CN114315852B - Method for preparing 3, 4-dimethylbenzylidene sorbitol with zero byproduct - Google Patents
Method for preparing 3, 4-dimethylbenzylidene sorbitol with zero byproduct Download PDFInfo
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- DKBCURTUXYMRFB-LXTVHRRPSA-N (2r,3r,4s,5r)-7-(3,4-dimethylphenyl)hept-6-ene-1,2,3,4,5,6-hexol Chemical compound CC1=CC=C(C=C(O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)C=C1C DKBCURTUXYMRFB-LXTVHRRPSA-N 0.000 title claims abstract description 47
- 239000006227 byproduct Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- POQJHLBMLVTHAU-UHFFFAOYSA-N 3,4-Dimethylbenzaldehyde Chemical compound CC1=CC=C(C=O)C=C1C POQJHLBMLVTHAU-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 120
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- 239000003054 catalyst Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 229940078552 o-xylene Drugs 0.000 claims description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 11
- 239000000600 sorbitol Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
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- 229950005499 carbon tetrachloride Drugs 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 8
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002667 nucleating agent Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
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- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- 238000007265 chloromethylation reaction Methods 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
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- 238000001879 gelation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a method for preparing 3, 4-dimethylbenzylidene sorbitol with zero byproduct. Comprises the preparation of 3, 4-dimethylbenzaldehyde; post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzaldehyde; preparing 3, 4-dimethylbenzylidene sorbitol; post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzylidene sorbitol. The invention, from the preparation of 3, 4-dimethylbenzylidene sorbitol to the synthesis of target product 3, 4-dimethylbenzylidene sorbitol, recovers solvent and byproduct materials during the reaction process, recycles the solvent and byproduct materials, is used as solvent and raw material for synthesizing new materials, does not generate waste materials, and has short production period and easy control of the process.
Description
Technical Field
The invention relates to synthesis of a nucleating agent and recycling of byproducts, in particular to a preparation method of 3, 4-dimethylbenzylidene sorbitol with zero byproducts.
Background
Sorbitol nucleating agent is the most active polypropylene transparent nucleating agent at home and abroad, and nucleating agent 3, 4-dimethylbenzylidene sorbitol (DMDBS) is used as a third-generation product of dibenzylidene sorbitol, can be used for any processing technology, has high dispersing and nucleating efficiency, can improve PP transparency efficiently, does not bring odor and taste to products, and is most suitable for high-grade packaging. At present, the nucleating agent 3, 4-dimethylbenzylidene sorbitol is synthesized by using p-toluenesulfonic acid as a catalyst and cyclohexane and methanol as solvents, but the gelation phenomenon is difficult to control in the reaction process, and the phenomenon that materials cannot be stirred and the reaction fails is very easy to occur. The proper catalyst and solvent are selected, so that the gel phenomenon is improved, the reaction yield is improved, and the reaction time is shortened.
And 3, 4-dimethylbenzaldehyde (3, 4-DBAL) is widely used as a synthesis raw material of a nucleating agent 3, 4-dimethylbenzylidene sorbitol for synthesizing fine chemicals such as medicines, pesticides, spices, beverages, foods and the like. The current synthesis method of 3, 4-dimethylbenzaldehyde mainly comprises the following steps: incomplete oxidation, chloromethylation, bromination hydrolysis, carbonylation. The low-temperature o-xylene carbonylation method is the preferred method for industrial production, the reaction selectivity and the yield are obviously improved under the action of a Lewis acid catalyst, but in the prior art, the selected catalyst is aluminum trichloride, the aluminum trichloride can generate heat to cause explosion after meeting water, the method has strong corrosiveness, and the byproduct of the reaction is difficult to recycle, so that the cost is increased and the environment is polluted. The method selects a proper catalyst to synthesize the 3, 4-dimethylbenzaldehyde, so that the whole reaction is recycled, and the method is the main direction of the current 3, 4-dimethylbenzaldehyde research.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the 3, 4-dimethylbenzylidene sorbitol reaction method which has the advantages of high product purity, high yield, simple process treatment, no waste, environmental protection and energy saving, short production period and easy process control.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a method for preparing 3, 4-dimethylbenzylidene sorbitol with zero byproduct comprises the following steps: preparation of 3, 4-dimethylbenzaldehyde and preparation of 3, 4-dimethylbenzylidene sorbitol.
The preparation of the 3, 4-dimethylbenzaldehyde comprises the following steps: putting o-xylene, concentrated hydrochloric acid, a catalyst and a solvent into a reactor, cooling the obtained mixed solution to 0 ℃, introducing carbon monoxide gas for 0.5h, heating the reaction system to 5 ℃, carrying out heat preservation reaction for 8h, adding water for hydrolysis, separating a water layer, distilling an oil phase at normal pressure to recover the solvent, and standing the recovered solvent; and then distilling the rest materials under the pressure of minus 0.1MPa, obtaining o-xylene at the temperature of 80-100 ℃, continuing to distill, and collecting distillate at the temperature of 110-160 ℃ as 3, 4-dimethylbenzaldehyde.
The preparation of the 3, 4-dimethylbenzylidene sorbitol comprises the following steps: adding 3, 4-dimethylbenzaldehyde, sorbitol, a catalyst and a solvent into a reaction kettle with a water separator, heating and refluxing for reaction for 1h, slowly steaming out part of the solvent for 0.5h, and stopping the reaction when the temperature reaches 95 ℃ after the solvent is separated for later use; adding methanol into the reaction kettle, continuously carrying out reflux reaction for 1h, slowly steaming out part of the methanol for 0.5h, and stopping the reaction when the temperature reaches 97 ℃ after the methanol is separated into water for standby; adding methanol into the reaction kettle again, continuing to reflux for 1h, slowly steaming out part of the methanol for 0.5h, and stopping the reaction when the temperature reaches 99 ℃ after the methanol is separated into water for later use; cooling the reaction system to 50-60 ℃, adding sodium hydroxide methanol solution, neutralizing for 10min, filtering, washing with methanol, vacuum drying the obtained solid at 90 ℃, and pulverizing to obtain 3, 4-dimethylbenzylidene sorbitol.
Further, the method comprises the following steps: post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzaldehyde. The post-treatment of the byproduct generated after the preparation of 3, 4-dimethylbenzaldehyde comprises the following steps: after the preparation of 3, 4-dimethylbenzaldehyde is finished, slowly distilling the residual byproducts in the reactor to 180 ℃ for 2 hours under-0.1 MPa, and collecting distillate in the slow distillation process; collecting the distillate, solvent recovered by oil phase normal pressure distillation in the preparation process of 3, 4-dimethylbenzaldehyde, o-xylene, concentrated hydrochloric acid and catalyst, repeating the preparation steps of 3, 4-dimethylbenzaldehyde, and obtaining 3, 4-dimethylbenzaldehyde again.
Further, the method comprises the following steps: post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzylidene sorbitol. The post-treatment of the by-product generated after the preparation of 3, 4-dimethylbenzylidene sorbitol comprises the following steps: after the preparation of the 3, 4-dimethylbenzylidene sorbitol is finished, collecting filtrate obtained by filtering and filtrate obtained by washing methanol, distilling the filtrate in a reactor at the normal pressure and the temperature of 65 ℃ to recover methanol, slowly distilling the residual materials in the reactor after distillation to 180 ℃ under the pressure of-0.098 MPa, and collecting distillate in the slow distillation process; collecting the distillate, solvent, sorbitol and catalyst obtained after the first water diversion in the preparation process of 3, 4-dimethylbenzylidene sorbitol, repeating the preparation steps of 3, 4-dimethylbenzylidene sorbitol, and obtaining 3, 4-dimethylbenzylidene sorbitol again.
Further, in the above method, in the preparation step of 3, 4-dimethylbenzaldehyde, the molar ratio of o-xylene to concentrated hydrochloric acid to catalyst=1:12:1.3.
Further, in the above method, in the preparation step of 3, 4-dimethylbenzaldehyde, the catalyst is AlCl 3 、ZnCl 2 、CuCl 2 Or FeCl 3 。
Further, in the above method, in the preparation step of 3, 4-dimethylbenzaldehyde, the solvent is dichloromethane, dichloroethane, toluene or tetrachloromethane.
Further, in the above method, in the preparation step of 3, 4-dimethylbenzylidene sorbitol, the molar ratio of sorbitol to 3,4 dimethylbenzaldehyde to catalyst=1:2-2.5:0.05.
Further, in the above method, in the preparation step of 3, 4-dimethylbenzylidene sorbitol, the catalyst is p-toluenesulfonic acid or dodecylbenzenesulfonic acid.
Further, in the above method, in the step of preparing 3, 4-dimethylbenzylidene sorbitol, the solvent is cyclohexane, n-hexane, toluene or xylene.
The beneficial effects of the invention are as follows:
1. the invention starts from the synthesis of 3, 4-dimethylbenzaldehyde, and the byproducts are treated and circularly participate in the reaction, so that the synthesis of 3, 4-dimethylbenzylidene sorbitol is realized, and the byproducts are recycled.
2. The method has the advantages of simple and environment-friendly reaction process, simple byproduct treatment, short reaction time and easy control of the reaction process.
3. The catalyst and the solvent used in the synthesis process are recycled and reused, so that the method is simple in treatment and high in recycling rate.
4. The invention has the advantages of high purity and yield of the synthesized product, and safe and simple operation.
Drawings
FIG. 1 is a gas chromatograph of the 3, 4-dimethylbenzaldehyde prepared in example 1.
FIG. 2 is an infrared spectrum of 3, 4-dimethylbenzylidene sorbitol prepared in example 1.
Detailed Description
The invention is further illustrated by the following specific examples of implementation which are intended to be illustrative in more detail only and are not intended to limit the invention in any way. It will be clear to those skilled in the art that hereinafter, unless specifically indicated, the starting materials and operating methods selected for the present invention are well known in the art.
Example 1
A method for preparing 3, 4-dimethylbenzylidene sorbitol with zero byproduct comprises the following steps: 1) 3, 4-dimethylbenzaldehyde preparation; 2) Post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzaldehyde; 3) Preparing 3, 4-dimethylbenzylidene sorbitol; 4) Post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzylidene sorbitol. The method comprises the following steps:
1) The preparation of 3, 4-dimethylbenzaldehyde comprises the following steps:
o-xylene (106 g,1 mol), concentrated hydrochloric acid (38.4 g,12 mol), catalyst FeCl 3 (212 g,1.3 mol) and 1000mL of tetrachloromethane as a solvent were charged into a reactor, and the resulting mixture was heatedCooling to 0deg.C, introducing CO gas for 0.5 hr, heating the reaction system to 5deg.C, reacting at constant temperature for 8 hr, adding 200mL water for hydrolysis, and removing FeCl 3 Separating out a water layer, distilling an oil phase to 80 ℃ under normal pressure, and recovering solvent tetrachloromethane for later use; and then heating and distilling the residual materials in the reactor under the pressure of minus 0.1MPa, obtaining o-xylene at the temperature of 80-100 ℃, continuing to distill, and collecting distillate at the temperature of 110-160 ℃ to obtain 3, 4-dimethylbenzaldehyde.
The result is shown in figure 1, and the obtained 3,4 dimethylbenzaldehyde has a content of 99.5% and a yield of 86.4% as shown in figure 1.
2) Post-treatment of by-products generated after the preparation of 3, 4-dimethylbenzaldehyde, comprising the steps of;
after the preparation of 3, 4-dimethylbenzaldehyde is finished, slowly distilling the residual byproducts in the reactor to 180 ℃ for 2 hours under the pressure of-0.1 MPa, and collecting distillate in the slow distillation process, wherein the distillate is 3, 4-dimethylbenzaldehyde isomer; finally, collecting the residual little material in the reactor and then calcining at high temperature.
Collecting 1.6g of distillate, 100mL of solvent tetrachloromethane recovered by atmospheric distillation of oil phase in the preparation process of 3, 4-dimethylbenzaldehyde, 9g of o-xylene, 3.84g of concentrated hydrochloric acid and a catalyst FeCl 3 21.2 g, repeating the preparation steps of the 3, 4-dimethylbenzaldehyde to obtain the 3, 4-dimethylbenzaldehyde again, and detecting by gas chromatography, wherein the content reaches 99.12%, and the yield reaches 84.8%.
After the preparation of 3, 4-dimethylbenzaldehyde is finished, the residual CO gas in the reaction tail gas is burnt to prevent air pollution. The tetrachloromethane recovered after atmospheric distillation is continuously used for new 3, 4-dimethylbenzaldehyde synthesis reaction. After the 3, 4-dimethylbenzaldehyde is obtained by reduced pressure distillation, the residual byproduct material is 3, 4-dimethylbenzaldehyde isomer, the material is distilled again by negative pressure, and after the residual trace hydrochloric acid is decomposed, the material is steamed to 180 ℃, and the addition of o-xylene and concentrated hydrochloric acid can be continued to synthesize new 3, 4-dimethylbenzaldehyde. Ferric hydroxide formed after ferric chloride hydrolysis has adsorption effect and can be used for industrial wastewater treatment.
3) Preparing 3, 4-dimethylbenzylidene sorbitol; the method comprises the following steps:
3, 4-dimethylbenzaldehyde (306.2 g,2.28 mol), 98 percent sorbitol (200 g,1.07 mol), catalyst dodecylbenzenesulfonic acid (18 g,0.055 mol) and solvent dimethylbenzene 2000mL are taken and put into a reaction kettle with a water knockout drum, after heating and refluxing for 1h, part of solvent dimethylbenzene is slowly distilled off for 0.5h, the dimethylbenzene is water-dispersed for standby, and the reaction is stopped when the temperature reaches 95 ℃; 400mL of methanol is added into a reaction kettle, after the reflux is continued for 1h, stirring is increased, part of the methanol and a small amount of dimethylbenzene are slowly distilled off for 0.5h, the methanol is separated into water for standby, the dimethylbenzene is separated into water for standby, and the reaction is stopped when the temperature reaches 97 ℃; adding 400mL of methanol into the reaction kettle again, continuously refluxing for 1h, slowly steaming out part of the methanol and a small amount of dimethylbenzene for 0.5h, separating water from the methanol for later use, separating water from a small amount of dimethylbenzene for later use, and stopping the reaction when the temperature reaches 99 ℃; after the reaction system is cooled to 50-60 ℃, sodium hydroxide methanol solution (5 g of sodium hydroxide is dissolved in 250mL of methanol) is added, after neutralization for 10min, filtration and washing are carried out with 2000mL of methanol for 2 times, the obtained solid is dried in vacuum for 12h at 90 ℃, and crushed to obtain 432.51g of a product which is 3, 4-dimethylbenzylidene sorbitol, the yield is 95.14%, and the melting point is 258.6-259.3 ℃ detected by a digital melting point instrument.
FIG. 2 is an infrared spectrum of the prepared 3, 4-dimethylbenzylidene sorbitol.
The xylene distilled off for the first time is used for the next reaction after being subjected to water division. The water-containing methanol obtained by the second distillation and the third distillation and a small amount of dimethylbenzene are separated, and the water-containing methanol is used for washing materials and the dimethylbenzene solution is used for experimental reaction.
4) Post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzylidene sorbitol, comprising the steps of:
after the preparation of 3, 4-dimethylbenzylidene sorbitol is finished, collecting filtrate obtained by filtering and filtrate obtained by washing methanol in a reactor, distilling at normal pressure and 65 ℃ to recover methanol, slowly distilling the residual materials in the reactor after distillation to 180 ℃ under-0.098 MPa, and collecting distillate in the slow distillation process, wherein the distillate is a mixture containing a small amount of 3, 4-dimethylbenzaldehyde and monoacetal condensate.
The preparation procedure of 3, 4-dimethylbenzylidene sorbitol was repeated with the addition of 50mL of methanol each time, taking 5.62g of the collected distillate and 25g of 3, 4-dimethylbenzylidene formaldehyde produced after the post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzylidene sorbitol, 200mL of solvent xylene obtained after the first water separation in the preparation process of 3, 4-dimethylbenzylidene sorbitol, 20g of 98% sorbitol and 1.8g of dodecylbenzenesulfonic acid catalyst.
Comparative example 1
Adding 32g of 3, 4-dimethylbenzaldehyde, 20g of 98% sorbitol, 1.8g of p-toluenesulfonic acid and 200mL of dimethylbenzene into a reaction bottle, heating and refluxing for reaction for 1h, slowly steaming out part of solvent dimethylbenzene for 0.5h, and stopping the reaction until the temperature reaches 95 ℃. 50mL of methanol is added, the reflux is continued for 1h, the gel phenomenon is serious during the reflux, the stirring is increased, 1000mL of methanol is added, the reflux is continued for 1h, the gel phenomenon is not improved, 200mL of dimethylbenzene and 200mL of methanol solvent are continuously added, part of solvent is distilled off during the reaction, the gel phenomenon is still not improved, the material cannot continue to react, and the experiment is stopped.
Comparative example 2
Adding 32g of 3, 4-dimethylbenzaldehyde, 20g of 98% sorbitol, 3.6g of p-toluenesulfonic acid and 200mL of dimethylbenzene into a reaction bottle, heating and refluxing for reaction for 1h, slowly steaming out part of solvent for 0.5h, and stopping the reaction until the temperature reaches 95 ℃. 50mL of methanol is added for refluxing for 1h, the gel phenomenon is serious in the reaction process, stirring is increased, and the reflux is continued after 1L of methanol solvent is added, so that the phenomenon is not improved yet. The solvent is continuously distilled off slowly for 1h, the reaction is stopped when the temperature reaches 97 ℃, and the gel phenomenon is improved. 1L of methanol is added, reflux is continued for 1h, and the reaction is stopped after the temperature reaches 99 ℃ after the reaction is slowly distilled off for 1 h. Cooling, adding sodium hydroxide methanol solution (5 g sodium hydroxide is dissolved in 250mL methanol), neutralizing for 10min, filtering, and washing with 200mL methanol for 2 times.
And after the product is dried, detecting that the melting point is 212.2-228.6 ℃, wherein the result of the product does not reach the standard.
Claims (4)
1. A method for preparing 3, 4-dimethylbenzylidene sorbitol with zero byproduct is characterized by comprising the following steps of;
1) Preparation of 3, 4-dimethylbenzaldehyde: putting o-xylene, concentrated hydrochloric acid, a catalyst and solvent tetrachloromethane into a reactor, cooling the obtained mixed solution to 0 ℃, introducing carbon monoxide gas of 0.5. 0.5h, heating the reaction system to 5 ℃, preserving heat for reaction of 8h, adding water for hydrolysis, separating a water layer, distilling the oil phase at normal pressure to recover the solvent, and standing the recovered solvent; distilling the rest material under-0.1 MPa to obtain o-xylene at 80-100 ℃, continuing to distill, and collecting distillate at 110-160 ℃ to obtain 3, 4-dimethylbenzaldehyde;
2) Post-treatment of by-products produced after the preparation of 3, 4-dimethylbenzaldehyde: after the preparation of 3, 4-dimethylbenzaldehyde is finished, slowly distilling the residual byproducts in the reactor to 180 ℃ with 2h under-0.1 MPa, and collecting distillate in the slow distillation process; collecting distillate, solvent recovered by oil phase normal pressure distillation in the preparation process of 3, 4-dimethylbenzaldehyde, o-xylene, concentrated hydrochloric acid and catalyst, repeating the preparation steps of 3, 4-dimethylbenzaldehyde, and obtaining 3, 4-dimethylbenzaldehyde again;
3) Preparation of 3, 4-dimethylbenzylidene sorbitol: adding 3, 4-dimethylbenzaldehyde, sorbitol, catalyst dodecylbenzenesulfonic acid and solvent dimethylbenzene into a reaction kettle with a water separator, heating and refluxing to react 1. 1h, slowly steaming out part of the solvent with 0.5h, separating water from the solvent for later use, and stopping the reaction when the temperature reaches 95 ℃; adding methanol into the reaction kettle, continuously refluxing for reaction 1h, slowly steaming out part of the methanol by using 0.5h, and after the methanol is separated into water for standby, stopping the reaction when the temperature reaches 97 ℃; adding methanol into the reaction kettle again, continuing to reflux for reaction 1h, slowly steaming away part of the methanol by 0.5h, and stopping the reaction when the temperature reaches 99 ℃ after the methanol is separated into water for later use; cooling the reaction system to 50-60 ℃, adding sodium hydroxide methanol solution, neutralizing for 10min, filtering, washing with methanol, vacuum drying the obtained solid at 90 ℃, and pulverizing to obtain 3, 4-dimethylbenzylidene sorbitol;
4) Post-treatment of by-products produced after preparation of 3, 4-dimethylbenzylidene sorbitol: after the preparation of the 3, 4-dimethylbenzylidene sorbitol is finished, collecting filtrate obtained by filtering and filtrate obtained by washing methanol, distilling the filtrate in a reactor at the normal pressure and the temperature of 65 ℃ to recover methanol, slowly distilling the residual materials in the reactor after distillation to 180 ℃ under the pressure of-0.098 MPa, and collecting distillate in the slow distillation process; collecting the distillate, solvent, sorbitol and catalyst obtained after the first water diversion in the preparation process of 3, 4-dimethylbenzylidene sorbitol, repeating the preparation steps of 3, 4-dimethylbenzylidene sorbitol, and obtaining 3, 4-dimethylbenzylidene sorbitol again.
2. The process according to claim 1, wherein in the preparation of 3, 4-dimethylbenzaldehyde, the molar ratio of o-xylene to concentrated hydrochloric acid to catalyst = 1 to 12 to 1.3.
3. The process of claim 1, wherein in the step of preparing 3, 4-dimethylbenzaldehyde, the catalyst is AlCl 3 、ZnCl 2 、CuCl 2 Or FeCl 3 。
4. The method according to claim 1, wherein in the preparation step of 3, 4-dimethylbenzylidene sorbitol, sorbitol is 3,4 dimethylbenzaldehyde catalyst=1:2-2.5:0.05 in molar ratio.
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| CN1775780A (en) * | 2005-12-19 | 2006-05-24 | 大庆石油管理局 | Method for preparing 3, 4-dimethyl benzal sorbic alcohol |
| CN1865211A (en) * | 2006-06-23 | 2006-11-22 | 江苏工业学院 | High purity 3,4-dimethyl benzaldehyde preparation method |
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| CN1775780A (en) * | 2005-12-19 | 2006-05-24 | 大庆石油管理局 | Method for preparing 3, 4-dimethyl benzal sorbic alcohol |
| CN1865211A (en) * | 2006-06-23 | 2006-11-22 | 江苏工业学院 | High purity 3,4-dimethyl benzaldehyde preparation method |
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