CN114436780A - Preparation method of bisphenol Z and bisphenol Z - Google Patents
Preparation method of bisphenol Z and bisphenol Z Download PDFInfo
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- CN114436780A CN114436780A CN202011201129.0A CN202011201129A CN114436780A CN 114436780 A CN114436780 A CN 114436780A CN 202011201129 A CN202011201129 A CN 202011201129A CN 114436780 A CN114436780 A CN 114436780A
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- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000011973 solid acid Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012467 final product Substances 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 239000008096 xylene Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003377 acid catalyst Substances 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006386 neutralization reaction Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000011521 glass Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- SIWVGXQOXWGJCI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-ethenylbenzenesulfonic acid Chemical compound C=CC1=CC=CC=C1C=C.OS(=O)(=O)C1=CC=CC=C1C=C SIWVGXQOXWGJCI-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- -1 sulfhydryl compound Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of bisphenol Z and bisphenol Z. The preparation method comprises the following steps: phenol and cyclohexanone are used as raw materials, solid acid is used as a catalyst, and bisphenol Z is obtained through catalytic dehydration reaction and post-treatment of filtration, distillation and recrystallization; the solid acid is ion exchange resin or molecular sieve. The method does not use corrosive liquid acid catalyst in the reaction process, and has simple operation process, thereby having no high requirement on production equipment. Most importantly, a large amount of water is not needed for cleaning after the reaction, so that the generation of waste water is greatly reduced, alkali is not needed for neutralization, the existence of salt is reduced, and the product quality is improved. In addition, compared with the liquid acid catalyst, the solid acid catalyst can be reused, thereby reducing the investment cost of the catalyst.
Description
Technical Field
The invention relates to the technical field of polycarbonate, in particular to a preparation method of bisphenol Z as a raw material for preparing polycarbonate and bisphenol Z.
Background
Polycarbonate is used as a functional material, has excellent impact resistance and strength, and has excellent light transmittance, so that the polycarbonate has wide application. Bisphenol Z is an important polycarbonate monomer, and because cyclohexane groups are introduced into a molecular chain, the bisphenol Z type polycarbonate has good photoelectric property, the mechanical strength is improved, the surface wear resistance and the scratch resistance are improved, and the service life of the material can be effectively prolonged. Bisphenol Z is increasingly favored as an important functional monomer for modifying polycarbonate, and the preparation technology of bisphenol Z has profound significance for the manufacture, application and development of new materials.
The preparation method of bisphenol Z at present mainly takes phenol and cyclohexanone as raw materials, takes hydrogen chloride, concentrated hydrochloric acid or concentrated hydrochloric acid/glacial acetic acid as a catalyst and a sulfhydryl compound as a cocatalyst, prepares a crude product through Friedel-Crafts alkylation reaction, and then obtains a final product after water washing or alkali neutralization, water washing and recrystallization. Such methods are reported, for example, in patents US 5269883, CN1696090A, US6414200B 1.
The preparation method has the disadvantages that corrosive hydrogen chloride or concentrated hydrochloric acid is used as a catalyst, the requirement on production equipment is high, and in the subsequent treatment process, water needs to be added for cleaning, so that a large amount of wastewater is generated. In addition, the addition of alkaline solution for neutralization and deacidification can generate salt, and salt ions are unfavorable for subsequent application, so that desalting treatment is required, the process is complicated, the investment in equipment, three-waste treatment and the like is increased, the product cost is increased finally, and the large-scale industrial production is not facilitated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of bisphenol Z and bisphenol Z.
The invention relates to a preparation method of bisphenol Z, which takes phenol and cyclohexanone as raw materials and solid acid as a catalyst, and the bisphenol Z is obtained by catalytic dehydration reaction and post-treatment of filtration, distillation and recrystallization. Compared with the prior method using a liquid acid catalyst, the preparation method is suitable for large-scale industrial production, and has the main advantages that no corrosive liquid acid catalyst is used in the reaction process, and the operation process is simple, so that the method has no high requirement on production equipment. Most importantly, a large amount of water is not needed for cleaning after the reaction, so that the generation of waste water is greatly reduced, alkali is not needed for neutralization, the existence of salt is reduced, and the product quality is improved. In addition, compared with the liquid acid catalyst, the solid acid catalyst can be reused, thereby reducing the investment cost of the catalyst.
One of the objects of the present invention is to provide a process for producing bisphenol Z.
The method comprises the following steps:
phenol and cyclohexanone are used as raw materials, solid acid is used as a catalyst, and bisphenol Z is obtained through catalytic dehydration reaction, filtration, distillation and recrystallization post-treatment;
the solid acid is ion exchange resin or molecular sieve.
In a preferred embodiment of the present invention,
the ion exchange resin is a strong acid cation exchange resin, such as: amberlyst 15 resin catalyst, NKC-9 resin catalyst, sulfonic acid type resin catalyst, and the like.
In a preferred embodiment of the present invention,
the molecular sieve is an acidic molecular sieve, such as: ZSM-5 molecular sieve catalyst, sulfonic acid type MCM-41 molecular sieve catalyst, SAPO-34 molecular sieve catalyst and the like.
Compared with the traditional method using liquid acid catalyst, the method using solid acid as catalyst has the main advantages of no corrosive liquid acid catalyst used in the reaction process and simple operation process, thus having no high requirement on production equipment. Most importantly, a large amount of water is not needed for cleaning after the reaction, so that the generation of waste water is greatly reduced, alkali is not needed for neutralization, the existence of salt is reduced, and the product quality is improved. In addition, compared with the liquid acid catalyst, the solid acid catalyst can be reused, thereby reducing the investment cost of the catalyst.
In a preferred embodiment of the present invention,
the method comprises the following steps:
mixing phenol, cyclohexanone and a catalyst, adding a solvent, heating and stirring under normal pressure or reduced pressure, and performing azeotropic reflux dehydration; after the reaction is finished, the reaction solution is filtered, and the filtrate is subjected to reduced pressure distillation to remove the solvent and phenol, so as to obtain a crude product.
In a preferred embodiment of the present invention,
the molar ratio of phenol to cyclohexanone is 2-10; preferably 3-4;
the solvent is toluene or xylene;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 150ml to 1000 ml;
the dosage of the catalyst is 5 wt% -15 wt% of the cyclohexanone.
In a preferred embodiment of the present invention,
the reaction temperature is between room temperature and 110 ℃, and preferably between room temperature and 60 ℃; and/or the presence of a gas in the gas,
the reaction time is 3 to 14 hours, preferably 6 to 7 hours.
In a preferred embodiment of the present invention,
the method further comprises the following steps:
and recrystallizing the crude product to obtain the final product.
In a preferred embodiment of the invention
The recrystallization solvent is methanol, ethanol or ethyl acetate.
Another object of the present invention is to provide bisphenol Z obtainable by said process.
The invention can adopt the following technical scheme:
the preparation method of the bisphenol Z takes phenol and cyclohexanone as raw materials, and the molar ratio of the phenol to the cyclohexanone is 2-10. Solid acid is used as catalyst, including ion exchange resin and molecular sieve catalyst. Mixing the reactant and the catalyst, adding a solvent, heating and stirring the solvent including toluene and xylene, preferably toluene under normal pressure or reduced pressure, and performing azeotropic reflux dehydration at the reaction temperature of room temperature to 110 ℃. The reaction time is 3-14 hours. After the reaction is finished, the reaction solution is filtered, and the filtrate is subjected to reduced pressure distillation to remove the solvent and phenol, so as to obtain a crude product. Recrystallizing the crude product with solvent such as methanol, ethanol, ethyl acetate, etc., preferably ethanol. After recrystallization, the final product is obtained with a yield of 80% or more, more preferably 85% or more, and up to 92%.
The invention has the following effects:
the invention relates to a preparation method of bisphenol Z, which takes phenol and cyclohexanone as raw materials and solid acid as a catalyst, and the bisphenol Z is obtained by catalytic dehydration reaction, filtration, distillation and recrystallization post-treatment. Compared with the prior method using a liquid acid catalyst, the preparation method is suitable for large-scale industrial production, and has the main advantages that no corrosive liquid acid catalyst is used in the reaction process, and the operation process is simple, so that the method has no high requirement on production equipment. Most importantly, a large amount of water is not needed for cleaning after the reaction, so that the generation of waste water is greatly reduced, alkali is not needed for neutralization, the existence of salt is reduced, and the product quality is improved. In addition, compared with the liquid acid catalyst, the solid acid catalyst can be reused, thereby reducing the investment cost of the catalyst.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with the claims defining the existence of materials, methods, procedures, means, or components, or the like, that are regarded as being "known to one of ordinary skill in the art", "prior art", or the like, it is intended that the subject matter so derived encompass those materials, methods, procedures, means, or components which have been conventionally used in the art at the time of filing this application, but which may not be so commonly used at the present time, but will become known in the art as being suitable for a similar purpose.
The endpoints of the ranges and any values disclosed in the present document are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes.
Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the examples are all commercially available.
Example 1
84.7g (0.9mol) of phenol, 29.5g (0.3mol) of cyclohexanone, 3g of Amberlyst 15 ion-exchange resin as a catalyst, and 100ml of toluene were charged into a glass reaction flask equipped with a thermometer, a stirrer, a water separator, and a condensing reflux unit, respectively, and heated to reflux (110 ℃ C.) for 6 hours. Cooling to room temperature after the reaction is finished, filtering, distilling the filtered filtrate under reduced pressure to remove toluene and phenol, and recrystallizing the crude product in ethanol to obtain a final product 74.2g, wherein the yield is 88%, and the melting point of the product is 190-192 ℃.
Example 2
56.5g (0.6mol) of phenol, 29.5g (0.3mol) of cyclohexanone, 3g of Amberlyst 15 ion exchange resin as a catalyst, and 100ml of toluene were put into a glass reaction vessel equipped with a thermometer and a stirrer, respectively, and stirring was continued at room temperature for 8 hours. Filtering after the reaction is finished, distilling the filtered filtrate under reduced pressure to remove toluene and phenol, and recrystallizing the crude product in ethanol to obtain 70.9g of a final product, wherein the yield is 92 percent, and the melting point of the product is 190-192 ℃.
Example 3
56.5g (0.6mol) of phenol, 29.5g (0.3mol) of cyclohexanone, 3g of Amberlyst 15 ion exchange resin as a catalyst, and 100ml of xylene were charged into a glass reaction flask equipped with a thermometer, a stirrer, a water separator, and a reflux condenser, respectively, and heated to 80 ℃ for 4 hours. Cooling to room temperature after the reaction is finished, filtering, distilling the filtered filtrate under reduced pressure to remove xylene and phenol, and recrystallizing the crude product in ethyl acetate to obtain a final product of 64.4g, wherein the yield is 80 percent, and the melting point of the product is 190-192 ℃.
Example 4
Phenol, cyclohexanone, Amberlyst 15 ion exchange resin as catalyst and xylene are added into a glass reaction bottle with thermometer, stirrer, water separator and condensating reflux unit, and heated to 60 deg.c for 4 hr. And after the reaction is finished, cooling to room temperature, filtering, distilling the filtered filtrate under reduced pressure to remove xylene and phenol, and recrystallizing the crude product in ethyl acetate to obtain the final product with the yield of 91.2%.
The molar ratio of phenol to cyclohexanone is 5;
the dosage of the catalyst is 15 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 949 ml.
Example 5
Phenol, cyclohexanone, Amberlyst 15 ion exchange resin as catalyst and xylene are added into a glass reaction bottle with thermometer, stirrer, water separator and condensating reflux unit, and heated to 30 deg.c for 5 hr. And after the reaction is finished, cooling to room temperature, filtering, distilling the filtered filtrate under reduced pressure to remove xylene and phenol, and recrystallizing the crude product in ethyl acetate to obtain the final product with the yield of 89.0%.
The molar ratio of phenol to cyclohexanone is 6;
the dosage of the catalyst is 5 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 678 ml.
Example 6
Phenol, cyclohexanone, a catalyst NKC-9 resin and toluene are respectively added into a glass reaction bottle provided with a thermometer, a stirring device, a water separator and a condensing reflux device, and the mixture is heated to 30 ℃ for 7 hours. And after the reaction is finished, cooling to room temperature, filtering, distilling the filtered filtrate under reduced pressure to remove toluene and phenol, and recrystallizing the crude product in ethyl acetate to obtain the final product with the yield of 90.0%.
The molar ratio of phenol to cyclohexanone is 2;
the dosage of the catalyst is 5 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 339 ml.
Example 7
Phenol, cyclohexanone, a catalyst NKC-9 resin and toluene are respectively added into a glass reaction bottle provided with a thermometer, a stirring device, a water separator and a condensing reflux device, and the mixture is heated to 110 ℃ for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction solution is filtered, the filtered filtrate is subjected to reduced pressure distillation to remove toluene and phenol, and the crude product is recrystallized in ethyl acetate to obtain a final product with the yield of 87.0%.
The molar ratio of phenol to cyclohexanone is 3;
the dosage of the catalyst is 15 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 678 ml.
Example 8
Phenol, cyclohexanone, catalyst NKC-9 resin and toluene are added into a glass reaction bottle provided with a thermometer, a stirring device, a water separator and a condensing reflux device respectively, and the mixture is heated to 60 ℃ for 5 hours. After the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, the filtered filtrate is subjected to reduced pressure distillation to remove toluene and phenol, and the crude product is recrystallized in ethyl acetate to obtain the final product with the yield of 89.0%.
The molar ratio of phenol to cyclohexanone is 5;
the dosage of the catalyst is 10 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 508 ml.
Example 9
Phenol, cyclohexanone, catalyst ZSM-5 molecular sieve and xylene are respectively added into a glass reaction bottle provided with a thermometer, a stirring device, a water separator and a condensation reflux device, and the room temperature lasts for 8 hours. And after the reaction is finished, filtering, distilling the filtered filtrate under reduced pressure to remove xylene and phenol, and recrystallizing the crude product in ethyl acetate to obtain the final product with the yield of 90.8%.
The molar ratio of phenol to cyclohexanone is 2;
the dosage of the catalyst is 10 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 339 ml.
Example 10
Phenol, cyclohexanone, catalyst ZSM-5 molecular sieve and xylene are respectively added into a glass reaction bottle provided with a thermometer, a stirring device, a water separator and a condensation reflux device, and the mixture is heated to 60 ℃ for 6 hours. And after the reaction is finished, cooling to room temperature, filtering, distilling the filtered filtrate under reduced pressure to remove xylene and phenol, and recrystallizing the crude product in ethyl acetate to obtain the final product with the yield of 90.0%.
The molar ratio of phenol to cyclohexanone is 3;
the dosage of the catalyst is 5 percent of that of the cyclohexanone;
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 847 ml.
The invention relates to a preparation method of bisphenol Z, which takes phenol and cyclohexanone as raw materials and solid acid as a catalyst, and the bisphenol Z is obtained by catalytic dehydration reaction, filtration, distillation and recrystallization post-treatment. Compared with the prior method using a liquid acid catalyst, the preparation method is suitable for large-scale industrial production, and has the main advantages that no corrosive liquid acid catalyst is used in the reaction process, and the operation process is simple, so that the method has no high requirement on production equipment. Most importantly, no large amount of water is needed for cleaning after the reaction, thus greatly reducing the generation of waste water, not using alkali for neutralization, reducing the existence of salt and improving the product quality. In addition, compared with the liquid acid catalyst, the solid acid catalyst can be reused, thereby reducing the investment cost of the catalyst.
Claims (10)
1. A process for producing bisphenol Z, characterized in that said process comprises:
phenol and cyclohexanone are used as raw materials, solid acid is used as a catalyst, and bisphenol Z is obtained through catalytic dehydration reaction, filtration, distillation and recrystallization post-treatment;
the solid acid is ion exchange resin or molecular sieve.
2. The method of claim 1, wherein:
the ion exchange resin is a strong acid cation exchange resin.
3. The method of claim 1, wherein:
the molecular sieve is an acidic molecular sieve.
4. The method of claim 1, wherein the method comprises:
mixing phenol, cyclohexanone and a catalyst, adding a solvent, heating and stirring under normal pressure or reduced pressure, and performing azeotropic reflux dehydration; after the reaction is finished, the reaction solution is filtered, and the filtrate is subjected to reduced pressure distillation to remove the solvent and phenol, so as to obtain a crude product.
5. The method of claim 4, wherein:
the molar ratio of phenol to cyclohexanone is 2-10; preferably 3-4; and/or the presence of a gas in the gas,
the solvent is toluene or xylene.
6. The method of claim 4, wherein:
the reaction temperature is between room temperature and 110 ℃, and preferably between room temperature and 60 ℃; and/or the presence of a gas in the gas,
the reaction time is 3 to 14 hours, preferably 6 to 7 hours.
7. The method of claim 4, wherein:
the dosage ratio of the cyclohexanone to the solvent is as follows: 100 g: 150ml to 1000 ml; and/or
The dosage of the catalyst is 5 wt% -15 wt% of the cyclohexanone.
8. The method according to any one of claims 4 to 7, wherein:
and recrystallizing the crude product to obtain the final product.
9. The method of claim 8, wherein:
the recrystallization solvent is methanol, ethanol or ethyl acetate.
10. Bisphenol Z obtainable by a process according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160110A (en) * | 2022-07-22 | 2022-10-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing bisphenol Z |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1205794A (en) * | 1966-09-22 | 1970-09-16 | Union Carbide Corp | Process for the preparation of paraphenylphenol |
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| CN115160110A (en) * | 2022-07-22 | 2022-10-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing bisphenol Z |
| CN115160110B (en) * | 2022-07-22 | 2024-02-20 | 中国科学院成都有机化学有限公司 | Method for synthesizing bisphenol Z |
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