CN112574006A - Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol - Google Patents
Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol Download PDFInfo
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- CN112574006A CN112574006A CN202011626529.6A CN202011626529A CN112574006A CN 112574006 A CN112574006 A CN 112574006A CN 202011626529 A CN202011626529 A CN 202011626529A CN 112574006 A CN112574006 A CN 112574006A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- JVJMRLZNFIEHGR-UHFFFAOYSA-N 4-tert-butyl-2-(1-phenylethyl)phenol Chemical compound C=1C(C(C)(C)C)=CC=C(O)C=1C(C)C1=CC=CC=C1 JVJMRLZNFIEHGR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 95
- 229920005989 resin Polymers 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 104
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 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 description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002608 ionic liquid Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- -1 Alpha-methylbenzyl Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
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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
- C07C37/14—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 by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol. The preparation method comprises the following steps: step A: washing the resin with water, adding the resin into a beaker filled with 1-8% of acid solution, stirring and acidifying the resin and the acid solution at a ratio of 300g to 1L, filtering the obtained resin, washing the obtained resin with water to be neutral, repeating the washing for 3-5 times, drying the obtained resin in a constant-temperature oven at a temperature of less than or equal to 60 ℃, and storing the dried resin in a dryer. The preparation method of the 4-tert-butyl-2 (alpha-methylbenzyl) phenol adopts resin as a catalyst, the resin is easy to separate from reactants, and complex post-treatment is not needed; the catalyst has good catalytic effect and high catalytic selectivity, and the resin can be repeatedly used and is easy to realize continuity; no corrosion to equipment and low requirements on equipment materials; the reaction process generates less waste, and the waste treatment is simplified; meanwhile, the method has the advantages of low energy consumption, simplicity in operation, environmental friendliness and the like.
Description
Technical Field
The invention relates to a preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol.
Background
The 4-tert-butyl-2 (alpha-methylbenzyl) phenol prepared by the invention is an important extractant for extracting and separating rubidium and cesium from lithium extraction mother liquor by a lepidolite-lime method, and has the advantages of high extraction efficiency, strong selectivity and the like. Domestic research is mainly focused on the performance of different reaction catalysts and related process research. The synthesis method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol includes two synthesis methods, namely direct synthesis and indirect synthesis, wherein the direct synthesis method is the mainstream synthesis method, namely 4-tert-butylphenol and styrene are used as starting materials, and Lewis acid or acidic phenol is usedThe catalyst (2) is prepared by Friedel-crafts alkylation (F-C reaction) catalyzed by heteropoly acid, resin, acidic ionic liquid and the like. Alpha-methylbenzyl enters ortho-position of phenolic hydroxyl in synthetic reaction to generate alpha-methylbenzylt-BAMBP. The synthesis reaction process is shown below.
Inorganic acid catalysis
Inorganic acids such as sulfuric acid, phosphoric acid, etc., are cheap and easily available, have wide application range, and are commonly used catalysts in industry. Uses concentrated phosphoric acid as catalyst and 4-tert-butylphenol and styrene as raw materials to synthesizetBAMBP, the relevant optimized synthesis conditions were determined by condition experiments. And a certain exploration is made on the vacuum rectification process for synthesizing the crude product.
Chloroaluminate ionic liquid catalysis
The ionic liquid is also called as room-temperature ionic liquid, and refers to a liquid compound with only ions and no molecules at room temperature. Its vapor pressure is approximately equal to zero, and it has the characteristics of non-volatility, non-flammability, wide range of existing liquid phase temperature and no coordination ability. The Lewis acid ionic liquid has the characteristic of non-volatile solid acid, has the characteristic of high reaction activity due to the liquid property, is not easy to corrode equipment, is easy to separate and can be repeatedly used, so that the Lewis acid ionic liquid is a catalytic system with wide prospect.
Using 1-alkylpyridine or 1-methyl-3-alkylimidazole quaternary ammonium salt and AlCl3Synthesizing chloroaluminate ionic liquid which is liquid at room temperature and is used as an F-C reaction catalyst. The method comprises the steps of adding a certain amount of 4-tert-butyl benzene, n-heptane and ionic liquid into a reaction bottle, keeping the reaction temperature constant, slowly dropwise adding styrene while stirring, stirring for reacting for a period of time, and separating out an organic phase after the reaction is stopped. Washing, drying and removing solvent to obtaint-crude product of BAMBP. Separating with silica gel column chromatography to obtain colorless extractt-BAMBP. The method is complex in operation, and the product and the reactant are difficult to separate.
Heteropolyacid catalysis
Catalytic synthesis by using Keggin type 12-phosphotungstic acidtBAMBP, in a way that styrene is dropwise added into a system at a certain temperature by using n-heptane as a reaction solvent, and the reaction is continued for 60min after the dropwise addition is finished. Stopping heating, filtering out the catalyst, and stopping the reaction to obtain a light yellow transparent liquid; distilling to remove n-heptane to obtain yellow viscous liquidt-BAMBP crude product. The optimal conditions of the reaction are as follows: the reaction temperature is 90 ℃, the catalyst dosage is 1 percent (the mass ratio of heteropoly acid to 4-tert-butylphenol), the reaction time is 90min, n (4-tert-butylphenol)/n (styrene) =1/1.3, the proper conversion rate of 4-tert-butylphenol is 95 percent under the condition,tthe yield of-BAMBP was 62.4%. This method does not separate the product from the reactants well and yields the product are low.
Disclosure of Invention
The present invention is directed to the traditiontThe preparation method of BAMBP has the problems of complex process, difficult separation of products and catalysts, low product yield, poor production safety and the like. The preparation method is simple in operation, high in yield, easy in separation of the catalyst and the product, and capable of realizing industrial production, and is a preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol by taking p-tert-butylphenol and styrene as reactants and resin as a reaction catalyst.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol comprises the following steps.
Step A: washing the resin with water, adding the resin into a beaker filled with 1-8% of acid solution, stirring and acidifying the resin and the acid solution at a ratio of 300g to 1L for 2-6h, filtering to obtain resin, washing the resin with water to be neutral, repeating the washing for 3-5 times, drying the obtained resin in a constant-temperature oven at a temperature of less than or equal to 60 ℃, and storing the dried resin in a dryer;
and B: weighing 500g of 4-tert-butylphenol and 1-5% of acidified resin in the step A based on the mass of the 4-tert-butylphenol, adding the resin into a 2L three-neck flask, adding a magnetic stirrer, heating to 120 ℃, heating until the solid 4-tert-butylphenol is dissolved, slowly dropwise adding styrene into the three-neck flask through a constant pressure funnel, wherein the addition of the styrene is 1-1.5 times of the molar mass of the 4-tert-butylphenol, the dropwise adding speed is controlled to be 400g for 2 hours, the system temperature in the dropwise adding process is controlled to be basically constant, and after the dropwise adding is finished, the reaction temperature in the kettle is increased to 120-140 ℃ for reaction for 2 hours;
and C: after the reaction is finished, sieving the solution by using a screen to separate the resin from the crude product solution, washing the resin by using styrene and then repeatedly using the resin, distilling and purifying the obtained mixed solution of the styrene and the crude product, and using the distilled styrene and 4-tert-butylphenol as raw materials for the next reaction;
step D: distilling with reduced pressure distillation device, heating the system to 100 deg.C under 0.08MPa vacuum degree to evaporate styrene as far as possible, steam temperature is 40-60 deg.C, collecting styrene, replacing condenser tube when no liquid flows out, raising system temperature to 160 deg.C, collecting 4-tert-butylphenol, steam temperature is 150 deg.C, distilling to obtain 4-tert-butylphenol, raising system temperature to 280 deg.C, continuing reduced pressure distillation, collecting product fractiontBAMBP, when the temperature drops rapidly, the reaction is finished, and complex organic substances are discarded.
Further, the resin of step a is a strong acid cation exchange resin.
Further, the acid of the step A is hydrochloric acid or sulfuric acid.
Further, the resin obtained in the step A is dried in a constant temperature oven at 60 ℃ for more than 12 h.
Further, the dropping temperature of the styrene in the step B is consistent with the reaction temperature.
Further, the screen of the step C is 200 meshes.
The invention discloses a preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol, which adopts styrene and 4-tert-butylphenol as raw materials and cation exchange resin as a catalyst and comprises the following steps: 1. acidizing the resin; 2.4-tert-butyl-2 (alpha-methylbenzyl) phenol; 3. and (5) distillation, separation and purification. The invention has the beneficial effects that: the adopted resin is a catalyst, the resin is easy to separate from reactants, and complex post-treatment is not needed; the catalyst has good catalytic effect and high catalytic selectivity, and the resin can be repeatedly used and is easy to realize continuity; no corrosion to equipment and low requirements on equipment materials; the reaction process generates less waste, and the waste treatment is simplified; meanwhile, the method has the advantages of low energy consumption, simplicity in operation, environmental friendliness and the like.
Drawings
Fig. 1 is a process flow diagram for small preparation of 4-tert-butyl-2 (α -methylbenzyl) phenol according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, the present invention provides a method for preparing 4-tert-butyl-2 (α -methylbenzyl) phenol, including the following steps:
step A, acidizing resin: washing the resin with water, adding the resin into a beaker filled with 1-8% of acid solution, stirring and acidifying the resin and the acid solution for 2-6h, filtering to obtain resin, washing the resin with water to be neutral, repeating the experiment for 3-5 times, drying the obtained resin in a constant-temperature oven at the temperature of less than or equal to 60 ℃, and storing the dried resin in a dryer;
step B, synthesis of 4-tert-butyl-2 (α -methylbenzyl) phenol: weighing 500g of 4-tert-butylphenol and 1-5% of the acidified resin in the step A by mass of the 4-tert-butylphenol, adding the resin into a 2L three-neck flask, adding a magnetic stirrer, heating to 120 ℃, and heating until the solid 4-tert-butylphenol is dissolved; slowly dripping styrene into the three-neck flask through a constant pressure funnel, wherein the addition amount of the styrene is 1-1.5 times of the molar mass of 4-tert-butylphenol, the dripping speed is controlled to be 400g for 2 hours, and the system temperature is controlled to be basically constant in the dripping process; after the dropwise addition is finished, the reaction temperature in the kettle is raised to 120-140 ℃ for reaction for 2 h;
step C, washing and separating: after the reaction is finished, sieving the solution by using a screen to separate the resin from the crude product solution, washing the resin by using styrene and then repeatedly using the washed resin, distilling and purifying the obtained mixed solution of the styrene and the crude product, and using the distilled styrene and the p-tert-butylphenol as raw materials for the next reaction;
d, distillation, separation and purification: distilling with a reduced pressure distillation device, heating the system to 100 deg.C under 0.08MPa vacuum degree to evaporate styrene as far as possible, wherein the steam temperature is 40-60 deg.C, and collecting styrene; when no obvious liquid flows out, the condenser pipe is replaced, the temperature of the system is gradually increased to 160 ℃, the collection of the 4-tert-butylphenol is started, and the steam temperature is 150 ℃. The process should be well insulated and the distilled 4-tert-butylstyrene is very easy to condense into solid and cause blockage and danger. After 4-tert-butylphenol is distilled out, the temperature of the system is raised to 280 ℃, the reduced pressure distillation is continued, and the product fraction is collectedtBAMBP, when the temperature drops rapidly, the reaction is finished, and the final complex organic matters with high boiling points are discarded.
Further, the resin in step a is a strong acid cation exchange resin, and the acidic solution can be a hydrochloric acid or sulfuric acid solution.
Further, the acid in the step A is at least one of hydrochloric acid and sulfuric acid.
Further, the resin obtained in the step A is dried in a constant temperature oven at 60 ℃ for more than 12 h.
Further, the dropping temperature of the styrene in the step B is kept consistent with the reaction temperature as much as possible.
Further, the screen of the step C is 200 meshes.
Example 1:
step A, acidizing resin: washing the resin with water, adding the resin into a beaker filled with 1-8% of an acid solution, stirring and acidifying for 4h, filtering to obtain a resin, washing the resin with water to be neutral, repeating the experiment for 3 times, drying the obtained resin in a constant-temperature oven at 60 ℃, and storing the dried resin in a dryer;
step B, synthesis of 4-tert-butyl-2 (α -methylbenzyl) phenol: weighing 500g of p-tert-butylphenol and 5% of acidified resin in the step A by mass, adding the resin into a 2L three-neck flask, adding a magnetic stirrer, heating to 120 ℃, and heating until solid p-tert-butylphenol is dissolved; slowly dripping styrene into the three-neck flask through a constant pressure funnel, wherein the addition amount of the styrene is 1.05 times of the molar mass of 4-tert-butylphenol, the dripping speed is controlled to be 400g for 2 hours, and the system temperature is controlled to be basically constant in the dripping process; after the dropwise addition is finished, the reaction temperature in the kettle is raised to 130 ℃ for reaction for 2 hours,tyield of BAMBP 64.07%;
step C, washing and separating: after the reaction is finished, sieving the solution by using a screen to separate the resin from the crude product solution, washing the resin by using styrene and then repeatedly using the washed resin, distilling and purifying the obtained mixed solution of the styrene and the crude product, and using the distilled styrene and the p-tert-butylphenol as raw materials for the next reaction;
d, distillation, separation and purification: distilling with a reduced pressure distillation device, heating the system to 100 deg.C under 0.08MPa vacuum degree to evaporate styrene as far as possible, wherein the steam temperature is 40-60 deg.C, and collecting styrene; when no obvious liquid flows out, the condenser pipe is replaced, the temperature of the system is gradually increased to 160 ℃, the collection of the 4-tert-butylphenol is started, and the steam temperature is 150 ℃. The process should be well insulated and the distilled 4-tert-butylstyrene is very easy to condense into solid and cause blockage and danger. After 4-tert-butylphenol is distilled out, the temperature of the system is raised to 280 ℃, the reduced pressure distillation is continued, and the product fraction is collectedtBAMBP, when the temperature drops rapidly, the reaction is finished, and the final complex organic matters with high boiling points are discarded.
Example 2:
step A, acidizing resin: washing the resin with water, adding the resin into a beaker filled with 1-8% of an acid solution, stirring and acidifying for 4h, filtering to obtain a resin, washing the resin with water to be neutral, repeating the experiment for 3 times, drying the obtained resin in a constant-temperature oven at 60 ℃, and storing the dried resin in a dryer;
step B, synthesis of 4-tert-butyl-2 (α -methylbenzyl) phenol: weighing 500g of p-tert-butylphenol and 2% by mass of p-tert-butylphenol of the acidified resin obtained in the step A, adding the weighed p-tert-butylphenol and acidified resin into a 2L three-neck flask, adding a magnetic stirrer, heating to 120 ℃, and heating until solid p-tert-butylphenol is dissolved; slowly dripping styrene into the three-neck flask through a constant pressure funnel, wherein the addition amount of the styrene is 1.1 times of the molar mass of 4-tert-butylphenol, the dripping speed is controlled to be 400g for 2 hours, and the system temperature is controlled to be basically constant in the dripping process; after the dropwise addition is finished, the reaction temperature in the kettle is raised to 130 ℃ for reaction for 2 hours,tthe yield of-BAMBP is 85%
Step C, washing and separating: after the reaction is finished, sieving the solution by using a screen to separate the resin from the crude product solution, washing the resin by using styrene and then repeatedly using the washed resin, distilling and purifying the obtained mixed solution of the styrene and the crude product, and using the distilled styrene and the p-tert-butylphenol as raw materials for the next reaction;
d, distillation, separation and purification: distilling with a reduced pressure distillation device, heating the system to 100 deg.C under 0.08MPa vacuum degree to evaporate styrene as far as possible, wherein the steam temperature is 40-60 deg.C, and collecting styrene; when no obvious liquid flows out, the condenser pipe is replaced, the temperature of the system is gradually increased to 160 ℃, the collection of the 4-tert-butylphenol is started, and the steam temperature is 150 ℃. The process should be well insulated and the distilled 4-tert-butylstyrene is very easy to condense into solid and cause blockage and danger. After 4-tert-butylphenol is distilled out, the temperature of the system is raised to 280 ℃, the reduced pressure distillation is continued, and the product fraction is collectedtBAMBP, when the temperature drops rapidly, the reaction is finished, and the final complex organic matters with high boiling points are discarded.
Example 3:
step A, acidizing resin: washing the resin with water, adding the resin into a beaker filled with 1-8% of an acid solution, stirring and acidifying for 4h, filtering to obtain a resin, washing the resin with water to be neutral, repeating the experiment for 3 times, drying the obtained resin in a constant-temperature oven at 60 ℃, and storing the dried resin in a dryer;
step B, synthesis of 4-tert-butyl-2 (α -methylbenzyl) phenol: weighing 500g of p-tert-butylphenol and 2% by mass of p-tert-butylphenol of the acidified resin obtained in the step A, adding the weighed p-tert-butylphenol and acidified resin into a 2L three-neck flask, adding a magnetic stirrer, heating to 140 ℃, and heating until solid p-tert-butylphenol is dissolved; slowly dripping styrene into the three-neck flask through a constant pressure funnel, wherein the addition amount of the styrene is 1.05 times of the molar mass of 4-tert-butylphenol, the dripping speed is controlled to be 400g for 2 hours, and the system temperature is controlled to be basically constant in the dripping process; after the dropwise addition is finished, the reaction temperature in the kettle is raised to 130 ℃ for reaction for 2 hours,tthe yield of-BAMBP is 78%
Step C, washing and separating: after the reaction is finished, sieving the solution by using a screen to separate the resin from the crude product solution, washing the resin by using styrene and then repeatedly using the washed resin, distilling and purifying the obtained mixed solution of the styrene and the crude product, and using the distilled styrene and the p-tert-butylphenol as raw materials for the next reaction;
d, distillation, separation and purification: distilling with a reduced pressure distillation device, heating the system to 100 deg.C under 0.08MPa vacuum degree to evaporate styrene as far as possible, wherein the steam temperature is 40-60 deg.C, and collecting styrene; when no obvious liquid flows out, the condenser pipe is replaced, the temperature of the system is gradually increased to 160 ℃, the collection of the 4-tert-butylphenol is started, and the steam temperature is 150 ℃. The process should be well insulated and the distilled 4-tert-butylstyrene is very easy to condense into solid and cause blockage and danger. After 4-tert-butylphenol is distilled out, the temperature of the system is raised to 280 ℃, the reduced pressure distillation is continued, and the product fraction is collectedtBAMBP, when the temperature drops rapidly, the reaction is finished, and the final complex organic matters with high boiling points are discarded.
TABLE 1 analysis of the composition of crude products under different reaction conditions
The above description is only intended to illustrate a few specific embodiments of the present invention, but not to limit the scope of the present invention, and any person skilled in the art should be considered as falling within the scope of the present invention by making equivalent changes or simple modifications according to the technical solution and concept of the present invention.
Claims (6)
1. A preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol comprises the following steps:
step A: washing the resin with water, adding the resin into a beaker filled with 1-8% of acid solution, stirring and acidifying the resin and the acid solution at a ratio of 300g to 1L for 2-6h, filtering to obtain resin, washing the resin with water to be neutral, repeating the washing for 3-5 times, drying the obtained resin in a constant-temperature oven at a temperature of less than or equal to 60 ℃, and storing the dried resin in a dryer;
and B: weighing 500g of 4-tert-butylphenol and 1-5% of acidified resin in the step A based on the mass of the 4-tert-butylphenol, adding the resin into a 2L three-neck flask, adding a magnetic stirrer, heating to 120 ℃, heating until the solid 4-tert-butylphenol is dissolved, slowly dropwise adding styrene into the three-neck flask through a constant pressure funnel, wherein the addition of the styrene is 1-1.5 times of the molar mass of the 4-tert-butylphenol, the dropwise adding speed is controlled to be 400g for 2 hours, the system temperature in the dropwise adding process is controlled to be basically constant, and after the dropwise adding is finished, the reaction temperature in the kettle is increased to 120-140 ℃ for reaction for 2 hours;
and C: after the reaction is finished, sieving the solution by using a screen to separate the resin from the crude product solution, washing the resin by using styrene and then repeatedly using the resin, distilling and purifying the obtained mixed solution of the styrene and the crude product, and using the distilled styrene and 4-tert-butylphenol as raw materials for the next reaction;
step D: distilling with reduced pressure distillation device, heating the system to 100 deg.C under 0.08MPa vacuum degree to evaporate styrene as far as possible, steam temperature is 40-60 deg.C, collecting styrene, replacing condenser tube when no liquid flows out, heating the system to 160 deg.C, collecting 4-tert-butylphenol, steam temperature is 150 deg.C, and distillingAfter 4-tert-butylphenol is distilled off, the temperature of the system is raised to 280 ℃, the reduced pressure distillation is continued, and product fractions are collectedtBAMBP, when the temperature drops rapidly, the reaction is finished, and complex organic substances are discarded.
2. The process of claim 1, wherein the preparation process comprises the steps of: the resin of the step A is a strong acid cation exchange resin.
3. The process of claim 1, wherein the preparation process comprises the steps of: the acid in the step A is hydrochloric acid or sulfuric acid.
4. The process of claim 1, wherein the preparation process comprises the steps of: and B, drying the resin obtained in the step A in a constant-temperature oven at 60 ℃ for more than 12 h.
5. The process of claim 1, wherein the preparation process comprises the steps of: and the dripping temperature of the styrene in the step B is consistent with the reaction temperature.
6. The process of claim 1, wherein the preparation process comprises the steps of: and the screen of the step C is 200 meshes.
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| CN115819188A (en) * | 2022-12-07 | 2023-03-21 | 达高工业技术研究院(广州)有限公司 | Preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol |
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| CN114591147A (en) * | 2022-05-10 | 2022-06-07 | 天津天大天海化工新技术有限公司 | Method for synthesizing 4-tert-butyl-2- (alpha-methylbenzyl) phenol |
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| CN115819188A (en) * | 2022-12-07 | 2023-03-21 | 达高工业技术研究院(广州)有限公司 | Preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol |
| CN115819188B (en) * | 2022-12-07 | 2023-08-15 | 达高工业技术研究院(广州)有限公司 | Preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol |
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