CN112661726B - Preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene - Google Patents
Preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene Download PDFInfo
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- CN112661726B CN112661726B CN202011588810.5A CN202011588810A CN112661726B CN 112661726 B CN112661726 B CN 112661726B CN 202011588810 A CN202011588810 A CN 202011588810A CN 112661726 B CN112661726 B CN 112661726B
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Abstract
The invention belongs to the technical field of epoxy resin synthesis, and discloses a preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene, which comprises the following steps: s1: adding 9-fluorenone, a cocatalyst and a modified carrier catalyst into a solvent, stirring for reaction, and purifying to obtain bisphenol fluorene; s2: and (3) stirring the bisphenol fluorene and epoxy chloropropane to react under an alkaline condition, and purifying to obtain the 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene. The invention has the advantages of simple synthetic route, easy reaction treatment, little pollution and corrosion in the production process and high product yield.
Description
Technical Field
The invention relates to the technical field of epoxy resin synthesis, in particular to a preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene.
Background
As an important thermosetting resin, epoxy resin is widely used in the fields of composite material substrates, insulating material adhesives and the like due to its characteristics of good heat resistance, chemical resistance, strong wear resistance and strong adhesion.
The epoxy resin with a multi-benzene ring fluorene structure is the epoxy resin which is found to be the lowest in water absorption rate and good in mechanical property and heat resistance, the cross-linking density of the resin after curing can be reduced, and the increase of the number of benzene rings can not only improve the rigidity of the molecular chains and improve the glass transition temperature of the resin, but also increase the non-polarity of the molecules and reduce the water absorption of the resin, so that the moisture and heat resistance of the resin is greatly improved. Wherein, the 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene is one of the common epoxy resins with a multi-benzene ring fluorene structure.
9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene is mainly synthesized from bisphenol fluorene and epichlorohydrin.
The prior bisphenol fluorene synthesis process is that phenol and 9-fluorenone are subjected to condensation reaction under the catalysis of sulfuric acid or a gas hydrogen chloride catalyst and a proper amount of mercapto carboxylic acid at a certain reaction temperature, and a crude product generated by the reaction is refined by a solvent to obtain a bisphenol fluorene product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene, which has the advantages of simple synthetic route, easy reaction treatment, small pollution, small corrosion and high product yield.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene, which comprises the following steps:
s1: adding 9-fluorenone, a cocatalyst and a modified carrier catalyst into a solvent, stirring for reaction, and purifying to obtain bisphenol fluorene;
s2: and (3) stirring the bisphenol fluorene and epoxy chloropropane to react under an alkaline condition, and purifying to obtain the 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene.
The synthetic route of the above reaction is as follows:
as a preferred technical scheme of the invention, in S1, the modified carrier catalyst is prepared by loading phosphotungstic acid on a modified carrier; the modified carrier is prepared by oxidizing a multi-walled carbon nano tube.
As a preferred technical solution of the present invention, the oxidation step of the modified carrier is: adding the multi-walled carbon nano-tube and concentrated nitric acid into a reaction kettle, sealing, carrying out oxidation reaction, and purifying to obtain the modified carrier.
As a preferred technical solution of the present invention, the modified supported catalyst is loaded by the following steps: and dissolving the phosphotungstic acid in deionized water, then adding the modified carrier, heating and stirring, filtering and drying to obtain the modified carrier catalyst.
In a preferred embodiment of the present invention, in S1, the cocatalyst is one of mercaptopropionic acid and mercaptoacetic acid.
As a preferable technical scheme of the invention, in S1, the mass ratio of 9-fluorenone to the modified supported catalyst is 1: (0.02-0.1); the mass ratio of the modified supported catalyst to the cocatalyst is 1: (0.05-0.2).
Preferably, in S1, the mass ratio of the 9-fluorenone, the modified supported catalyst and the cocatalyst is 20: 1: 0.1.
compared with the prior art, the invention has the following beneficial effects:
(1) the method has the advantages of simple synthetic route, easy reaction treatment and high product yield, the yield of the product in S1 is higher than 71%, and the yield of the product in S2 is higher than 90.1%.
(2) The modified carrier catalyst used in the S1 is solid, is easy to recover and can be recycled; the catalyst is repeatedly used for 3 times without influencing the catalytic performance.
(3) In the reaction process, no strong acid reagent is used, so that the environmental pollution is small and the corrosion to equipment is small.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 liquid chromatogram of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene in example 2;
FIG. 2 liquid chromatogram of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene in example 3;
FIG. 3 liquid chromatogram of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene in example 4;
FIG. 4 liquid chromatogram of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene in example 5.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it should be understood that they are presented herein only to illustrate and explain the present invention and not to limit the present invention.
Example 1
Preparation of supported catalysts
(1) Preparation of modified carrier: multiwalled carbon nanotubes (10g) were weighed into a reaction vessel, followed by addition of 20mL of concentrated nitric acid, sealing, and reaction at 160 ℃ for 6 hours. The reaction solution was filtered under vacuum, and the filter cake was washed with deionized water to neutrality, then washed twice with an ethanol solution, and then placed in an oven and dried at 80 ℃ for 4 hours to obtain oxidized multi-walled carbon nanotubes (9.5g) containing a carboxyl structure.
(2) Preparation of modified supported catalyst: phosphotungstic acid (1g) was weighed and dissolved in deionized water (100mL), and the oxidized multiwalled carbon nanotubes (10g) were added and stirred at 50 ℃ for 5 hours. The reaction solution was filtered, and the resulting solid was washed with deionized water 3 times, and then the solid was placed in an oven and baked at 50 ℃ for 4 hours to obtain a modified supported catalyst (10 g).
The phosphotungstic acid is colorless, off-white powdery solid or light yellow fine crystal, is easy to dissolve in water, can be loaded into a cavity of the modified carrier, namely the oxidized multi-walled carbon nanotube in the loading process, and can also form a stable hydrogen bond structure with a carboxyl structure, so that the loading amount of the phosphotungstic acid in the modified carrier is increased, and the stable modified carrier catalyst is formed.
Example 2
The synthetic route of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene is as follows:
(1) preparation of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene.
S1: 9-fluorenone (50g, 277mmol), phenol (105g, 1116mmol), modified supported catalyst (2.5g) and mercaptopropionic acid (0.25g) were added to a three-necked flask and stirred at 100 ℃ for 5 hours. And filtering the reaction solution to obtain a filter cake containing the modified carrier catalyst and a filtrate containing the product. The obtained filtrate was distilled under reduced pressure to remove other fractions, to obtain a crude product. The crude product was dissolved in toluene, recrystallized, filtered and the resulting solid dried under vacuum to give bisphenol fluorene (72g, 205mmol, molar yield 74.1%).
S2: dimethylformamide (300mL) was added to a three-necked beaker followed by bisphenol fluorene (50g, 142.7mmol), epichlorohydrin (22.2g, 239.9mmol) and anhydrous potassium carbonate (70g, 506.5mmol) and stirred at 80 ℃ for 3 hours. The reaction solution was filtered, and the filtrate was added to water (1400mL) and stirred to precipitate. Then, filtration was again carried out, and the obtained cake was washed 2 times with water and dried to obtain 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene (52g, 112.4mmol, molar yield 93.7%).
(2) And (4) purifying the supported catalyst.
The cake containing the modified supported catalyst obtained in S1 of example 2 was washed 3 times with deionized water, and then placed in an oven and baked at 50 ℃ for 4 hours to obtain 2.4g of a supported catalyst used 1 time.
Examples 3 to 5
The purified supported catalyst used 1 time in example 2 was reused 3 times as in example 2, and the rest of the reaction conditions were the same as in example 2, to obtain the reaction results of examples 3 to 5, as shown in table 1 below:
TABLE 1 catalyst usage and product yield in examples 3-5
As can be seen from Table 1, the catalyst was used 3 times again, and there was slight loss during the use, but it still had catalytic performance, and the catalytic performance was basically unchanged. The yield of the product obtained in S1 is not much different from that of the product obtained in S1 of example 2, and the product yield is over 71 percent.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene is characterized by comprising the following steps:
s1: mixing 9-fluorenone, phenol, a cocatalyst and a modified carrier catalyst, stirring for reaction, and purifying to obtain bisphenol fluorene;
s2: stirring the bisphenol fluorene and epoxy chloropropane to react under an alkaline condition, and purifying to obtain 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene;
wherein in S1, the cocatalyst is one of mercaptopropionic acid and mercaptoacetic acid; the modified carrier catalyst is prepared by loading phosphotungstic acid on a modified carrier; the modified carrier is prepared by oxidizing a multi-wall carbon nano tube.
2. The preparation method of 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene according to claim 1, wherein the modified carrier is oxidized by the following steps: adding the multi-walled carbon nano-tube and concentrated nitric acid into a reaction kettle, sealing, carrying out oxidation reaction, and purifying to obtain the modified carrier.
3. The method for preparing 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene according to claim 1 or 2, wherein the modified supported catalyst is loaded by the following steps: and dissolving the phosphotungstic acid in deionized water, then adding the modified carrier, heating and stirring, filtering and drying to obtain the modified carrier catalyst.
4. The method for preparing 9, 9-bis [4- (2, 3-epoxypropoxy) phenyl ] fluorene according to claim 1, wherein the mass ratio of 9-fluorenone to modified supported catalyst in S1 is 1: 0.02-1: 0.1; the mass ratio of the modified carrier catalyst to the cocatalyst is 1: 0.05-1: 0.2.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250049A (en) * | 2018-03-25 | 2018-07-06 | 王强 | A kind of green synthesis method of bisphenol fluorene |
| CN108863728A (en) * | 2017-12-08 | 2018-11-23 | 黄骅市信诺立兴精细化工股份有限公司 | A kind of preparation method of 9,9- bis- (4- hydroxyaryl) compound of fluorene class |
| CN109388025A (en) * | 2017-08-07 | 2019-02-26 | 东友精细化工有限公司 | Photosensitive composition, the colour filter comprising the composition and the display device comprising the colour filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109388025A (en) * | 2017-08-07 | 2019-02-26 | 东友精细化工有限公司 | Photosensitive composition, the colour filter comprising the composition and the display device comprising the colour filter |
| CN108863728A (en) * | 2017-12-08 | 2018-11-23 | 黄骅市信诺立兴精细化工股份有限公司 | A kind of preparation method of 9,9- bis- (4- hydroxyaryl) compound of fluorene class |
| CN108250049A (en) * | 2018-03-25 | 2018-07-06 | 王强 | A kind of green synthesis method of bisphenol fluorene |
Non-Patent Citations (1)
| Title |
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| 双酚芴丙烯酸酯清洁生产工艺研究;宋国强等;《现代化工》;20121130;第32卷(第11期);第77-80页 * |
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