CN116621695A - Synthesis method for preparing dimethyl sebacate by using high specific surface area silica supported perfluorinated sulfonic acid resin catalyst - Google Patents
Synthesis method for preparing dimethyl sebacate by using high specific surface area silica supported perfluorinated sulfonic acid resin catalyst Download PDFInfo
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- CN116621695A CN116621695A CN202310648616.9A CN202310648616A CN116621695A CN 116621695 A CN116621695 A CN 116621695A CN 202310648616 A CN202310648616 A CN 202310648616A CN 116621695 A CN116621695 A CN 116621695A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 29
- 150000003460 sulfonic acids Chemical class 0.000 title claims abstract description 22
- 229940014772 dimethyl sebacate Drugs 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000004821 distillation Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000805 composite resin Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical group CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 2
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 2
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method for preparing dimethyl sebacate by using a high specific surface area silica supported perfluorinated sulfonic acid resin catalyst, which comprises the following steps: dispersing high specific surface area silicon dioxide into a mixed solution of ethanol, water and hydrochloric acid, namely a solution A, dispersing perfluorinated sulfonic acid resin into absolute ethanol, namely a solution B, mixing the solution A and the solution B, evaporating the mixture under water bath stirring to obtain a solid, and washing, acidifying and drying the solid to obtain the silicon dioxide loaded perfluorinated sulfonic acid resin catalyst; sequentially adding sebacic acid and methanol into a reaction kettle, and then adding a silica supported perfluorinated sulfonic acid resin catalyst for catalytic reaction to obtain a product dimethyl sebacate; the silica supported perfluorinated sulfonic acid resin catalyst synthesized by the method has the advantages of simple synthesis method, high catalytic reaction activity and high reaction selectivity in the synthesis of dimethyl sebacate.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and chemical synthesis, and particularly relates to a synthesis method for preparing dimethyl sebacate by using a high specific surface area silica supported perfluorinated sulfonic acid resin catalyst.
Background
Dimethyl sebacate is used as an organic chemical product with wide application. Can be used as plasticizer, softener and solvent for cellulose resin, vinyl resin and synthetic rubber. Is widely used as a main raw material for producing light stabilizers UV-770, UV-750, UV-123, etc. Can also be used as an intermediate for organic synthesis.
The main method for preparing dimethyl sebacate at present is that sebacic acid and methanol are esterified under acid catalysis to generate. The acid catalyst mainly comprises sulfuric acid, p-toluenesulfonic acid and other homogeneous catalysts. The selectivity of the dimethyl sebacate is improved by adding methanol for many times, and the concentrated sulfuric acid is used as a catalyst, so that equipment is easy to corrode, the concentrated sulfuric acid is difficult to recycle, and a large amount of acid wastewater is generated to pollute the environment. In the processes of washing deacidification and distillation dehydration, the product is easy to return acid and deepen in color.
The perfluorinated sulfonic acid resin is the strongest known solid super acid and has the characteristics of good heat resistance, high chemical stability, high mechanical strength and the like. As a green solid acid catalyst, the catalyst has better catalytic activity and selectivity for a plurality of reactions. The perfluorinated sulfonic acid resin is a novel strong acid solid acid catalyst for replacing concentrated sulfuric acid or p-toluenesulfonic acid in organic synthesis reaction, and is widely applied to the fields of petrochemical industry, fine chemical industry and the like as a catalyst. Solves the problems of large consumption, high cost, poor selectivity, need of adding methanol for many times, corrosion equipment, large discharge of neutralization wastewater, catalyst recovery and the like caused by the prior use of concentrated sulfuric acid or p-toluenesulfonic acid as a catalyst.
Disclosure of Invention
In order to solve the problems, the invention discloses a synthetic method for preparing dimethyl sebacate by using a high specific surface area silica supported perfluorinated sulfonic acid resin catalyst.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a synthesis method for preparing dimethyl sebacate by using a high specific surface area silica supported perfluorinated sulfonic acid resin catalyst, comprising the following steps:
sequentially adding sebacic acid and methanol into a 1000 mL four-mouth bottle provided with a nitrogen protection and distillation device, then adding a high specific surface area silicon dioxide loaded perfluorosulfonic acid resin catalyst, and reacting for 4-10 hours at 50-80 ℃ to obtain a product dimethyl sebacate, wherein the synthetic route is as follows:
；
the preparation method of the high specific surface area silica supported perfluorinated sulfonic acid resin catalyst comprises the following steps:
step (1): dispersing the silicon dioxide with high specific surface area into a mixed solution of absolute ethyl alcohol, water and hydrochloric acid, and marking as a solution A;
step (2): dispersing a certain amount of perfluorinated sulfonic acid resin into absolute ethyl alcohol, and marking the mixture as a solution B;
step (3): mixing the solution A and the solution B, heating in a water bath, stirring, evaporating to dryness to obtain a solid, washing with water for 3 times, acidifying with 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the silica-supported perfluorinated sulfonic acid resin catalyst.
Further, the mass ratio of the macroporous sulfonic acid type resin catalyst loaded by metal aluminum to the dimethyl sebacate is 1: 60-100.
Further, the molar ratio of the dimethyl sebacate to the 2, 6-tetramethyl-4-hydroxypiperidine nitroxide is 1: 3-1: 5.
further, the specific surface area silica in the step (1) is any one of MCM-41 and fumed silica.
Further, the concentration of the hydrochloric acid in the step (1) is 1 mol/L-5 mol/L.
Further, the adding amount of the perfluorinated sulfonic acid resin in the step (2) is 6-24 g.
Further, the water bath temperature in the step (3) is 60-80 ℃.
The beneficial effects of the invention are as follows:
(1) The composite catalyst of the high specific surface area silica supported perfluorinated sulfonic acid resin is synthesized for the first time by adopting an impregnation method, and the synthesis method is simple;
(2) The high specific surface area silica supported perfluorinated sulfonic acid resin catalyst consists of nano particles with smaller size, the spherical morphology (shown in figure 1) provides more active sites, and the specific surface area is higher (shown in figure 2), so that the reactivity is improved;
(3) The novel use of the high specific surface area silica supported perfluorosulfonic acid resin catalyst is a catalyst for synthesizing dimethyl sebacate, and the solid catalyst has high activity, can be repeatedly used, has good repeatability, and still keeps high activity and selectivity after being repeated for 30 times.
Drawings
FIG. 1 is a scanning electron microscope image of an MCM-41 supported perfluorosulfonic acid resin composite catalyst synthesized in example 1 of the present invention;
FIG. 2 is a schematic diagram showing N of an MCM-41 supported perfluorosulfonic acid resin composite catalyst synthesized in example 1 of the present invention 2 Adsorption-desorption isotherms and pore size distribution curves.
Detailed Description
The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.
The compound purchasers and models used in the following examples are shown in table 1 below; other chemical reagents used, unless otherwise specified, were obtained by conventional commercial means:
；
example 1
(1) 30g of MCM-41 was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 1M hydrochloric acid, designated as solution A;
(2) 6g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 60 ℃ to obtain a solid, washing for 3 times, acidifying 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the MCM-41 supported perfluorosulfonic acid resin composite catalyst, wherein the catalyst number is CAT-1, and an SEM (scanning electron microscope) diagram of the obtained catalyst is shown in figure 1;
(4) Sebacic acid (202.0 g, 1.0 mol), methanol (112 g, 3.5 mol) and 4.0 g CAT-1 are added into a 1000 mL four-mouth bottle provided with a nitrogen protection and distillation device, the temperature is raised to 75 ℃ for reaction, after 6 h, the reaction is finished, excessive methanol and water generated by the reaction are distilled out under reduced pressure, and colorless transparent liquid 217.4g is obtained through reduced pressure rectification, and the yield is 94.5%; n of the catalyst 2 Adsorption-desorption isotherms and pore size distribution curves as shown in figure 2.
Example 2
(1) 30g of fumed silica was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 1M hydrochloric acid, and the mixed solution was designated as solution A;
(2) 6g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 60 ℃ to obtain a solid, washing for 3 times, acidifying 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the fumed silica supported perfluorosulfonic acid resin composite catalyst, wherein the number of the catalyst is CAT-2;
(4) To a 1000 mL four-necked flask equipped with a nitrogen-protected and distillation apparatus, sebacic acid (202.0 g, 1.0 mol), methanol (128 g, 3.5 mol) and 5.0g CAT-2 were added, the temperature was raised to 75 ℃ for reaction, after 8 hours, the reaction was completed, excess methanol and water produced in the reaction were distilled off under reduced pressure, and 207.7g of colorless transparent liquid was obtained by distillation under reduced pressure, with a yield of 90.3%.
Example 3
(1) 30g of MCM-41 was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 3M hydrochloric acid, designated as solution A;
(2) 6g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 60 ℃ to obtain a solid, washing for 3 times, acidifying 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the MCM-41 supported perfluorosulfonic acid resin composite catalyst, wherein the number of the catalyst is CAT-3;
(4) To a 1000 mL four-necked flask equipped with a nitrogen-protected and distillation apparatus, sebacic acid (202.0 g, 1.0 mol), methanol (112 g, 3.5 mol) and 4.0 g CAT-3 were added, the temperature was raised to 75 ℃ to react, after 6 h, the reaction was completed, excess methanol and water produced in the reaction were distilled off under reduced pressure, and then 215.5g of colorless transparent liquid was obtained by distillation under reduced pressure, and the yield was 93.7%.
Example 4
(1) 30g of MCM-41 was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 5M hydrochloric acid, designated as solution A;
(2) 6g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 60 ℃ to obtain a solid, washing for 3 times, acidifying 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the MCM-41 supported perfluorosulfonic acid resin composite catalyst, wherein the number of the catalyst is CAT-4;
(4) To a 1000 mL four-necked flask equipped with a nitrogen-protected and distillation apparatus, sebacic acid (202.0 g, 1.0 mol), methanol (144 g, 4.5 mol) and 4.5 g of CAT-6 were added, the temperature was raised to 80℃to effect a reaction, after 8h the reaction was completed, excess methanol and water produced in the reaction were distilled off under reduced pressure, and then a colorless transparent liquid 209.8g was obtained by distillation under reduced pressure, with a yield of 91.2%.
Example 5
(1) 30g of MCM-41 was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 1M hydrochloric acid, designated as solution A;
(2) 24g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 60 ℃ to obtain a solid, washing for 3 times, acidifying 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the MCM-41 supported perfluorosulfonic acid resin composite catalyst, wherein the number of the catalyst is CAT-5;
(4) To a 1000 mL four-necked flask equipped with a nitrogen-protected and distillation apparatus, sebacic acid (202.0 g, 1.0 mol), methanol (96 g, 3.0 mol) and 3.5 g CAT-6 were added, the temperature was raised to 65 ℃ to react, after 5 h, the reaction was completed, excess methanol and water produced in the reaction were distilled off under reduced pressure, and 219.0g of colorless transparent liquid was obtained by distillation under reduced pressure, with a yield of 95.2%.
Example 6
(1) 30g of MCM-41 was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 1M hydrochloric acid, designated as solution A;
(2) 24g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 80 ℃ to obtain a solid, washing for 3 times, acidifying 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the MCM-41 supported perfluorosulfonic acid resin composite catalyst, wherein the number of the catalyst is CAT-6;
(4) To a 1000 mL four-necked flask equipped with a nitrogen-protected and distillation apparatus, sebacic acid (202.0 g, 1.0 mol), methanol (102.4 g, 3.0 mol) and 6.0g of CAT-6 were added, the temperature was raised to 70℃to effect a reaction, after 6 h the reaction was completed, excess methanol and water produced by the reaction were distilled off under reduced pressure, and then 220.4g of colorless transparent liquid was obtained by distillation under reduced pressure, with a yield of 95.8%.
Comparative example 1
The purpose was to compare with example 1 to illustrate the effect of the acidification step on the catalyst activity.
(1) 30g of MCM-41 was weighed and dispersed into a mixed solution of 200ml of ethanol, 25ml of water and 10ml of 1M hydrochloric acid, designated as solution A;
(2) 6g of perfluorosulfonic acid resin is weighed and dispersed into absolute ethyl alcohol, and is marked as solution B;
(3) Mixing the solution A and the solution B, evaporating the solvent under the condition of water bath stirring at 80 ℃ to obtain a solid, washing with water for 3 times, and drying at 100 ℃ to obtain the MCM-41 supported perfluorosulfonic acid resin composite catalyst, wherein the number of the catalyst is CAT-7;
(4) To a 1000 mL four-necked flask equipped with a nitrogen-protected, distillation apparatus, sebacic acid (202.0 g, 1.0 mol), methanol (160 g, 5.0 mol) and 5.0g of CAT-7 were added, the temperature was raised to 80℃to effect a reaction, after 8h the reaction was completed, excess methanol and water produced in the reaction were distilled off under reduced pressure, and then 137.5g of colorless transparent liquid was obtained by distillation under reduced pressure, with a yield of 59.8%.
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.
Claims (7)
1. The synthesis method for preparing dimethyl sebacate by using the high specific surface area silica supported perfluorinated sulfonic acid resin catalyst is characterized by comprising the following steps: sequentially adding sebacic acid and methanol into a 1000 mL four-mouth bottle provided with a nitrogen protection and distillation device, then adding a silica supported perfluorosulfonic acid resin catalyst, and reacting for 4-10 hours at 50-80 ℃ to obtain a product dimethyl sebacate, wherein the reaction route is as follows:
；
the preparation method of the high specific surface area silica supported perfluorinated sulfonic acid resin catalyst comprises the following steps:
step (1): the silicon dioxide with high specific surface area is dispersed into a mixed solution of absolute ethyl alcohol, water and hydrochloric acid and is marked as a solution A;
step (2): dispersing a certain amount of perfluorinated sulfonic acid resin into absolute ethyl alcohol, and marking the mixture as a solution B;
step (3): mixing the solution A and the solution B, heating in a water bath, stirring, evaporating to dryness to obtain a solid, washing with water for 3 times, acidifying with 400ml of 2mol/L hydrochloric acid for 4 hours, and drying at 100 ℃ to obtain the silica-supported perfluorinated sulfonic acid resin catalyst.
2. The method for preparing a high specific surface area silica supported perfluorosulfonic acid resin catalyst according to claim 1, wherein the mass ratio of the silica supported perfluorosulfonic acid resin catalyst to sebacic acid is 1: 60-100.
3. The method for preparing a high specific surface area silica supported perfluorosulfonic acid resin catalyst according to claim 1, wherein the molar ratio of sebacic acid to methanol is 1: 3-1: 5.
4. the method for preparing a high specific surface area silica supported perfluorosulfonic acid resin catalyst according to claim 1, wherein the high specific surface area silica in step (1) is MCM-41, fumed silica.
5. The method for preparing a high specific surface area silica supported perfluorosulfonic acid resin catalyst according to claim 1, wherein the concentration of hydrochloric acid in the step (1) is 1mol/L to 5mol/L.
6. The method for preparing a high specific surface area silica supported perfluorosulfonic acid resin catalyst according to claim 1, wherein the amount of perfluorosulfonic acid resin added in step (2) is 6g to 24g.
7. The method for preparing a high specific surface area silica supported perfluorosulfonic acid resin catalyst according to claim 1, wherein the water bath temperature in step (3) is 60 ℃ to 80 ℃.
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| CN202310648616.9A CN116621695A (en) | 2023-06-02 | 2023-06-02 | Synthesis method for preparing dimethyl sebacate by using high specific surface area silica supported perfluorinated sulfonic acid resin catalyst |
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| CN202310648616.9A CN116621695A (en) | 2023-06-02 | 2023-06-02 | Synthesis method for preparing dimethyl sebacate by using high specific surface area silica supported perfluorinated sulfonic acid resin catalyst |
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| CN202310648616.9A Pending CN116621695A (en) | 2023-06-02 | 2023-06-02 | Synthesis method for preparing dimethyl sebacate by using high specific surface area silica supported perfluorinated sulfonic acid resin catalyst |
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