CN112225646B - Preparation method of bisphenol TMC - Google Patents

Preparation method of bisphenol TMC Download PDF

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CN112225646B
CN112225646B CN202010972605.2A CN202010972605A CN112225646B CN 112225646 B CN112225646 B CN 112225646B CN 202010972605 A CN202010972605 A CN 202010972605A CN 112225646 B CN112225646 B CN 112225646B
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acid
crown
tmc
catalyst
crown ether
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CN112225646A (en
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丁可
王磊
王文
刘运海
曾伟
魏志涛
黎雷
赵欣
靳少华
蒋玉鑫
陈永
宋延方
杨洋
黎源
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a preparation method of bisphenol TMC. The method comprises the following steps: in the presence of condensation catalyst and cocatalyst, 3,3, 5-trimethylcyclohexanone (TMC for short) and phenol are condensed to prepare bisphenol TMC. The condensation catalyst is mercapto sulfonic acid with carbon atom number of 1-10, preferably mercapto methanesulfonic acid and/or 2-mercapto ethanesulfonic acid. The auxiliary agent is crown ether, preferably one or more of 12-crown ether-4, 15-crown ether-5 and 18-crown ether-6. The mercapto sulfonic acid is used as a catalyst, and the corrosion of the catalyst to a reaction system is far less than that of the prior art, so that the equipment investment and the loss are reduced; the yield of the BPTMC-4,4 body is high, the byproduct BPTMC-2,4 body isomer is less, the separation is easy, the product quality is high, and the method is more suitable for being used as a polymerization monomer.

Description

Preparation method of bisphenol TMC
Technical Field
The invention relates to a preparation method of bisphenol TMC.
Background
The bisphenol TMC (BPTMC) system is named as 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, and the structural formula is
Figure BDA0002684640970000011
Bisphenol TMC is an important chemical raw material, is used as a high polymer material intermediate, and is widely applied to the fields of epoxy resin synthesis, polycarbonate synthesis, phenolic resin synthesis, high-performance coating and the like. The research and development of the bisphenol TMC have important significance on the manufacture, application and development of new materials.
Patent US4964890 teaches that the condensation acid catalyst can be chosen from HCl, HBr, HF, BF3、AlCl3、ZnCl2、SnCl4、PCl3、POCl3Phosphoric acid, hydrochloric acid, sulfuric acid, acetic anhydride and resin. In this patent, a catalyst selected from the group consisting of C1-C18 mercaptans, hydrogen sulfide, thiophenes, thioacids, and thioethers are used as co-catalysts. In the embodiment, HCl gas is used as a catalyst, dodecanethiol is used as a cocatalyst, and the yield of BPTMC is only 79%. The process has the defects of large catalyst consumption, high corrosivity, complex post-treatment, low yield and the like.
Patent CN104292079A uses composite catalyst to prepare BPTMC. The composite catalyst consists of a main catalyst and a secondary catalyst, wherein the main catalyst consists of ferric chloride, copper chloride and aluminum chloride, the secondary catalyst is strong acid resin, and the mass ratio of the main catalyst to the secondary catalyst is (7): 3. since the reaction produces water, ferric chloride, cupric chloride and aluminum chloride are very susceptible to hydrolysis, produce hydrochloric acid, are very corrosive and cause catalyst loss. The patent also has the disadvantages of complex catalyst composition, low reaction activity, large catalyst dosage and the like. The patent gives no reaction results and the BPTMC yield is unknown.
The catalyst used in patent US6284931B1 is selected from concentrated hydrochloric acid, HCl gas, 60-98% sulfuric acid, 85% phosphoric acid and methanesulfonic acid, preferably HCl gas is the catalyst and 1-12 carbon mercaptans are the co-catalyst. When HCl gas is used as a catalyst, HCl is continuously introduced into the reaction system until HCl is saturated. A small amount of water is preferably added into the system to increase the solubility of HCl, under the preferable conditions, the conversion rate of TMC is more than 96%, and the selectivity of BPTMC is about 90%.
Patent JPH05213803(A) compares the reaction effect of HCl, benzene sulfonic acid and methane sulfonic acid, the HCl catalytic effect is obviously stronger than benzene sulfonic acid and methane sulfonic acid. In this patent, strong acid resin is also used as a catalyst, a fixed bed is used, and phenol: mercaptopropionic acid 30: 1:0.15, reaction temperature of 40-45 ℃ and space velocity of 0.25h-1The highest TMC conversion is only 55%. The mercaptopropionic acid used in this patent is used as a promoter and not as a catalyst alone.
The prior literature does not report that only mercaptan, mercaptocarboxylic acid and the like are adopted as BPTMC catalysts. In order to achieve a satisfactory TMC conversion rate, hydrochloric acid or HCl and other strong inorganic acids are generally used as catalysts, and mercaptan and other mercapto compounds are used as cocatalysts. The catalytic effect is poor by using organic acid or acidic resin. The prior art has the defects of high corrosivity, low yield of the BPTMC, more BPTMC isomers, difficult separation and the like when the BPTMC is prepared.
Disclosure of Invention
The invention aims to provide a bisphenol TMC preparation method, which reduces the corrosivity to equipment, improves the yield of the bisphenol TMC, simplifies the post-treatment process and further reduces the energy consumption of subsequent separation under a milder condition.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of bisphenol TMC comprises the following steps: in the presence of condensation catalyst and cocatalyst, 3,3, 5-trimethylcyclohexanone (TMC for short) and phenol are condensed to prepare bisphenol TMC.
The possible mechanism for the reaction of phenol with TMC under acidic conditions to form bisphenol TMC is shown below.
Figure BDA0002684640970000031
TMC firstly reacts with hydrogen ions to generate carbonium ions 1, the carbonium ions 1 react with a molecule of sulfhydryl compound to generate an intermediate 1, the intermediate 1 is dehydrated under acidic conditions to generate carbonium ions 2, the carbonium ions 2 react with a molecule of phenol to generate an intermediate 2, the intermediate 2 is subjected to sulfhydrylation to remove the sulfhydryl compound under acidic conditions to obtain carbonium ions 3, and the carbonium ions 3 react with phenol to generate bisphenol TMC (BPTMC-4, 4-isomer). The transfer of hydrogen ions in different materials and the rapid generation of carbenium ions are key factors affecting the reaction rate.
From the above reaction mechanism, the content of hydrogen ions in the reaction system greatly affects the reaction. In the prior art, strong inorganic acid such as sulfuric acid, hydrochloric acid or HCl and the like is generally used as a catalyst to achieve a satisfactory TMC conversion rate, so that the hydrogen ion content of a system is ensured, and the catalytic effect is poor by using organic acid or solid acid.
The condensation catalyst is mercapto sulfonic acid, which is an organic acid selected from mercapto sulfonic acid containing n carbon atoms, m mercapto groups and x sulfonic acid groups. Wherein n is selected from 1 to 10, preferably 1 to 2, m is selected from 1 to 5, preferably 1 to 2, and x is selected from 1 to 5, preferably 1 to 2.
Examples of suitable mercaptosulfonic acids include, but are not limited to, one or more of mercaptomethanesulfonic acid, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 3-mercaptobutanesulfonic acid, 2-mercaptobutanesulfonic acid, 5-mercaptopentanesulfonic acid, 4-mercaptopentanesulfonic acid, 3-mercaptopentanesulfonic acid, 2, 3-mercaptopropanesulfonic acid, 3, 4-mercaptobutanesulfonic acid, 2, 3-mercaptobutanesulfonic acid, 3, 4-mercaptopentanesulfonic acid, 2, 3-mercaptopentanesulfonic acid, 4, 5-mercaptopentanesulfonic acid; more preferably one or more of mercaptomethanesulfonic acid, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 3-mercaptobutanesulfonic acid, 2-mercaptobutanesulfonic acid and 5-mercaptopentanesulfonic acid; particular preference is given to mercaptomethanesulfonic acid and/or 2-mercaptoethanesulfonic acid.
In the process for the preparation of bisphenol TMC according to the invention, the inorganic Bronsted acid or Lewis acid catalysts disclosed in patent US4964890A are not used.
The mercapto group of the mercapto sulfonic acid has stronger nucleophilicity, and can promote the generation of the carbonium ion 2 and the carbonium ion 3, particularly the generation rate of the carbonium ion 3, when the condensation reaction is carried out, thereby promoting the rate of generating the bisphenol TMC by the reaction and improving the yield of the product.
The mercapto sulfonic acid alone can also be used as a catalyst for the condensation of phenol and bisphenol TMC, but has the following problems: firstly, the sulfydryl sulfonic acid is weaker in acidity than strong inorganic acids such as sulfuric acid, hydrochloric acid or HCl and the like, fewer hydrogen ions are ionized, the concentration of the system hydrogen ions is lower, and the reaction activity is not high; in addition, only mercapto sulfonic acid is used as a catalyst, except for a target product, a large proportion of isomer by-products (such as BPTMC-2,4 bodies) are generated, and the selectivity of the BPTMC-4,4 bodies is not high.
Figure BDA0002684640970000051
The process of the invention adopts crown ether as a cocatalyst, and adopts the mercapto sulfonic acid as a condensation catalyst, so that the effect of adopting sulfuric acid, hydrochloric acid or HCl in other processes can be achieved. The crown ether has good intermolecular action with hydrogen in the sulfydryl sulfonic acid, is beneficial to the ionization of hydrogen in the sulfonic acid group and the increase of the concentration of hydrogen ions in a system.
The crown ether of the invention can increase the content of effective hydrogen ions in a reaction system and accelerate the generation rate of three types of carbonium ions, thereby promoting the reaction to generate bisphenol TMC.
The adjuvants of the present invention are crown ethers, suitable examples include, but are not limited to, one or more of 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, aza-12-crown-4, aza-18-crown-6, diaza-12-crown-4, diaza-18-crown-6, dibenzo-18-crown-6; one or more of 12-crown-4, 15-crown-5, and 18-crown-6 are preferred.
In addition, the crown ether of the invention is adopted as a cocatalyst, which has an unexpected effect, the oxygen atom in the crown ether and the phenolic hydroxyl group in the phenol form a strong hydrogen bond effect, and the crown ether has larger steric hindrance, so that the 4 th position of the phenol can be completely exposed, and the 2 nd position has larger steric hindrance effect of the crown ether. Thus, when the carbonium ion 3 attacks phenol, the carbonium ion can easily attack the 4 th position of phenol, so that bisphenol TMC (BPTMC-4,4 body) is generated, the generation of BPTMC-2,4 body is reduced, and the selectivity of a target product is improved.
Too little catalyst has too slow a reaction rate, and adding too much catalyst does not significantly increase the reaction rate or the reaction yield, which is economically inappropriate. The amount of the mercapto sulfonic acid used as the condensation catalyst is 1-100%, preferably 10-20% of the molar amount of the 3,3, 5-trimethylcyclohexanone.
The amount of the crown ether used in the invention is 0.05-10%, preferably 1-5% of the molar weight of 3,3, 5-trimethylcyclohexanone.
In order to ensure the interaction between the mercapto sulfonic acid and the crown ether, enhance the hydrogen ion content of the system, and ensure that the crown ether effectively increases the selectivity of bisphenol TMC (BPTMC-4,4 body), as a preferable scheme, the molar ratio of the crown ether to the mercapto sulfonic acid is 1-100: 100, preferably 5-20: 100.
the condensation reaction can be carried out in a batch and continuous manner, preferably a batch reaction; the hydrogenation reactor is selected from a reaction kettle, a fixed bed or a slurry bed, and preferably the reaction kettle.
The molar ratio of phenol to TMC is 2-10: 1, preferably 4 to 6: 1.
the reaction temperature in the invention is 0-60 ℃, preferably 20-30 ℃.
The method has the following advantages:
1) the mercapto sulfonic acid is used as a catalyst, and the corrosion of the catalyst to a reaction system is far less than that of the prior art, so that the equipment investment and the loss are reduced;
2) the yield of the BPTMC-4,4 isomer is high, the byproduct BPTMC-2,4 isomer is less, the separation is easy, the product quality is high, and the method is more suitable for being used as a polymerization monomer.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The gas chromatography was determined by Shimadzu GC-2010plus gas analysis. The conditions of the analysis were: a chromatographic column: 30mDB-WAX, ID.:0.32mm, FD.:0.25 μm; 50-230 ℃,3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400 mL/min; sample introduction amount: 0.2. mu.L. Conversion and selectivity were calculated using area normalization.
Example 1
141g (1.5mol) of phenol, 35g (0.25mol) of TMC, 3.6g (0.025mol) of 2-mercaptoethanesulfonic acid and 0.70g of 12-crown-4 (0.004mol) are added into a 500mL reaction kettle, nitrogen is introduced for deoxygenation, and the mixture is heated and stirred in a water bath at 30 ℃ for 6 hours, wherein the TMC conversion rate is 98.9%, the yield of BPTMC-4,4 bodies is 93.7%, and the yield of 2,4 bodies as byproducts is 1.4%.
Example 2
141g of phenol, 35g of TMC, 6.4g of mercaptomethanesulfonic acid and 0.44g of 12-crown-4 are added into a 500mL reaction kettle, nitrogen is introduced to remove oxygen, and the mixture is heated and stirred in a water bath at 25 ℃ for 6 hours, wherein the TMC conversion rate is 99.1%, the BPTMC-4 yield is 93.5%, and the byproduct yield of 2 and 4 is 1.6%.
Example 3
141g of phenol, 35g of TMC, 7.1g of 2-mercaptoethanesulfonic acid and 0.88g of 15-crown-5 are added into a 500mL reaction kettle, nitrogen is introduced to remove oxygen, and the mixture is heated and stirred for 8 hours in a water bath at the temperature of 20 ℃, wherein the TMC conversion rate is 98.5 percent, the yield of BPTMC-4,4 bodies is 93.1 percent, and the yield of 2 and 4 bodies as byproducts is 1.5 percent.
Example 4
141g of phenol, 35g of TMC, 5.1g of mercaptomethanesulfonic acid and 0.7g of 12-crown-4 are added into a 500mL reaction kettle, nitrogen is introduced to remove oxygen, and the mixture is heated and stirred in a water bath at 30 ℃ for 8 hours, wherein the TMC conversion rate is 99.3%, the BPTMC-4 yield and the 4-body yield are 93.3%, and the by-product yield is 2, and the 4-body yield is 1.5%.
Example 5
141g of phenol, 35g of TMC, 5.7g of 2-mercaptoethanesulfonic acid and 0.88g of 15-crown-5 are added into a 500mL reaction kettle, nitrogen is introduced to remove oxygen, and the mixture is heated and stirred for 6 hours in a water bath at 30 ℃ until the TMC conversion rate is 99.1 percent, the yield of BPTMC-4, 4-body is 93.4 percent, and the yield of 2 and 4-body as a byproduct is 1.1 percent.
Comparative example 1
The same procedure as in example 1 was repeated except that 12-crown-4 was not added, except that the conversion of TMC was 55.7%, the yield of BPTMC-4, 4-mer was 32.9%, and the yield of by-product 2, 4-mer was 12.1%.
Comparative example 2
The same procedure as in example 1 was repeated except that 3.6g of ethanesulfonic acid was used instead of 1.8g of 2-mercaptoethanesulfonic acid, and the TMC conversion was 18.7% and the BPTMC-4, 4-mer yield was 9.9%.
Comparative example 3
10g of concentrated hydrochloric acid (37 wt%) was used instead of mercaptoethanesulfonic acid under the same conditions as in example 1, with a TMC conversion of 8.7% and a BPTMC-4, 4-mer yield of 5.9%.
Comparative example 4
1.2g of methyl mercaptan was used instead of mercaptoethanesulfonic acid under otherwise the same conditions as in example 1, with a TMC conversion of less than 1%.
Comparative example 5
141g (1.5mol) of phenol, 35g (0.25mol) of TMC, 2.3g (0.025mol) of 2-mercaptoacetic acid and 0.70g of 12-crown-4 (0.004mol) are added into a 500mL reaction kettle, nitrogen is introduced to remove oxygen, and the mixture is heated and stirred in a water bath at 30 ℃ for 6 hours, wherein the TMC conversion rate is 80.9%, the yield of BPTMC-4,4 bodies is 73.7%, and the yield of 2,4 bodies as byproducts is 3.4%.
Comparative example 6
141g (1.5mol) of phenol, 35g (0.25mol) of TMC, 2.3g (0.025mol) of 2-mercaptoacetic acid and 0.70g of 12-crown-4 (0.004mol) are added into a 500mL reaction kettle, nitrogen is introduced to remove oxygen, 0.2mol of HC1 gas is continuously introduced into a water bath at 30 ℃ and stirred for 6 hours, the conversion rate of TMC is 98.9 percent, the yield of BPTMC-4,4 bodies is 87.7 percent, and the yield of the 2,4 bodies as a byproduct is 7.4 percent.
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.

Claims (13)

1. A preparation method of bisphenol TMC comprises the following steps: in the presence of a condensation catalyst and crown ether, 3,3, 5-trimethylcyclohexanone and phenol are condensed to prepare bisphenol TMC; the condensation catalyst is mercapto sulfonic acid with 1-10 carbon atoms.
2. The method of claim 1, wherein the mercaptosulfonic acid is selected from one or more of mercaptomethanesulfonic acid, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 3-mercaptobutanesulfonic acid, 2-mercaptobutanesulfonic acid, 5-mercaptopentanesulfonic acid, 4-mercaptopentanesulfonic acid, 3-mercaptopentanesulfonic acid, 2, 3-dimercaptopropanesulfonic acid, 3, 4-dimercaptobutanesulfonic acid, 2, 3-dimercaptobutanesulfonic acid, 3, 4-dimercaptopentanesulfonic acid, 2, 3-dimercaptopentanesulfonic acid, 4, 5-dimercaptopentanesulfonic acid.
3. A method according to claim 1, wherein the crown ether is selected from one or more of 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, aza-12-crown-4, aza-18-crown-6, diaza-12-crown-4, diaza-18-crown-6, dibenzo-18-crown-6.
4. The process according to claim 1, wherein the condensation catalyst mercaptosulfonic acid is used in an amount of 1 to 100% by mole based on the amount of 3,3, 5-trimethylcyclohexanone.
5. The process according to claim 1, wherein the condensation catalyst mercaptosulfonic acid is used in an amount of 10 to 20% by mole based on the amount of 3,3, 5-trimethylcyclohexanone.
6. The process according to claim 1, wherein said crown ether is used in an amount of 0.05 to 10% based on the molar amount of 3,3, 5-trimethylcyclohexanone.
7. The process according to claim 1, wherein the amount of crown ether is 1-5% by mole of 3,3, 5-trimethylcyclohexanone.
8. The process according to claim 1, characterized in that the molar ratio of crown ether to mercaptosulfonic acid is from 1 to 100: 100.
9. the process according to claim 1, characterized in that the molar ratio of crown ether to mercaptosulfonic acid is from 5 to 20: 100.
10. the process according to claim 1, wherein the molar ratio of phenol to 3,3, 5-trimethylcyclohexanone is from 2 to 10: 1.
11. the process of claim 1, wherein the molar ratio of phenol to 3,3, 5-trimethylcyclohexanone is from 4 to 6: 1.
12. the process according to claim 1, wherein the reaction temperature is 0-60 ℃.
13. The process according to claim 1, wherein the reaction temperature is 20-30 ℃.
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