Preparation method of 4, 4 '-(1, 3-dimethyl butylidene) diphenol
By using thiol resin as a solid phase catalyst, the problems of high corrosion and low yield of synthesis of 4,4'-(1,3-dimethylbutylene)diphenol in the prior art were solved, and an efficient and environmentally friendly preparation method was achieved, which was suitable for industrial production.
Patent Information
- Application Number
- CN202510385328.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-07-04
AI Technical Summary
The method for synthesizing 4,4'-(1,3-dimethylbutylene)diphenol in the prior art has high corrosion, difficulty in controlling and low yield, making it difficult to achieve industrial production.
The thiol resin was used as a solid phase catalyst, and the reaction was carried out by phenol, methyl isobutyl ketone and catalyst at a specific temperature, the resin was removed by filtration, and the phenol was recovered under reduced pressure. A solvent was added to the residue to cool down and a white solid was precipitated to obtain a high-purity 4,4'-(1,3-dimethylbutylene)diphenol.
It realizes the preparation of simple, safe, low pollution, high yield and high purity 4,4'-(1,3-dimethylbutylene)diphenol, which is suitable for large-scale production, reduces energy consumption and improves the feasibility of industrial amplification.
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Figure CN120247660A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 4,4'-(1,3-dimethylbutylene)diphenol. Background Art
[0002] Polycarbonate is an amorphous thermoplastic material with excellent properties, showing special properties in terms of cold resistance, impact resistance and heat resistance. According to the different monomers that make up polycarbonate, it can be divided into several categories such as alicyclic, aliphatic, aromatic, etc. Among them, aromatic polycarbonate with good mechanical properties has a relatively high commercial value.
[0003] 4,4'-(1,3-Dimethylbutylene)diphenol is an important polyimide monomer, and the polycarbonate synthesized by using it has broad application prospects.
[0004] Currently, the common synthesis method mainly uses resorcinol and m-chloronitrobenzene as starting materials and is synthesized through a hydrogen chloride gas catalysis method. The hydrogen chloride gas in this reaction process is highly corrosive, difficult to control, and the yield is relatively low, basically less than 20%, making it difficult to industrialize the production. Summary of the Invention In view of this, this invention aims to propose a preparation method of 4,4'-(1,3-dimethylbutylene)diphenol to solve at least one technical problem in the background art.
[0006] To achieve the above object, the technical solution of this invention is realized as follows: A preparation method of 4,4'-(1,3-dimethylbutylene)diphenol, comprising the following steps: reacting phenol, methyl isobutyl ketone, mercapto resin, and catalyst at a certain temperature, filtering to remove the resin to obtain a filtrate, recovering phenol from the filtrate under reduced pressure, adding a solvent to the residue, cooling to precipitate a white solid, and drying to obtain 4,4'-(1,3-dimethylbutylene)diphenol.
[0007] Further, the reaction temperature is 40 - 80 °C.
[0008] Further, the mercapto resin includes one or more of D190, LSC-400, and HCD-104. Preferably, the mercapto resin is D190 type resin.
[0009] Further, the catalyst includes one or more of concentrated sulfuric acid, concentrated hydrochloric acid, and phosphoric acid. Preferably, the catalyst is concentrated hydrochloric acid.
[0010] Further, the molar ratio of phenol, catalyst, and methyl isobutyl ketone is 2 - 3:1 - 1.5:1.
[0011] Further, the mass ratio of the mercapto resin to phenol is 0.8 - 1.5:1.
[0012] Further, the solvent includes one or more of methanol, ethanol, and acetonitrile. Preferably, the solvent is ethanol.
[0013] A 4,4'-(1,3-dimethylbutylene)diphenol prepared by the above preparation method of 4,4'-(1,3-dimethylbutylene)diphenol has a metal ion concentration of less than 300 ppb and a chromaticity YI of less than 1.
[0014] The mercapto resin, as a solid-phase catalyst, can be recovered by simple filtration, washed, dried, and reused (usually recyclable 3 - 5 times), significantly reducing the discharge of acidic waste liquid, which conforms to the principles of green chemistry. The mercapto resin has both catalytic and ion-removing effects. After resin filtration, the reaction system does not contain soluble catalysts, eliminating steps such as neutralization and water washing, and high-purity products can be obtained directly by extraction.
[0015] Compared with the prior art, the preparation method of a 4,4'-(1,3-dimethylbutylene)diphenol of the present invention has the following advantages: 1. The preparation method of the present invention uses a new process system, which is simple to prepare, safe to operate, has little environmental pollution, has a high yield and high purity of the synthesized product, and is suitable for large-scale production.
[0016] 2. The present application uses a solid-phase catalyst (mercapto resin), which is suitable for a packed column reactor, can realize continuous production, and improves the feasibility of industrial scale-up. The energy consumption of the present application is low, and the reaction temperature is 40 - 80 °C, significantly lower than that of traditional reactions (usually above 100 °C), saving energy costs. Description of the Drawings
[0017] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments and descriptions of the present invention are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 is the synthesis route diagram of 4,4'-(1,3-dimethylbutylene)diphenol in the present invention; Figure 2 is the HPLC diagram of 4,4'-(1,3-dimethylbutylene)diphenol prepared in Example 1 of the present invention. Detailed Embodiments
[0018] It should be noted that, without conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.
[0019] The present invention will be described in detail below with reference to the drawings and in conjunction with the embodiments.
[0020] Example 1 100 g of phenol, 42.57 g of methyl isobutyl ketone, 62.61 g of concentrated hydrochloric acid and 90 g of D190 resin were added to a 2 L three-necked flask, and the temperature was raised to 70 °C and kept for reaction for 4 h. After the reaction was completed, the mercapto resin was removed by hot filtration. The filtrate was subjected to vacuum distillation of unreacted phenol at 90 °C and 0.1 Mpa. 200 g of ethanol was added to the remaining residue, and the temperature was lowered to 0 °C with stirring. A large amount of white crystals precipitated out and were dried in vacuo at 100 °C for 12 h to obtain 125.62 g of 4,4'-(1,3-dimethylbutylene) diphenol, with a molar yield of 87.45%, a purity of 99.95%, a metal ion content of 181 ppb, and YI = 0.87 (the yield is calculated based on phenol).
[0021] Example 2 100 g of phenol, 43.66 g of methyl isobutyl ketone, 62.61 g of concentrated hydrochloric acid and 80 g of LSC-400 resin were added to a 2 L three-necked flask, and the temperature was raised to 65 °C and kept for reaction for 4 h. After the reaction was completed, the mercapto resin was removed by hot filtration. The filtrate was subjected to vacuum distillation of unreacted phenol at 90 °C and 0.1 Mpa. 200 g of ethanol was added to the remaining residue, and the temperature was lowered to -5 °C with stirring. A large amount of white crystals precipitated out and were dried in vacuo at 100 °C for 12 h to obtain 123.09 g of 4,4'-(1,3-dimethylbutylene) diphenol, with a molar yield of 85.69%, a purity of 99.87%, a metal ion content of 198 ppb, and YI = 0.97 (the yield is calculated based on phenol).
[0022] Example 3 100 g of phenol, 44.36 g of methyl isobutyl ketone, 62.61 g of concentrated hydrochloric acid and 100 g of HCD-104 resin were added to a 2 L three-necked flask, and the temperature was raised to 80 °C and kept for reaction for 4 h. After the reaction was completed, the mercapto resin was removed by hot filtration. The filtrate was subjected to vacuum distillation of unreacted phenol at 90 °C and 0.1 Mpa. 200 g of methanol was added to the remaining residue, and the temperature was lowered to 0 °C with stirring. A large amount of white crystals precipitated out and were dried in vacuo at 100 °C for 12 h to obtain 124.64 g of 4,4'-(1,3-dimethylbutylene) diphenol, with a molar yield of 86.77%, a purity of 99.88%, a metal ion content of 189 ppb, and YI = 0.92 (the yield is calculated based on phenol).
[0023] Example 4 100 g of phenol, 42.57 g of methyl isobutyl ketone, 62.61 g of concentrated hydrochloric acid and 90 g of D190 resin were added to a 2 L three-necked flask, and the temperature was raised to 40 °C and the reaction was carried out under insulation for 4 h. After the reaction was completed, the mercapto resin was removed by hot filtration. The filtrate was subjected to vacuum distillation of unreacted phenol at 90 °C and 0.1 Mpa. 200 g of ethanol was added to the remaining residue, and the temperature was lowered to 0 °C with stirring. A large amount of white crystals precipitated out and were dried in vacuo at 100 °C for 12 h to obtain 124.22 g of 4,4'-(1,3-dimethylbutylene) diphenol, with a molar yield of 86.48%, a purity of 99.93%, a metal ion content of 179 ppb, and YI = 0.88 (the yield is calculated based on phenol).
[0024] Example 5 The recovered resin in Example 1 was added to 500 g of deionized water and impregnated for 24 h, and then dried in vacuo at 110 °C for 24 h and denoted as D190-recovered.
[0025] 100 g of phenol, 42.57 g of methyl isobutyl ketone, 62.61 g of concentrated hydrochloric acid and D190-recovered resin were added to a 2 L three-necked flask, and the temperature was raised to 70 °C and the reaction was carried out under insulation for 4 h. After the reaction was completed, the mercapto resin was removed by hot filtration. The filtrate was subjected to vacuum distillation of unreacted phenol at 90 °C and 0.1 Mpa. 200 g of ethanol was added to the remaining residue, and the temperature was lowered to 0 °C with stirring. A large amount of white crystals precipitated out and were dried in vacuo at 100 °C for 12 h to obtain 124.21 g of 4,4'-(1,3-dimethylbutylene) diphenol, with a molar yield of 86.47%, a purity of 99.89%, a metal ion content of 201 ppb, and YI = 0.89 (the yield is calculated based on phenol).
[0026] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
Claims
1. A method for preparing 4,4'-(1,3-dimethylbutylene) diphenol, characterized in that: It includes the following steps: React phenol, methyl isobutyl ketone, mercapto resin, and a catalyst at a certain temperature, filter to remove the resin to obtain a filtrate, recover phenol from the filtrate under reduced pressure, add a solvent to the residue, cool to precipitate a white solid, and dry to obtain 4,4'-(1,3-dimethylbutylene) diphenol.
2. The preparation method of 4,4'-(1,3-dimethylbutylene) diphenol according to claim 1, characterized in that: The reaction temperature is 40 - 80 °C.
3. The preparation method of 4,4'-(1,3-dimethylbutylene) diphenol according to claim 1, characterized in that: The mercapto resin includes one or more of D190, LSC-400, and HCD-104. Preferably, the mercapto resin is D190 type resin.
4. The preparation method of 4,4'-(1,3-dimethylbutylene) diphenol according to claim 1, characterized in that: The catalyst includes one or more of concentrated sulfuric acid, concentrated hydrochloric acid, and phosphoric acid. Preferably, the catalyst is concentrated hydrochloric acid.
5. The preparation method of 4,4'-(1,3-dimethylbutylene) diphenol according to claim 1, characterized in that: The molar ratio of phenol, catalyst, and methyl isobutyl ketone is 2 - 3:1 - 1.5:
1.
6. The preparation method of 4,4'-(1,3-dimethylbutylene) diphenol according to claim 1, characterized in that: The mass ratio of mercapto resin to phenol is 0.8 - 1.5:
1.
7. The preparation method of 4,4'-(1,3-dimethylbutylene) diphenol according to claim 1, characterized in that: The solvent includes one or more of methanol, ethanol, and acetonitrile. Preferably, the solvent is ethanol. A 4,4'-(1,3-dimethylbutylene)diphenol prepared by the method for preparing 4,4'-(1,3-dimethylbutylene)diphenol according to any one of claims 1-7, characterized in that: The metal ion concentration is less than 300 ppb, and the colority YI is less than 1.