阅读说明：本技术 一种双酚芴系化合物的制备方法 (Preparation method of bisphenol fluorene compound ) 是由 林敬浤 洪瑞聪 郭芳吟 李昇峰 于 2018-11-07 设计创作，主要内容包括：本发明提供了一种双酚芴系化合物的制备方法,该方法包括下列步骤：在含巯基的催化剂存在下,使9-芴酮及具有酚结构部分的化合物熔融并进行预反应；逐滴加入助催化剂进行缩合反应,得到具有具式(I)的双酚芴系化合物的混合物；以及以不溶该具式(I)的双酚芴系化合物的溶剂在60至90℃的温度下搅拌浸洗及过滤该混合物,得到该具式(I)的双酚芴系化合物。本发明的制备方法制程简单,且能有效降低反应副产物的形成,有利于工业化制备双酚芴系化合物,符合高纯度、高效率且低成本的生产需求。<Image he="322" wi="486" file="DDA0001856989030000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a preparation method of a bisphenol fluorene compound, which comprises the following steps: melting 9-fluorenone and a compound having a phenol structure moiety in the presence of a mercapto group-containing catalyst and carrying out a pre-reaction; dropwise adding a cocatalyst to carry out condensation reaction to obtain a mixture of bisphenol fluorene compounds with the formula (I); and stirring and washing and filtering the mixture at a temperature of 60 to 90 ℃ with a solvent in which the bisphenol fluorene compound of formula (I) is insoluble to obtain the bisphenol fluorene compound of formula (I). The preparation method has simple process, can effectively reduce the formation of reaction by-products, is beneficial to the industrial preparation of the bisphenol fluorene compounds, and meets the requirements of high purity, high efficiency and low costThe production requirement for cost.)

1. A process for preparing bisphenol fluorene compound of formula (I),

wherein R is one selected from the group consisting of hydroxy naphthyl and hydroxy phenyl unsubstituted or substituted by phenyl or C1-C10 alkyl;

the method comprises the following steps:

melting 9-fluorenone and a compound having a phenol moiety in the presence of a mercapto group-containing catalyst and pre-reacting for 1 to 10 minutes, wherein the compound having a phenol moiety is one selected from the group consisting of naphthol and phenol unsubstituted or substituted with phenyl or C1-C10 alkyl;

dropwise adding a cocatalyst at the temperature of 60-80 ℃ to carry out condensation reaction to obtain a mixture of the bisphenol fluorene compound with the formula (I); and

the bisphenol fluorene compound of formula (I) is obtained by stirring, washing and filtering the mixture at a temperature of 60 to 90 ℃ with a solvent in which the bisphenol fluorene compound of formula (I) is insoluble.

2. The method of claim 1, wherein the thiol-based catalyst is one selected from the group consisting of thiols containing C1-C10 alkyl groups or C6-C12 aryl groups and mercaptocarboxylic acids.

3. The method according to claim 2, wherein the mercaptocarboxylic acid is 3-mercaptopropionic acid, mercaptoacetic acid, or mercaptobenzoic acid.

4. The method of claim 1, wherein the molar ratio of the mercapto-containing catalyst to the 9-fluorenone is 0.1:1 to 3: 1.

5. The method according to claim 4, wherein the mercapto group-containing catalyst is 3-mercaptopropionic acid.

6. The method of claim 5, wherein the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 0.15:1 to 0.30: 1.

7. The method according to claim 1, wherein the compound having a phenol moiety comprises one selected from the group consisting of naphthol, alkylphenol, hydroxybiphenyl, and phenol.

8. The method of claim 1, wherein the molar ratio of the compound having a phenolic moiety to the 9-fluorenone is from 2:1 to 7: 1.

9. The method according to claim 8, wherein the compound having a phenol moiety is hydroxybiphenyl.

10. The method of claim 1, wherein the pre-reaction temperature is the same as the condensation reaction temperature.

11. The method of claim 1, wherein the cocatalyst is a dehydrating agent.

12. The method according to claim 11, wherein the dehydrating agent is one selected from the group consisting of sulfuric acid, calcium oxide, chlorosulfonic acid, phosphoric acid, polyphosphoric acid, and various acid anhydrides.

13. The method of claim 1, wherein the molar ratio of the promoter to the 9-fluorenone is 0.5:1 to 2: 1.

14. The method of claim 13, wherein the promoter is sulfuric acid.

15. The method of claim 1, wherein the cocatalyst is added at a rate of 0.9 to 9.0 ml/min.

16. The method of claim 1, wherein the condensation reaction is carried out for a reaction time of 0.5 to 2 hours.

17. The method according to claim 1, wherein the solvent in which the bisphenol fluorene compound of formula (I) is insoluble is a benzene-based solvent substituted with a halogen group or at least one C1-C5 alkyl group.

18. The method of claim 17, wherein the benzene-based solvent comprises one selected from the group consisting of benzene, toluene, xylene, chlorobenzene, and mesitylene.

19. A process for preparing bisphenol fluorene compound of formula (II),

the method comprises the following steps:

melting 9-fluorenone and hydroxybiphenyl in the presence of a catalyst of 3-mercaptopropionic acid and pre-reacting at a temperature of 60 to 80 ℃ for 1 to 10 minutes, wherein the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 0.15:1 to 0.30: 1;

dropwise adding sulfuric acid at a temperature of 60-80 ℃ to perform a condensation reaction for 1-2 hours to obtain a mixture of the bisphenol fluorene compound having the formula (II), wherein the molar ratio of the sulfuric acid to the 9-fluorenone is 0.5: 1-2: 1, and the dropwise adding speed of the sulfuric acid is 0.9-9.0 ml/min; and

the bisphenol fluorene compound of formula (II) is obtained by stirring, washing and filtering the mixture with a solvent which does not dissolve the bisphenol fluorene compound of formula (II) at a temperature of 60 to 90 ℃.

Technical Field

The invention relates to a method for preparing bisphenol fluorene compounds, in particular to a method for preparing bisphenol fluorene compounds by a solvent-free melting mode.

Background

The fluorene derivative material has a rigid plane structure and good thermal stability and photochemical stability, so that the fluorene derivative material can be used as a raw material of products such as epoxy resin and novel heat-resistant polycarbonate with high heat resistance and good optical performance. Due to the unique structure, the bisphenol fluorene compound can improve the refractive index, high transparency and easy solubility of the prepared polymer, so that the bisphenol fluorene compound can be used as a raw material or an improver of a separation film material, epoxy resin and polyester in the field of electronic liquid crystal, can be widely applied to the fields of military affairs, aviation, electronics and automobiles such as aircraft structural materials, missile warheads, engine nozzles and the like, and is recently paid attention to various fields.

The traditional production method of bisphenol fluorene mostly adopts a sulfuric acid method, although the preparation method has the advantages of low temperature and high yield, the reaction time of the preparation method is as long as more than 10 hours, and in order to meet the purity requirement, a recrystallization method is required for purification treatment, the process is complicated and time-consuming, and the industrial production is not facilitated.

In view of the above, it is necessary to provide a method for industrially advantageously preparing bisphenol fluorene compounds, so as to solve the problems in the prior art.

Disclosure of Invention

In order to solve the above problems, the present invention provides a process for producing a bisphenol fluorene compound of the following formula (I),

wherein R is one selected from the group consisting of hydroxy naphthyl and hydroxy phenyl unsubstituted or substituted by phenyl or C1-C10 alkyl;

the method comprises the following steps: melting 9-fluorenone and a compound having a phenol moiety in the presence of a mercapto group-containing catalyst and pre-reacting for 1 to 10 minutes, wherein the compound having a phenol moiety is one selected from the group consisting of naphthol and phenol unsubstituted or substituted with phenyl or C1-C10 alkyl; dropwise adding a cocatalyst at the temperature of 60-80 ℃ to carry out condensation reaction to obtain a mixture of the bisphenol fluorene compound with the formula (I); and stirring and washing and filtering the mixture at a temperature of 60 to 90 ℃ with a solvent in which the bisphenol fluorene compound of formula (I) is insoluble to obtain the bisphenol fluorene compound of formula (I).

The invention also provides a preparation method of the bisphenol fluorene compound with the following formula (II),

the method comprises the following steps: melting 9-fluorenone and hydroxybiphenyl in the presence of a catalyst of 3-mercaptopropionic acid and pre-reacting at a temperature of 60 to 80 ℃ for 1 to 10 minutes, wherein the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 0.15:1 to 0.30: 1; dropwise adding sulfuric acid at a temperature of 60-80 ℃ to perform a condensation reaction for 1-2 hours to obtain a mixture of the bisphenol fluorene compound having the formula (II), wherein the molar ratio of the sulfuric acid to the 9-fluorenone is 0.5: 1-2: 1, and the dropwise adding speed of the sulfuric acid is 0.9-9.0 ml/min; and stirring and washing and filtering the mixture at a temperature of 60 to 90 ℃ with a solvent in which the bisphenol fluorene compound of formula (II) is insoluble to obtain the bisphenol fluorene compound of formula (II).

In the preparation method of the bisphenol fluorene compound, the catalyst and the cocatalyst are added in a molten state at proper time, so that the low-temperature reaction can be facilitated, and the reaction time can be shortened to reduce the formation of reaction byproducts; moreover, the reaction mixture is leached and filtered by a solvent of an insoluble bisphenol fluorene compound, the process is simple, the by-product and the unreacted compound with a phenol structure part can be effectively separated, the production requirements of high purity, high efficiency and low cost are met, and the industrial application value is realized.

Drawings

Embodiments of the invention are described by way of example with reference to the accompanying drawings:

FIG. 1 is a graph showing the purity of a bisphenol fluorene-based compound of example 1 of the present invention by High Performance Liquid Chromatography (HPLC);

FIG. 2 is a graph showing the purity of a bisphenol fluorene-based compound of example 2 of the present invention by High Performance Liquid Chromatography (HPLC); and

FIG. 3 is a graph showing the purity of a bisphenol fluorene compound of example 3 of the present invention by High Performance Liquid Chromatography (HPLC).

Detailed Description

The following description of the embodiments of the present invention is provided for illustrative purposes, and the present invention is not limited to the embodiments described herein. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present disclosure. Moreover, all ranges and values herein are inclusive and combinable. Any number or point within the ranges set forth herein, e.g., any integer, may be treated as the minimum or maximum value to derive a lower range, etc.

According to the present invention, there is provided a process for producing a bisphenol fluorene compound of the following formula (I),

wherein R is one selected from the group consisting of hydroxy naphthyl and hydroxy phenyl unsubstituted or substituted by phenyl or C1-C10 alkyl;

the method comprises the following steps: melting 9-fluorenone and a compound having a phenol moiety in the presence of a mercapto group-containing catalyst and pre-reacting for 1 to 10 minutes, wherein the compound having a phenol moiety is naphthol and one selected from the group consisting of unsubstituted or phenyl-substituted phenols or C1-C10 alkyl-substituted phenols; dropwise adding a cocatalyst at the temperature of 60-80 ℃ to carry out condensation reaction to obtain a mixture of the bisphenol fluorene compound with the formula (I); and stirring and washing and filtering the mixture at a temperature of 60 to 90 ℃ with a solvent in which the bisphenol fluorene compound of formula (I) is insoluble to obtain the bisphenol fluorene compound of formula (I).

In the present invention, the term "melt" means a state of being heated to a temperature not lower than the melting point of the reactant or not lower than the temperature at which the reactant is deformable and then becomes fluid.

In the present invention, the term "mixture" means that the bisphenol fluorene compound as the reaction product includes an unreacted compound having a phenol moiety, a catalyst and a side reaction product (i.e., a by-product).

The hydroxyl group, phenyl group or alkyl group of the bisphenol fluorene compound of formula (I) may be substituted by one or more substituents on the naphthalene ring or benzene ring, and the substitution position of the hydroxyl group, phenyl group or alkyl group on the naphthalene ring or benzene ring is not particularly limited.

The bisphenol fluorene compound fully retains the hydroxyl on the compound with a phenol structure part and is used as a raw material for preparing condensation polymers such as epoxy resin, polyester, polyether, polycarbonate and the like; as the bisphenol fluorene compound has more benzene ring structures than fluorene materials, the prepared condensation polymer has good heat resistance, optical performance and flame retardance.

The invention relates to a preparation method of bisphenol fluorene compound with formula (I), which is a method for preparing bisphenol fluorene compound by solvent-free melting mode, and is characterized in that: the pre-reaction temperature is higher than the melting point temperature of the compound with the phenol structure part, and the dosage of the compound with the phenol structure part exceeds the reaction amount, so that the molten liquid of the compound with the phenol structure part is used as a reaction solvent, other organic solvents do not need to be added, the operation is simple, the reaction cost is low, and the environmental pollution is not easily caused.

The 9-fluorenone with the purity of more than 95 percent is preferably used.

The compound having a phenolic moiety may optionally have one or more inert substituents, and the presence of the inert substituents does not interfere with the condensation reaction of the compound having a phenolic moiety and 9-fluorenone. However, the compound having a phenol moiety must have at least one unsubstituted binding site for reacting with 9-fluorenone to form a bond.

In one embodiment, the compound having a phenolic moiety comprises one selected from the group consisting of naphthol, C1-C10 alkylphenol, hydroxybiphenyl, and phenol. Among these, the compound having a phenol moiety is preferably used in a purity of 98% or more.

In another embodiment, the molar ratio of the compound having a phenolic moiety and the 9-fluorenone is from 2:1 to 7: 1.

In a further embodiment, the compound having a phenolic moiety is hydroxybiphenyl, and the molar ratio of hydroxybiphenyl to 9-fluorenone is in particular from 3:1 to 6: 1.

The molar ratio of the compound having a phenolic moiety to the 9-fluorenone is preferably not less than 2:1, so as to avoid poor dissolution and by-product formation of monophenols due to insufficient content of the compound having a phenolic moiety.

The pre-reaction process needs to be continuously stirred at the same time, so that collision among the reactant 9-fluorenone, the compound with the phenol structure part and the catalyst containing the sulfydryl is increased, and the reaction is promoted. After the melting is completed, pre-reaction is carried out for 1 to 10 minutes at a temperature of 60 to 80 ℃ so that partial reactants firstly form an intermediate of the 9-fluorenone and the sulfydryl-containing catalyst, and condensation reaction can be carried out.

The sulfydryl-containing catalyst has higher activity, so that the reaction is favorably carried out under a milder condition. The catalyst containing sulfydryl is one of the group consisting of mercaptan containing C1-C10 alkyl or C6-C12 aryl and sulfydryl carboxylic acid. In one embodiment, the mercaptocarboxylic acid is 3-mercaptopropionic acid, mercaptoacetic acid, or mercaptobenzoic acid, with 3-mercaptopropionic acid being particularly preferred. Specifically, when the compound having a phenol moiety includes one selected from the group consisting of naphthol, C1-C10 alkylphenol, hydroxybiphenyl, and phenol, 3-mercaptopropionic acid is preferably used as a catalyst.

In another embodiment, the molar ratio of the mercapto-containing catalyst to the 9-fluorenone is from 0.1:1 to 3: 1.

In another embodiment, when the mercapto group-containing catalyst is 3-mercaptopropionic acid, the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is preferably 0.15:1 to 0.30: 1.

The condensation reaction is assisted by adding a cocatalyst to assist dehydration, promote the reaction and increase the reaction rate, wherein the cocatalyst preferably uses a dehydrating agent, such as: calcium oxide, and the dehydrating agent is preferably one capable of providing hydrogen ions, such as: sulfuric acid, chlorosulfonic acid, phosphoric acid, polyphosphoric acid or various types of anhydrides, such as sulfuric anhydride, chlorosulfonic anhydride or phosphoric anhydride, wherein the dehydrating agent is preferably sulfuric acid; the cocatalyst is added dropwise at a constant rate during the condensation reaction, while stirring is continued, and the temperature change is strictly controlled to avoid the formation of by-products due to too fast temperature rise.

Specifically, if the reaction temperature is too low, the reaction is slow; if the reaction temperature is too high, side reactions may occur, resulting in a decrease in yield. In one embodiment, the condensation reaction temperature is from 60 to 80 ℃. Wherein the condensation reaction temperature is preferably from 60 to 75 ℃.

In another embodiment, the condensation reaction temperature is the same as the pre-reaction temperature.

In one embodiment, the reaction time for the condensation reaction is from 0.5 to 2 hours. The reaction time of the condensation reaction is preferably from 1 to 1.5 hours.

In one embodiment, the molar ratio of the cocatalyst to the 9-fluorenone is 0.5:1 to 2: 1. According to a particular embodiment, the cocatalyst is sulfuric acid.

In another embodiment, the cocatalyst is sulfuric acid, and the molar ratio of the sulfuric acid to the 9-fluorenone is preferably from 0.6:1 to 1.2: 1.

In one embodiment, the cocatalyst is added at a rate of 0.9 to 9.0 ml/min.

The invention relates to a preparation method of bisphenol fluorene compound with formula (I), wherein, the adding time of the cocatalyst is needed after pre-reaction, so as to avoid the self combination of the cocatalyst of condensation reaction and unreacted catalyst containing sulfhydryl group to influence the yield; and the molar quantity of the cocatalyst is higher than that of the mercapto-containing catalyst, so that the bisphenol fluorene compound with high yield and high purity can be obtained.

In addition, the method for preparing the bisphenol fluorene compound of formula (I) of the present invention may be performed under normal pressure or in an inert gas atmosphere, wherein the inert gas includes nitrogen, argon, helium, or the like.

After the condensation reaction, since the viscous by-product formed in the reaction process is a product of incomplete conversion of 9-fluorenone, which is not beneficial for the rear-end application of the reaction product, the solvent which is insoluble in the bisphenol fluorene compound of formula (I) and has solubility for the by-product and the unreacted compound having a phenol structure portion is selected to stir and soak the reaction mixture, it should be noted that the soaking process is preferably operated at a high temperature of 60 to 90 ℃, otherwise it is not easy to completely separate the bisphenol fluorene compound of formula (I) from the reaction mixture.

The solvent insoluble in the bisphenol fluorene compound of the formula (I) is a benzene solvent substituted by halogen or at least one C1-C5 alkyl. For example, the benzene solvent includes one selected from the group consisting of benzene, toluene, xylene, chlorobenzene, and mesitylene.

In one embodiment, when toluene is used as the solvent insoluble in the bisphenol fluorene-based compound of formula (I), the temperature of the immersion cleaning is 60 to 90 ℃.

After the stirring immersion, the immersion liquid was removed by filtration to obtain a bisphenol fluorene-based compound of the formula (I). The filtration temperature should also be operated at a high temperature to avoid the precipitation of dissolved by-products and unreacted compounds having a phenolic moiety and remaining on the surface of the reaction product. In one embodiment, the soaking temperature is the same as the filtration temperature. The above-mentioned immersion-washing filtration step may be repeated as appropriate until a bisphenol fluorene compound having a high purity is obtained.

The filtered immersion cleaning solution can utilize reduced pressure distillation to recover unreacted compounds with phenol structural parts, and the unreacted compounds are refluxed to a reaction zone to be used as a reaction solvent, so that the environmental pollution is avoided, and the method is more suitable for industrial production.

The preparation method of the bisphenol fluorene compound of formula (I) of the present invention may further comprise neutralizing the bisphenol fluorene compound obtained by the leaching filtration with an alkaline aqueous solution after the leaching filtration step to remove the catalyst and the cocatalyst.

The alkali of the above-mentioned alkaline aqueous solution is an inorganic or organic alkali such as an alkali metal hydroxide or carbonate.

The neutralization treatment may be carried out by adding another water-soluble organic solvent as needed, or optionally at a high temperature.

The invention also provides a preparation method of the bisphenol fluorene compound with the following formula (II),

the method comprises the following steps:

melting 9-fluorenone and hydroxybiphenyl in the presence of a catalyst of 3-mercaptopropionic acid and pre-reacting at a temperature of 60 to 80 ℃ for 1 to 10 minutes, wherein the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 0.15:1 to 0.30: 1;

dropwise adding sulfuric acid at a temperature of 60-80 ℃ to perform a condensation reaction for 1-2 hours to obtain a mixture of the bisphenol fluorene compound having the formula (II), wherein the molar ratio of the sulfuric acid to the 9-fluorenone is 0.5: 1-2: 1, and the dropwise adding speed of the sulfuric acid is 0.9-9.0 ml/min; and

the bisphenol fluorene compound of formula (II) is obtained by stirring, washing and filtering the mixture with a solvent which does not dissolve the bisphenol fluorene compound of formula (II) at a temperature of 60 to 90 ℃.

The present invention is further illustrated in detail by examples.