CN112239405B - Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate - Google Patents
Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate Download PDFInfo
- Publication number
- CN112239405B CN112239405B CN201910643227.0A CN201910643227A CN112239405B CN 112239405 B CN112239405 B CN 112239405B CN 201910643227 A CN201910643227 A CN 201910643227A CN 112239405 B CN112239405 B CN 112239405B
- Authority
- CN
- China
- Prior art keywords
- reaction
- methanol
- catalyst
- synthesis method
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000001308 synthesis method Methods 0.000 title claims abstract description 31
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 129
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 230000035484 reaction time Effects 0.000 claims abstract description 19
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims abstract description 7
- LYLDIIUFTYRPPK-UHFFFAOYSA-N 1h-imidazole-2-sulfonic acid Chemical compound OS(=O)(=O)C1=NC=CN1 LYLDIIUFTYRPPK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 15
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical group OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical group OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 35
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000012856 packing Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthesis method of 2, 6-dimethyl naphthalene dicarboxylate (2, 6-NDC), which mainly solves the technical problems of long reaction time, low conversion rate, poor selectivity, poor catalyst recycling property and the like in the existing synthesis method. The synthesis method comprises the following steps of reacting 2, 6-naphthalene dicarboxylic acid with methanol by using imidazole sulfonic acid functionalized ionic liquid as a catalyst. The catalyst methanol solution is recycled at the temperature of 50-100 ℃ so that the re-reaction solution contains 1-10wt% of 2,6-NDC, thereby greatly reducing the reaction time in the recycling process and improving the efficiency of the whole process. The synthesis method can be used for high-efficiency synthesis of 2, 6-NDC.
Description
Technical Field
The invention relates to a method for synthesizing 2, 6-dimethyl naphthalene dicarboxylate (2, 6-NDC), which can effectively improve the reaction conversion rate, selectivity and catalyst circulation efficiency and shorten the reaction time.
Background
The benzene ring in the system is replaced by naphthalene ring with better rigidity compared with the traditional polyethylene terephthalate (PET), so that PEN has better performance compared with PET, and the potential application of the PEN covers all fields in which PET can be applied and can provide better performance. First PEN for CO 2 And O 2 The transmittance of the PET film is only about 30% of that of the traditional PET film, and PEN has better air tightness, so that the PEN film can better store food. Meanwhile, PEN has high modulus, high strength, stretching resistance and creep resistance, so that PEN can be used for manufacturing tires, conveyor belts, high-pressure conveying pipes and the like; finally, PEN has excellent chemical resistance and ultraviolet resistance, and is an excellent material for manufacturing various cables. In addition, the crystallization rate of PEN is reduced compared to PET, and transparent blow molded articles can be obtained.
The key to the production of PEN is to obtain monomers of polymeric grade. PEN production can take two routes, one is direct polymerization of 2, 6-naphthalene dicarboxylic acid (2, 6-NDA) with ethylene glycol; the other is transesterification polymerization of 2,6-NDC with ethylene glycol. The first route is simple in process, however, the melting point of the monomer 2,6-NDA is as high as 310 ℃, and meanwhile, the vapor pressure is low, and the solubility in various organic solvents is poor, so that the 2,6-NDA is difficult to purify by adopting an efficient separation method; the second route requires esterification of 2,6-NDA with methanol, followed by purification of the esterified product and polymerization with ethylene glycol, which is relatively complex compared to the first route and produces methanol as a byproduct of the polymerization process. However, the melting point of 2,6-NDC is far lower than that of 2,6-NDA, about 190 ℃, and the solubility of 2,6-NDC in organic solvents is far higher than that of 2,6-NDA, so that the purification of 2,6-NDC can be in the forms of crystallization, rectification and the like, and the transesterification synthesis of PEN by using 2,6-NDC is still the main method of industrial production at present.
In the second route, the esterification reaction of 2,6-NDA with methanol is critical. The catalyst used in the common esterification synthesis method is an inorganic acid catalyst, such as sulfuric acid or phosphoric acid. Wherein, when the concentrated sulfuric acid is used as a catalyst, the esterification yield of more than 80 percent can be achieved at 130 ℃. Patent US5254719 teaches that when concentrated sulfuric acid is used as the catalyst in the synthesis process, the metal catalyst added to the system in the early reaction can be dissolved, thereby removing the metal catalyst in the subsequent recrystallization step, so that the recrystallized rectifying tower bottoms are free of metal compounds, thereby preventing fouling of the tower bottoms during the rectifying process. However, in the synthesis method, the catalyst cannot be recycled, and a large amount of wastewater is generated in the synthesis process; meanwhile, equipment in the synthesis process is severely corroded, the equipment material requirement is high, and side reactions of dimethyl ether can be generated in the methanol in the synthesis process. Meanwhile, when inorganic acid is used as a catalyst, the catalyst cannot be recycled, and a large amount of wastewater is generated.
The esterification of 2,6-NDA is a spontaneous reaction process at high temperature, so that the synthesis process can be carried out without a catalyst at high temperature. However, to ensure a reaction rate, the reaction temperature is required to be higher than 200 ℃. To increase the reaction rate, patent US6013831 teaches that, after adding a small amount of molybdenum trioxide to the reaction system during synthesis at a high temperature of 270 ℃, the mass fraction of 2,6-NDC in the resulting crude ester product can reach 89.3%, the unreacted 2,6-NDA is only 3.8%, and the mass fraction of the naphthalene dicarboxylic monoesters (MM-2, 6-NDC) produced incompletely is also only 1.9%. Similar catalysts are also molybdenum trioxide, ammonium molybdate, titanium sulfate, ferrous sulfate, ferric sulfate, and the like. Meanwhile, li Yinghai compares the catalysts to find that the color of the esterification product obtained by the ammonium molybdate catalyst is the deepest, which is not beneficial to the later decolorization; the catalytic activity of molybdenum trioxide, ferric sulfate and ferrous sulfate is high, and the final product yield can reach more than 85%. However, the synthesis method not only needs higher reaction temperature, but also the added metal catalyst is easy to cause the fouling of the tower bottom in the subsequent rectification process and cannot be recycled.
Zhang Zhijiang it is pointed out that when 2,6-NDC is synthesized by using phosphotungstic acid as a catalyst, when the reaction temperature is 180 ℃, the molar ratio of alkyd is 80:1, the catalyst dosage is 1-3 wt% and the reaction time is 4-6 hours, the purity of the esterified product can reach 99% without recrystallization, and meanwhile, compared with the synthesis method by using sulfuric acid as the catalyst, the amount of wastewater in the process is greatly reduced. However, this synthesis method has a fatal disadvantage in that the alkyd ratio is excessively high, and the high purity of the esterified product is obtained on the basis of the consumption of raw materials.
From the above analysis, the known 2,6-NDC synthesis method has the following drawbacks: (1) The synthesis method has serious corrosion to equipment and generates a large amount of wastewater; (2) The reaction time in the synthesis process is long, the synthesis process needs to be carried out at high temperature and high pressure, and the energy consumption is huge; (3) The added catalyst in the synthesis process makes the post purification process difficult, and the catalyst is difficult to recycle.
Disclosure of Invention
The invention provides a synthesis method of 2,6-NDC based on the defects of the known synthesis method. The synthesis method has the advantages of less side reaction, high conversion rate, high selectivity, good catalyst circularity, short reaction time and the like. Meanwhile, the synthesis method disclosed by the invention is mild in reaction condition, does not introduce metal elements, and does not influence the later separation and purification process.
To achieve the above object, the solution of the present invention is as follows:
a method for synthesizing 2, 6-naphthalene dicarboxylic acid dimethyl ester comprises the following steps of reacting 2, 6-naphthalene dicarboxylic acid with methanol by using imidazole sulfonic acid functionalized ionic liquid as a catalyst.
In the technical scheme, the ionic liquid is imidazole sulfonic acid functionalized ionic liquid, and the catalyst is a compound with the following structural formula
Wherein R represents an alkyl group having 1 to 20 carbon atoms, preferably R is a methyl group, an ethyl group or a butyl group, n is an integer selected from 1 to 10, preferably 3 or 4, and X is an anion, preferably including hydrogen sulfate, hydrogen phosphate and p-toluenesulfonate.
In the above technical scheme, the addition amount of the 2, 6-dimethyl naphthalene dicarboxylate is 1-15wt%, preferably 1-10wt%, more preferably 2-7wt% of the addition amount of methanol in the reaction system.
In the technical scheme, the reaction is further added with 2, 6-dimethyl naphthalene dicarboxylate, and preferably the 2, 6-dimethyl naphthalene dicarboxylate added in the reaction system comprises a mixed solution containing 2, 6-dimethyl naphthalene dicarboxylate obtained by solid-liquid separation after the reaction of 2, 6-dimethyl naphthalene dicarboxylate and methanol is finished.
In the technical scheme, the solid-liquid separation temperature is 50-100 ℃, and the better separation temperature is 60-80 ℃.
In the technical scheme, the mixed solution containing the 2, 6-dimethyl naphthalene dicarboxylate obtained by solid-liquid separation also comprises an ionic liquid catalyst.
In the technical scheme, the adding amount of the catalyst ionic liquid is 0.1-5 wt% of the adding amount of the methanol in the reaction system, and the preferable adding amount is 0.1-2 wt%.
In the technical scheme, the mass ratio of the 2, 6-naphthalene dicarboxylic acid to the methanol is 1:3-1:15, and the preferable mass ratio is 1:5-1:10.
In the technical scheme, the reaction temperature is 60-170 ℃, the preferable reaction temperature is 80-150 ℃, the preferable reaction pressure is 0-3 Mpa, and the reaction time is 1-10 h.
In the above technical scheme, the method comprises a re-reaction step, preferably 2-10 times.
The synthesis method of the invention has the following beneficial effects:
the acidic functional ionic liquid can be recycled, the ionic liquid is not required to be recovered through rectification in the recycling process, and only the reacted methanol is required to be supplemented, so that the esterification rate can still reach more than 85% after the acidic functional ionic liquid is recycled for 3-8 times; the conversion rate of the 2,6-NDA is 60-100%, and the selectivity of the target product 2,6-NDC is good and can be close to 100% (more than 99.9%); the synthetic method can effectively inhibit etherification of the reaction raw material methanol and possible side reaction of 2,6-NDA at high temperature, the color value of the obtained product is obviously improved, and the b value is-5 < b <5; according to the synthesis method, the catalyst methanol solution is recycled at the temperature of 50-100 ℃, so that the re-reaction solution contains 1-10% by weight of 2,6-NDC, the reaction time in the recycling process is greatly reduced, and the efficiency of the whole process is improved. The synthesis method of the invention can be used for high-efficiency synthesis of 2, 6-NDC.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
[ example 1 ]
The ionic liquid synthesis according to the invention can be carried out as follows. The first step is the synthesis of the ylide. 1, 3-propane sultone was first melted into a liquid state in a water bath at 40℃and then 0.1mol of 1, 3-propane sultone was weighed into a 250ml three-necked flask, and dissolved by adding about 150ml of ethyl acetate. The three-neck flask is placed in an ice-water bath, the three-neck flask is provided with stirring, stirring is started, then 0.1mol of alkyl substituent imidazole is added dropwise, after the dropwise addition is finished, the three-neck flask is moved into a water bath kettle to be heated to 70 ℃, and stirring reaction is carried out for 6 hours. After the reaction was complete, the solid was filtered off with suction, washed 3 times with ethyl acetate and finally dried in vacuo or rotary evaporated to remove residual ethyl acetate. In the first reaction step, the main reactions are as follows:
the second reaction is to acid functionalize the ionic liquid. The ylide obtained in the reaction step 1 was put into a 250ml three-necked flask, and 150ml of water was added to dissolve the ylide. The three-necked flask was placed in an ice-water bath, the three-necked flask was equipped with stirring, stirring was started, then an equimolar amount of concentrated sulfuric acid was added dropwise, and after the dropwise addition was completed, the three-necked flask was moved into a water bath and heated to 70℃and stirred for 6 hours. After the reaction was completed, rotary evaporation and vacuum drying were employed to remove the water in the system. In the second reaction step, the main reactions are as follows:
synthesis by the above route
120g of methanol, 12g of 2,6-NDA and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reactor. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system was replaced with nitrogen gas 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. When the temperature in the kettle is increased to 130 ℃, starting timing, and stopping the reaction after 5 hours. The reaction product was pressed into a collection tank and after cooling to 40 c, the pressure was vented. The obtained product is filtered and then is put into a vacuum oven for drying. And finally, analyzing the obtained dry product by adopting high performance liquid chromatography. />
The results obtained are shown in Table 1:
table 1: composition of the product after the reaction
As can be seen from the data in Table 1, the selectivity of the product obtained by the first reaction can be close to 100%, and the conversion rate of the raw material 2,6-NDA can be more than 94%.
[ example 2 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA,3.4g of 2,6-NDC and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reaction vessel. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system was replaced with nitrogen gas 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. And after the temperature in the kettle is increased to 130 ℃, starting timing, and respectively carrying out experiments of reaction time periods of 2 hours, 3 hours and 4 hours. The reaction product was pressed into a collection tank and after cooling to 40 c, the pressure was vented. The obtained product is filtered and then is put into a vacuum oven for drying. And finally, analyzing the obtained dry product by adopting high performance liquid chromatography. The results obtained are shown in Table 2:
table 2: composition of the product after the reaction
As can be seen from the data in Table 2, the system reaches equilibrium after 3 hours for the first reaction by using the synthesis method of the present invention, which shows that the reaction rate is greatly improved after 2,6-NDC is added.
[ example 3 ]
Synthesis by the synthetic route of example 1
120g was charged into a 500ml stainless steel reaction vessel12g of 2,6-NDA and 1.2g of the ionic liquid catalyst described above. The system was purged with nitrogen 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 120 ℃, and stirring is started at the same time. When the temperature in the kettle is raised to 120 ℃, starting timing, and stopping the reaction after 5 hours. The reaction product was pressed into a collection tank and after cooling to 40 c, the pressure was vented. The obtained product is filtered and then is put into a vacuum oven for drying.
Comparative example 1
120g of methanol, 12g of 2,6-NDA and 0.6g of 98% concentrated sulfuric acid were charged into a 500ml stainless steel reaction vessel. The system was purged with nitrogen 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 120 ℃, and stirring is started at the same time. When the temperature in the kettle is raised to 120 ℃, starting timing, and stopping the reaction after 5 hours. The reaction product was pressed into a collection tank and after cooling to 40 c, the pressure was vented. The obtained product is filtered and then is put into a vacuum oven for drying.
The products obtained in example 3 and comparative example 1 were analyzed by liquid chromatography, and the composition of the reacted materials is shown in Table 3.
Table 3: composition of the product after the reaction
[ example 4 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reactor. The system was purged with nitrogen 3 times to remove air in the system, and then pressurized to 0.5Mpa. Heating is started to raise the temperature in the kettle to 100 ℃, and stirring is started at the same time. When the temperature in the kettle is raised to 100 ℃, starting timing, focusing on the reaction phenomenon in the kettle at any time, and recording the reaction time when the reaction system presents a clear liquid phaseAnd (3) the room(s). The reaction was continued until 5h later, the reaction was terminated. The reaction product was pressed into a collection tank and after cooling to 40 c, the pressure was vented. The obtained product is filtered by suction and then is put into a vacuum oven for drying, and the color of the dried product is observed.
Comparative example 2
120g of methanol, 12g of 2,6-NDA and 0.6g of 98% concentrated sulfuric acid were charged into a 500ml stainless steel reaction vessel. The system was purged with nitrogen 3 times to remove air in the system, and then pressurized to 0.5Mpa. Heating is started to raise the temperature in the kettle to 100 ℃, and stirring is started at the same time. When the temperature in the kettle is raised to 100 ℃, starting timing, focusing on the reaction phenomenon in the kettle at any time, and recording the reaction time when the reaction system presents a clear liquid phase. The reaction was continued until 5h later, the reaction was terminated. The reaction product was pressed into a collection tank and after cooling to 40 c, the pressure was vented. The obtained product is filtered by suction and then is put into a vacuum oven for drying, and the color of the dried product is observed.
Table 6 shows the time required for the reaction systems in example 4 and comparative example 2 to reach a clear point and the color value b of the dried product. As can be seen from Table 4, the quality of the product is higher by adopting the synthesis method disclosed by the invention, and the side reaction in the system is reduced.
Table 4: clear point time of different reaction processes and color of product after reaction
[ example 5 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reactor. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system is replaced by nitrogen for 3To remove air from the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. When the temperature in the kettle is increased to 130 ℃, starting timing, and stopping the reaction after 5 hours. When the temperature in the reaction kettle is changed to 60 ℃, solid-liquid separation is carried out, the solid phase is taken as a first reaction product, the liquid phase enters a collecting tank, and the liquid temperature in the collecting pipe is maintained at 60 ℃. 20g of fresh methanol was added to the liquid phase collection tank using a pump so that the 2,6-NDC content of the methanol solution was maintained at 2.32%. The obtained solution was subjected to the second and third reactions under the same conditions as the first reaction, and the reaction time period of both reactions was 3 hours. The three obtained products were dried and analyzed for product composition, and the results are shown in Table 5.
Table 5: influence of the number of cycles on the catalytic effect of the catalyst
As can be seen from Table 5, after the catalyst is recycled for 3 times by adopting the synthesis method of the invention, the esterification rate can still reach more than 90%, and the esterification rate is only reduced by 2.5%.
[ example 6 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reactor. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system was replaced with nitrogen gas 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. When the temperature in the kettle is increased to 130 DEG CAfter that, the time was started, and after 5 hours of reaction, the reaction was terminated. When the temperature in the reaction kettle is changed to 80 ℃, solid-liquid separation is carried out, the solid phase is taken as a first reaction product, the liquid phase enters a collecting tank, and the temperature of the liquid in the collecting pipe is maintained at 80 ℃. 20g of fresh methanol was added to the liquid phase collection tank using a pump so that the 2,6-NDC content of the methanol solution was maintained at 4.32%. The obtained solution was subjected to the second and third reactions under the same conditions as the first reaction, and the reaction time period of both reactions was 2 hours. The three obtained products were dried and analyzed for product composition, and the results are shown in Table 6.
[ comparative example 3 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reactor. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system was replaced with nitrogen gas 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. When the temperature in the kettle is increased to 130 ℃, starting timing, and stopping the reaction after 5 hours. When the temperature in the reaction kettle is changed to 30 ℃, solid-liquid separation is carried out, the solid phase is taken as a first reaction product, and the liquid phase enters a collecting tank. To the liquid phase collection tank, 20g of fresh methanol was added, and the obtained solution was subjected to the second reaction and the third reaction under the same conditions as those of the first reaction, and the reaction time period of both the two reactions was 2 hours. The three obtained products were dried and analyzed for product composition, and the results are also shown in Table 6.
Table 6: influence of the number of cycles on the catalytic effect of the catalyst
As can be seen from Table 6, the cyclic reaction of the synthesis method of the present invention can reach equilibrium in a short period of time, and the reaction time is greatly reduced.
[ example 7 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA, 5.3g of 2,6-NDC and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reaction vessel. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system was replaced with nitrogen gas 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. When the temperature in the kettle is increased to 130 ℃, starting timing, and stopping the reaction after 2 hours. When the temperature in the reaction kettle is changed to 80 ℃, solid-liquid separation is carried out, the solid phase is taken as a first reaction product, the liquid phase enters a collecting tank, and the temperature of the liquid in the collecting pipe is maintained at 80 ℃. 20g of fresh methanol was added to the liquid phase collection tank using a pump so that the 2,6-NDC content of the methanol solution was maintained at 4.32%. The obtained solution was subjected to the second and third reactions under the same conditions as the first reaction, and the reaction time period of both reactions was 2 hours. The three obtained products were dried and analyzed for product composition, and the results are shown in Table 7.
Table 7: influence of the number of cycles on the catalytic effect of the catalyst
As can be seen from Table 7, the reaction time is greatly reduced by adopting the synthesis method of the invention, and the catalyst is simple and convenient to recycle, and the methanol raw material can be recycled for a plurality of times.
[ example 8 ]
Synthesis by the synthetic route of example 1
120g of methanol, 12g of 2,6-NDA, 5.3g of 2,6-NDC and 1.2g of the ionic liquid catalyst described above were charged into a 500ml stainless steel reaction vessel. The top of the stainless steel reaction kettle is provided with a packing tower, and the packing tower is filled with molecular sieves to remove water generated in a reaction system, so that the reaction moves in a positive direction. At the beginning of the reaction, the whole system was replaced with nitrogen gas 3 times to remove air in the system, and then pressurized to 1Mpa. Heating is started to raise the temperature in the kettle to 130 ℃, and stirring is started at the same time. When the temperature in the kettle is increased to 130 ℃, starting timing, and stopping the reaction after 2 hours. When the temperature in the reaction kettle is changed to 80 ℃, solid-liquid separation is carried out, the solid phase is taken as a first reaction product, the liquid phase enters a collecting tank, and the temperature of the liquid in the collecting pipe is maintained at 80 ℃. 20g of fresh methanol was added to the liquid phase collection tank using a pump so that the 2,6-NDC content of the methanol solution was maintained at 4.32%. The obtained solution was subjected to the second and third reactions under the same conditions as the first reaction, and the reaction time period of both reactions was 2 hours. The three obtained products were dried and analyzed for product composition, and the results are shown in Table 8.
Table 8: influence of the number of cycles on the catalytic effect of the catalyst
Claims (18)
1. A method for synthesizing 2, 6-dimethyl naphthalene dicarboxylate includes such steps as reaction between 2, 6-dimethyl naphthalene dicarboxylate and methanol by using imidazole sulfonic acid functionalized ionic liquid as catalyst, and adding 2, 6-dimethyl naphthalene dicarboxylate.
2. The synthesis method according to claim 1, wherein the ionic liquid is an imidazole sulfonic acid functionalized ionic liquid, the catalyst is a compound having the following structural formula, wherein R represents an alkyl group with 1-20 carbon atoms, n is an integer selected from 1-10, and X is an anion.
3. The synthetic method according to claim 2, wherein R is methyl, ethyl or butyl, n is 3 or 4, and x is hydrogen sulfate, hydrogen phosphate or p-toluenesulfonate.
4. The method according to claim 1, wherein the amount of dimethyl 2, 6-naphthalate added is 1 to 15wt% of the amount of methanol added in the reaction system.
5. The method according to claim 4, wherein the amount of dimethyl 2, 6-naphthalate added is 1 to 10wt% based on the amount of methanol added in the reaction system.
6. The method according to claim 5, wherein the amount of dimethyl 2, 6-naphthalate added is 2 to 7wt% of the amount of methanol added in the reaction system.
7. The method according to claim 1, wherein the dimethyl-2, 6-naphthalenedicarboxylate added to the reaction system comprises a mixed solution containing dimethyl-2, 6-naphthalenedicarboxylate obtained by solid-liquid separation after the reaction between 2, 6-naphthalenedicarboxylic acid and methanol is completed.
8. The method according to claim 7, wherein the solid-liquid separation temperature is 50 to 100 ℃.
9. The method according to claim 8, wherein the solid-liquid separation temperature is 60 to 80 ℃.
10. The method according to claim 7, wherein the mixed solution containing dimethyl 2, 6-naphthalate obtained by the solid-liquid separation further comprises an ionic liquid catalyst.
11. The synthesis method according to claim 1, wherein the addition amount of the catalyst ionic liquid is 0.1-5 wt% of the addition amount of methanol in the reaction system.
12. The synthesis method according to claim 11, wherein the catalyst ionic liquid is added in an amount of 0.1 to 2wt% based on the amount of methanol added in the reaction system.
13. The synthesis method according to claim 1, wherein the mass ratio of the 2, 6-naphthalene dicarboxylic acid to the methanol is 1:3-1:15.
14. The synthesis method according to claim 13, wherein the mass ratio of the 2, 6-naphthalene dicarboxylic acid to the methanol is 1:5-1:10.
15. The synthesis method according to claim 1, wherein the reaction temperature is 60-170 ℃ and the reaction time is 1-10 h.
16. The method according to claim 15, wherein the reaction temperature is 80-150 ℃ and the reaction pressure is 0-3 MPa.
17. The method of synthesis according to claim 1, comprising a re-reaction step.
18. The method of claim 17, comprising 2-10 re-reaction steps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910643227.0A CN112239405B (en) | 2019-07-17 | 2019-07-17 | Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910643227.0A CN112239405B (en) | 2019-07-17 | 2019-07-17 | Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112239405A CN112239405A (en) | 2021-01-19 |
| CN112239405B true CN112239405B (en) | 2023-05-02 |
Family
ID=74167468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910643227.0A Active CN112239405B (en) | 2019-07-17 | 2019-07-17 | Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112239405B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820815A (en) * | 1954-04-08 | 1958-01-21 | Exxon Research Engineering Co | Synthetic lubricating compositions and process for their preparation |
| CN1253131A (en) * | 1998-10-29 | 2000-05-17 | 宝山钢铁(集团)公司 | Process for preparing multiring or fused-ring binary carboxylate by heteropoly acid catalysis |
| CN1296941A (en) * | 1999-11-17 | 2001-05-30 | 天津大学 | Process for preparing dimethyl 2,6-naphthalene-dicarboxylate |
| CN1956944A (en) * | 2004-05-20 | 2007-05-02 | Bp北美公司 | Recycling 2,6-naphthalenedicarboxylic acid (2,6-NDA) contained in polyethylene naphthalate in a process to produce diesters |
| CN102256923A (en) * | 2008-12-16 | 2011-11-23 | 巴斯夫欧洲公司 | Method for producing carboxylic acid esters |
| CN102256922A (en) * | 2008-12-16 | 2011-11-23 | 巴斯夫欧洲公司 | Production of carboxylic acid esters by stripping with alcohol vapor |
| CN106167449A (en) * | 2016-07-24 | 2016-11-30 | 遵义师范学院 | A kind of synthetic method of parahydroxyacet-ophenone |
| CN106916063A (en) * | 2015-12-25 | 2017-07-04 | 上虞新和成生物化工有限公司 | A kind of method that functionalized acidic ionic liquid catalysis prepares geranyl acetate |
| CN206767971U (en) * | 2017-03-10 | 2017-12-19 | 泰山医学院 | A kind of water absorber being attached to above the condenser of reaction and rectification device |
| CN107915626A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method and apparatus for producing methyl benzoate |
| CN109395776A (en) * | 2017-08-17 | 2019-03-01 | 华东理工大学 | A kind of alkylated reaction catalyst system and its preparation method and application |
-
2019
- 2019-07-17 CN CN201910643227.0A patent/CN112239405B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820815A (en) * | 1954-04-08 | 1958-01-21 | Exxon Research Engineering Co | Synthetic lubricating compositions and process for their preparation |
| CN1253131A (en) * | 1998-10-29 | 2000-05-17 | 宝山钢铁(集团)公司 | Process for preparing multiring or fused-ring binary carboxylate by heteropoly acid catalysis |
| CN1296941A (en) * | 1999-11-17 | 2001-05-30 | 天津大学 | Process for preparing dimethyl 2,6-naphthalene-dicarboxylate |
| CN1956944A (en) * | 2004-05-20 | 2007-05-02 | Bp北美公司 | Recycling 2,6-naphthalenedicarboxylic acid (2,6-NDA) contained in polyethylene naphthalate in a process to produce diesters |
| CN102256923A (en) * | 2008-12-16 | 2011-11-23 | 巴斯夫欧洲公司 | Method for producing carboxylic acid esters |
| CN102256922A (en) * | 2008-12-16 | 2011-11-23 | 巴斯夫欧洲公司 | Production of carboxylic acid esters by stripping with alcohol vapor |
| CN106916063A (en) * | 2015-12-25 | 2017-07-04 | 上虞新和成生物化工有限公司 | A kind of method that functionalized acidic ionic liquid catalysis prepares geranyl acetate |
| CN106167449A (en) * | 2016-07-24 | 2016-11-30 | 遵义师范学院 | A kind of synthetic method of parahydroxyacet-ophenone |
| CN107915626A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method and apparatus for producing methyl benzoate |
| CN206767971U (en) * | 2017-03-10 | 2017-12-19 | 泰山医学院 | A kind of water absorber being attached to above the condenser of reaction and rectification device |
| CN109395776A (en) * | 2017-08-17 | 2019-03-01 | 华东理工大学 | A kind of alkylated reaction catalyst system and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112239405A (en) | 2021-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| BRPI0610011A2 (en) | process for preparing alkyl (meth) acrylates | |
| CN113788793B (en) | Sulfonic acid functionalized imidazole ionic liquid catalyst and preparation method and application thereof | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN110452160B (en) | Preparation method of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide | |
| CN112239405B (en) | Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate | |
| CN111825549B (en) | Synthesis method of n-butyl glycolate | |
| CN104892410B (en) | A kind of methyl acrylate waste oil recovery process | |
| CN115232103B (en) | Preparation method of cyclic sulfate | |
| CN116574214A (en) | Polyion liquid catalyst and preparation method and application thereof | |
| CN112062677B (en) | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof | |
| CN108864010B (en) | Method for preparing phthalic anhydride from 5-hydroxymethylfurfural | |
| CN110354897B (en) | Preparation method and application of acidic polymerization ionic liquid resin catalyst | |
| US4281176A (en) | Preparation of ethyl carboxylates | |
| EP3995499A1 (en) | Method for preparing biogenic guanidine complex, method for preparing polyethylene terephthalate (pet), and method for preparing poly (ethylene isophthalate-co-terephthalate) (peit) | |
| CN110563579A (en) | Preparation method of dimethyl nylon acid | |
| CN103304413A (en) | Synthetic method of 2-hydroxyethyl methacrylate | |
| CN112694400B (en) | Preparation method of dimethyl 2, 6-naphthalene dicarboxylate | |
| CN107032986A (en) | A kind of method that presence of acidic ionic liquid catalyst synthesizes the propanol ether acetate of 2 methoxyl group 1 | |
| CN110790642A (en) | Method for synthesizing ethylene glycol mono-tert-butyl ether in alkaline ionic liquid | |
| CN110330460B (en) | Preparation method of p-hydroxy-phenyl-hydantoin | |
| CN113801125B (en) | Preparation method of cyclic anhydride | |
| CN113788775B (en) | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst, and preparation method and application thereof | |
| US20190382331A1 (en) | Process for preparing bis(2-hydroxyethyl) terephthalate | |
| CN109180475B (en) | Method for synthesizing diisooctyl terephthalate through rapid esterification without alkali washing and water washing | |
| CN109759131B (en) | Composite ionic liquid and method for catalytically synthesizing n-butyl carboxylate by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240702 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Country or region after: China Patentee after: Sinopec (Shanghai) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Country or region before: China Patentee before: SHANGHAI Research Institute OF PETROCHEMICAL TECHNOLOGY SINOPEC |
|
| TR01 | Transfer of patent right |