and during storage bin mobile product, it is necessary to be improved with vibrator etc.. Further, since rodability is poor, it is possible to can block pipeline；Powder may be attached to wall, and blowing is not clean.
When angle of repose is 25 ~ 39 degree, the mobility of product and transportability good, production efficiency is also high.
Angle of repose Measuring Apparatus for Stopping Angle, test method GB/T16913.5-1997.
2）The graininess 9 that this patent obtains, 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, particle diameter distribution 100 microns to 2000 microns, wherein, part of the particle diameter more than or equal to 180 microns at least accounts for whole more than 90%.
3）This patent obtains graininess 9, and 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, uses TGA-Q50 Thermogravimetric analyzer, 300 DEG C of thermogravimetric analysis, loss on drying is less than 1%.

Claims (8)

1. graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, it is characterised in that：Its particle diameter distribution 100 is micro- Rice is to 2000 microns；Wherein, particle diameter is more than or equal to 180 microns of part, at least accounts for whole more than 90%.
2. graininess 9 as claimed in claim 1,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, its feature exist In：The graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes TGA thermogravimetric analysis, loss on drying be 1% with Under.
Graininess 9,9- bis- 3. [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, it is characterised in that：Bis- [3- of graininess 9,9- Phenyl -4- (2- hydroxyl-oxethyls) phenyl] angle of repose of fluorenes is 25 ~ 39 degree.
4. graininess 9 as claimed in claim 3,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, its feature exist In：The graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes TGA thermogravimetric analysis, loss on drying be 1% with Under.
5. make the graininess 9 described in claim 1-4,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, its feature It is：The graininess 9, the production method of 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, comprises the following steps：
Step 1：9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes solution pass through aromatic hydrocarbon solvents crystallization, centrifugation Separation, the residual solvents amount in crystallization is 10%~30%：Step 2：[3- phenyl -4- (the 2- of 9,9- bis- obtained by step 1 crystallization Hydroxyl-oxethyl) phenyl] fluorenes crystalline solid by aperture is that 1mm~2mm being granulated by comminutor：Step 3：Obtained by step 2 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, dried by vacuum drying oven, so as to obtain graininess 9,9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes.
6. graininess 9 as claimed in claim 5, the production method of 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, It is characterized in that：The aromatic hydrocarbon solvents include benzene,toluene,xylene and mesitylene；It is preferred that toluene.
7. graininess 9 as claimed in claim 5, the production method of 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, It is characterized in that：The vacuum of the vacuum drying oven is 133~4000Pa, 60-120 DEG C of drying temperature, drying time 18-40 Hour.
8. graininess 9 as claimed in claim 5, the production method of 9- bis- [3- phenyl -4- (2- hydroxyl-oxethyls) phenyl] fluorenes, It is characterized in that：The comminutor is to wave comminutor.
CN201711256474.2A 2017-12-04 2017-12-04 Granular 9, 9-di [ 3-phenyl-4- (2-hydroxyethoxy) phenyl ] fluorene and preparation method thereof Active CN107935827B (en)

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CN201711256474.2A CN107935827B (en) 2017-12-04 2017-12-04 Granular 9, 9-di [ 3-phenyl-4- (2-hydroxyethoxy) phenyl ] fluorene and preparation method thereof
PCT/CN2017/114869 WO2019109276A1 (en) 2017-12-04 2017-12-06 Granular 9,9-bis[3-phenyl-4-(2-hydroxyethoxy)phenyl]fluorene and preparation method therefor
JP2020517247A JP6905293B2 (en) 2017-12-04 2017-12-06 Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene and its production method

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN117209365A (en) * 2023-09-15 2023-12-12 信诺立兴(沧州渤海新区)化工有限公司 Low metal ion granular phenyl diether fluorene and preparation method thereof

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CN103373908A (en) * 2012-04-23 2013-10-30 宿迁市永星化工有限公司 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and synthetic process thereof
CN104030899A (en) * 2014-06-06 2014-09-10 浙江中欣化工股份有限公司 Method for preparing 9,9-bis[(4-hydroxy oxyethyl) phenyl] fluorene
CN104144904A (en) * 2012-03-09 2014-11-12 本州化学工业株式会社 Method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, crystal of said compound, and method for producing said crystal
CN106242955A (en) * 2015-07-17 2016-12-21 宿迁市永星化工有限公司 The preparation of high-bulk-density 9,9-bis-[3-phenyl-4-(2-hydroxyl-oxethyl) phenyl] fluorenes crystal

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CN103317746A (en) * 2012-03-19 2013-09-25 宿迁市永星化工有限公司 Preparation technology of BPEF (4, 4'-(9-fluorenylidene) bis (2-phenoxy-ethanol)) with high bulk density
JP2018104353A (en) * 2016-12-27 2018-07-05 本州化学工業株式会社 Granular powder of fluorene compound

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Publication number Priority date Publication date Assignee Title
CN104144904A (en) * 2012-03-09 2014-11-12 本州化学工业株式会社 Method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, crystal of said compound, and method for producing said crystal
CN103373908A (en) * 2012-04-23 2013-10-30 宿迁市永星化工有限公司 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and synthetic process thereof
CN104030899A (en) * 2014-06-06 2014-09-10 浙江中欣化工股份有限公司 Method for preparing 9,9-bis[(4-hydroxy oxyethyl) phenyl] fluorene
CN106242955A (en) * 2015-07-17 2016-12-21 宿迁市永星化工有限公司 The preparation of high-bulk-density 9,9-bis-[3-phenyl-4-(2-hydroxyl-oxethyl) phenyl] fluorenes crystal
CN106349030A (en) * 2015-07-17 2017-01-25 宿迁市永星化工有限公司 Preparation of high stacking density 9,9-bi[3-phenyl-4-(2-hydroxy oxethyl)phenyl]fluorine crystal

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117209365A (en) * 2023-09-15 2023-12-12 信诺立兴(沧州渤海新区)化工有限公司 Low metal ion granular phenyl diether fluorene and preparation method thereof
CN117209365B (en) * 2023-09-15 2024-04-09 信诺立兴(沧州渤海新区)化工有限公司 Low metal ion granular phenyl diether fluorene and preparation method thereof

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