CN115057754B - Method for preparing pentamethylindane - Google Patents
Method for preparing pentamethylindane Download PDFInfo
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- CN115057754B CN115057754B CN202210534942.2A CN202210534942A CN115057754B CN 115057754 B CN115057754 B CN 115057754B CN 202210534942 A CN202210534942 A CN 202210534942A CN 115057754 B CN115057754 B CN 115057754B
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- PLAOCQIEAKPVEA-UHFFFAOYSA-N 1,2,2,3,3-pentamethyl-1h-indene Chemical compound C1=CC=C2C(C)(C)C(C)(C)C(C)C2=C1 PLAOCQIEAKPVEA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 49
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000006482 condensation reaction Methods 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 44
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 235000019257 ammonium acetate Nutrition 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 238000004821 distillation Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 241000402754 Erythranthe moschata Species 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 230000006837 decompression Effects 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 6
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- FNFBFCNKBWWBGR-UHFFFAOYSA-N 1,2,2,3,3,4-hexamethylinden-1-ol Chemical compound CC1=C2C(C(C(C2=CC=C1)(O)C)(C)C)(C)C FNFBFCNKBWWBGR-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GSDMSMSVHXZYMS-UHFFFAOYSA-N 1,2,2,3,3-pentamethylinden-1-ol Chemical compound C1=CC=C2C(C)(O)C(C)(C)C(C)(C)C2=C1 GSDMSMSVHXZYMS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing pentamethylindane. The method comprises the following steps: the method comprises the steps of preparing pentamethylindane by condensation reaction of alpha-methylstyrene and isoamylene as raw materials; the fluorocarboxylic acid is used as a catalyst, the ammonium acid is used as an auxiliary agent, and the condensation reaction is catalyzed under high pressure. And recovering the fluorocarboxylic acid after the reaction is completed. The ammonium acid is added in the reaction process to inhibit the self-polymerization of the raw materials, inhibit the generation of isomer II and improve the selectivity of the condensation reaction. The method has the advantages of recoverable catalyst, high selectivity, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing pentamethylindane.
Background
The jiale musk is a heterochromatic full-scale musk developed by international perfume company in the United states, has strong musk fragrance, has costustoot fragrance, is transparent and durable in fragrance retention, and can cover the fragrance of mildewed odor. At present, the Jiale musk is the synthesized musk spice with the largest usage amount, and is often combined with other musks for preparing perfume essence.
The industrialized preparation method of the jiale musk comprises the steps of preparing pentamethyl indane by adopting alpha-methylstyrene and isoamylene to react, preparing hexamethylindanol by catalyzing the pentamethyl indanol with epoxypropane, and then reacting with paraformaldehyde or methylal to cyclize the jiale musk. The three wastes in the route are large, the environmental pollution is serious, the requirements of national industrial policies and environmental regulations are not met, and the requirements of sustainable development of modern chemical enterprises are not met.
Japanese patent JP2002284666 reports that a-methylstyrene and tertiary amyl alcohol undergo a condensation reaction to form pentamethylindane and propylene oxide hydroxyisopropylation to form hexamethylindanol which is then cyclized with paraformaldehyde to yield jiale musk.
U.S. patent No. 4440966 reports the preparation of indane from isoamylene and α -methylstyrene using phosphoric acid as a catalyst, in which process phosphoric acid can be separated out after the reaction is completed for secondary reaction, and isoamylene is less expensive, thus the cost of raw materials is lower.
Pentamethylindane is an important intermediate for preparing jiale musk, and the condensation reaction needs to be completed under the catalysis of acid, and inorganic acid such as sulfuric acid, acetic acid, phosphoric acid and the like is usually selected, so that a large amount of waste acid is generated by using the inorganic acid, and the waste acid is difficult to treat. In the aspect of catalytic reaction effect, the acidity and the system solubility have important influence on catalysis, the condensation reaction of alpha-methylstyrene and isoamylene is used as raw materials to prepare the pentamethylindane, and common organic acid or inorganic acid such as sulfuric acid, phosphoric acid and the like are used for being influenced by the acidity and the compatibility with the raw materials, so that the catalytic effect is not ideal. For example, phosphoric acid is used as a catalyst, although the acidity of phosphoric acid is moderate, the phosphoric acid is not mutually dissolved with the raw materials of alpha-methylstyrene and isoamylene, the reaction only occurs at an interface, the requirements on the trafficiency are severe, the alpha-methylstyrene and the isoamylene are more self-polymerized products, and a product isomer compound II is generated in the reaction process. The reaction formula is as follows:
the research on synthesis of the jiale musk in the university of Chongqing's university's thesis reports that the effect of using sulfuric acid and acetic anhydride as catalysts is better because sulfuric acid is more acidic, and acetic anhydride is organic matters and has better intersolubility in raw materials, and the combination of the sulfuric acid and the acetic anhydride can be superimposed with advantages.
In the process of synthesizing pentamethylindane, the alpha-methylstyrene and isoamylene undergo self-polymerization reaction to generate byproducts, so that the utilization rate of raw materials is reduced, the production cost is increased, and the quality of the product is reduced due to the high proportion of the isomer compound II of the product. From the aspect of atom economy, the probability of self-polymerization and isomer reaction is required to be reduced, and the aim of controlling the production cost is fulfilled.
Disclosure of Invention
The invention provides a method for preparing pentamethylindane, which reduces the proportion of alpha-methylstyrene and isoamylene self-polymerization products, inhibits the generation of isomer compound II to a certain extent, and improves the selectivity of condensation reaction.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method of preparing pentamethylindane comprising the steps of: the method comprises the steps of preparing pentamethylindane by condensation reaction of alpha-methylstyrene and isoamylene as raw materials; the fluorocarboxylic acid is used as a catalyst, the ammonium acid is used as an auxiliary agent, and the condensation reaction is catalyzed under high pressure.
In the present invention, the molar ratio of the alpha-methylstyrene to the isoamylene is 1:2 to 2:1, preferably 1:1.1 to 1:1.5.
In the present invention, the condensation reaction temperature is 30 to 80 ℃, preferably 40 to 50 ℃.
In the present invention, the condensation reaction time is 2 to 12 hours, preferably 3 to 5 hours.
In the invention, the fluorocarboxylic acid is trifluoroacetic acid and/or pentafluoropropionic acid, and the catalyst is used in an amount of 10-50% of the molar amount of alpha-methylstyrene based on the molar amount of the fluorocarboxylic acid. The catalyst can be recycled, and the three-waste generation amount is reduced.
In the present invention, the condensation reaction pressure is 0.2 to 3.0MPaG, preferably 0.5 to 2.0MPaG.
In the invention, the pressure is required to be released to normal pressure after the reaction is completed, and after the fluorocarboxylic acid is recovered by heating, the reaction liquid is washed with water and separated to obtain the pentamethylindane crude product liquid.
In the invention, ammonium acid is added in the reaction process to reduce the proportion of the alpha-methylstyrene and isoamylene self-polymerization products, and the invention can play a role in reducing the isomer proportion of the products.
The ammonium acid is one or more of ammonium acetate, ammonium sulfate, ammonium carbonate and ammonium nitrate. Ammonium acetate and/or ammonium carbonate are preferred.
In order to achieve a good catalytic effect, as an scheme, the molar ratio of trifluoroacetic acid to ammonium acid is 1:1-10:1; as another alternative, the molar ratio of pentafluoropropionic acid to ammonium acid is from 5:1 to 20:1.
Trifluoroacetic acid and pentafluoropropionic acid are organic strong acids, have better solubility with alpha-methylstyrene and isoamylene, and can cause raw materials to polymerize under the strong acidic condition due to the fact that the trifluoroacetic acid or the pentafluoropropionic acid is too strong in acidity, the acidity of the system can be adjusted to reach moderate acid strength by adding ammonium acid into the system, and in addition, a small amount of ammonium acid can be dissolved in the trifluoroacetic acid and the pentafluoropropionic acid, the solubility of the system is not affected, and an ideal catalytic effect can be achieved. Reduces the proportion of the self-polymerization products of the alpha-methyl styrene and the isoamylene and improves the selectivity of the condensation reaction. In addition, the unexpected discovery can inhibit the formation of the isomer compound II to a certain extent after the ammonium acid is added, and presumably because the amine in the ammonium acid contains lone pair electrons, the lone pair electrons can regulate double bond breakage and have a limiting effect on a cyclization site, thereby inhibiting the isomer of the product. The raw materials are reasonably utilized, the selectivity of the product is improved, the post-treatment step is easier, and the overall process efficiency is improved.
Detailed Description
The following examples will further illustrate the process provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
The analysis method comprises the following steps:
gas chromatograph: agilent7820A, column HP-5 (30 m×320 μm×0.25 μm), sample inlet temperature: 120 ℃; the split ratio is 30:1; carrier gas flow rate: 1.5ml/min; heating program: maintaining at 50deg.C for 1min, heating to 90deg.C at 10deg.C/min, maintaining for 0min, heating to 180deg.C at 5deg.C/min, maintaining for 0min, and heating to 280deg.C at 30deg.C/min, maintaining for 6min. Detector temperature: 280 ℃.
Example 1
Under inert gas atmosphere, 34.2g of trifluoroacetic acid and 2.5g of ammonium acetate were added to the autoclave, the autoclave was sealed and then filled with 2.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 35 ℃. 118.1g of alpha-methylstyrene and 70.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 4 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 80 ℃ for distillation and recovery of trifluoroacetic acid, adding water for extraction and liquid separation, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.8%, the selectivity of pentamethyl indane is 78.31wt%, the selectivity of isopentene polymer is 9.05wt%, the selectivity of alpha-methyl styrene polymer is 7.92wt%, and the selectivity of pentamethyl indane isomer (formula II) is 4.72wt%.
Example 2
Under inert gas atmosphere, 57.0g of trifluoroacetic acid and 8.0g of ammonium nitrate were added to the autoclave, the autoclave was sealed and then filled with 1.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 45 ℃. 118.1g of alpha-methylstyrene and 70.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 3 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 80 ℃ for distillation and recovery of trifluoroacetic acid, adding water for extraction and liquid separation, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 76.25%, the selectivity of isopentene polymer is 9.21%, the selectivity of alpha-methyl styrene polymer is 8.12% and the selectivity of pentamethyl indane isomer (formula II) is 6.42%.
Example 3
Under inert gas atmosphere, 11.5g of trifluoroacetic acid and 9.6g of ammonium carbonate were added to the autoclave, the autoclave was sealed and then filled with 3.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 75 ℃. 118.1g of alpha-methylstyrene and 77.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 2 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 80 ℃ for distillation and recovery of trifluoroacetic acid, adding water for extraction and liquid separation, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 80.05%, the selectivity of isopentene polymer is 8.32%, the selectivity of alpha-methyl styrene polymer is 7.17%, and the selectivity of pentamethyl indane isomer (formula II) is 4.46%.
Example 4
Under inert gas atmosphere, 34.2g of trifluoroacetic acid and 7.7g of ammonium acetate were added to the autoclave, the autoclave was sealed and then filled with 1.5MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 35 ℃. 118.1g of alpha-methylstyrene and 84.2g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 4 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 80 ℃ for distillation and recovery of trifluoroacetic acid, adding water for extraction and liquid separation, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 83.16%, the selectivity of isopentene polymer is 8.52%, the selectivity of alpha-methyl styrene polymer is 4.05% and the selectivity of pentamethyl indane isomer (formula II) is 4.27%.
Example 5
Under inert gas atmosphere, 22.8g of trifluoroacetic acid and 8.1g of ammonium acetate were added to the autoclave, the autoclave was sealed and then filled with 2.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 50 ℃. 118.1g of alpha-methylstyrene and 91.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 3 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 80 ℃ for distillation and recovery of trifluoroacetic acid, adding water for extraction and liquid separation, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 77.34wt%, the selectivity of isopentene polymer is 12.93wt%, the selectivity of alpha-methyl styrene polymer is 4.21wt%, and the selectivity of pentamethyl indane isomer (formula II) is 5.52wt%.
Example 6
Under inert gas atmosphere, 65.6g of pentafluoropropionic acid and 7.6g of ammonium carbonate were added to the autoclave, the autoclave was sealed, then filled with 0.5MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 35 ℃. 118.1g of alpha-methylstyrene and 77.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 5 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 110 ℃, distilling to recover trifluoroacetic acid, adding water, extracting and separating liquid, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 78.55%, the selectivity of isopentene polymer is 8.74%, the selectivity of alpha-methyl styrene polymer is 7.45%, and the selectivity of pentamethyl indane isomer (formula II) is 5.26%.
Example 7
49.2g of pentafluoropropionic acid and 2.2g of ammonium acetate were charged into an autoclave under an inert gas atmosphere, the autoclave was sealed, then charged with 2.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 45 ℃. 118.1g of alpha-methylstyrene and 84.2g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 4 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 110 ℃, distilling to recover trifluoroacetic acid, adding water, extracting and separating liquid, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 80.11%, the selectivity of isopentene polymer is 9.26%, the selectivity of alpha-methyl styrene polymer is 4.57%, and the selectivity of pentamethyl indane isomer (formula II) is 6.06%.
Example 8
34.6g of pentafluoropropionic acid and 1.4g of ammonium sulfate were added to an autoclave under an inert gas atmosphere, the autoclave was sealed, then filled with 0.5MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 35 ℃. 118.1g of alpha-methylstyrene and 105.2g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 12 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 110 ℃, distilling to recover trifluoroacetic acid, adding water, extracting and separating liquid, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.8%, the selectivity of pentamethyl indane is 74.32wt%, the selectivity of isopentene polymer is 15.98wt%, the selectivity of alpha-methyl styrene polymer is 3.12wt%, and the selectivity of pentamethyl indane isomer (formula II) is 6.58wt%.
Comparative example 1
Under inert gas atmosphere, 34.2g of trifluoroacetic acid was added to the autoclave, the autoclave was sealed and then filled with 2.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 35 ℃. 118.1g of alpha-methylstyrene and 70.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 4 hours after the feeding is completed. Decompression after the reaction is finished, transferring the reaction solution into distillation equipment, heating to 80 ℃ for distillation and recovery of trifluoroacetic acid, adding water for extraction and liquid separation, and detecting by using an organic phase gas chromatography to obtain the product, wherein the conversion rate of alpha-methyl styrene is 99.9%, the selectivity of pentamethyl indane is 23.71wt%, the selectivity of isopentene polymer is 33.76wt%, the selectivity of alpha-methyl styrene polymer is 30.78wt%, and the selectivity of pentamethyl indane isomer (formula II) is 11.75wt%.
Comparative example 2
Under inert gas atmosphere, 8.0g of ammonium nitrate was added to the autoclave, the autoclave was sealed and then charged with 1.0MPa of nitrogen, stirring was started, and the temperature in the autoclave was set at 45 ℃. 118.1g of alpha-methylstyrene and 70.1g of isoamylene are mixed and pumped into an autoclave by using a booster pump, the flow is 5.0g/min, and the heating is continued for 3 hours after the feeding is completed. After the reaction is finished, the pressure is released, the reaction solution is transferred, water is added for extraction and liquid separation, the organic phase gas chromatography detection is carried out, the conversion rate of the alpha-methyl styrene is 15.8%, the selectivity of the pentamethyl indane is 2.52wt%, the selectivity of the isopentene polymer is 58.67wt%, the selectivity of the alpha-methyl styrene polymer is 38.56wt%, and the selectivity of the pentamethyl indane isomer (formula II) is 0.25wt%.
Claims (12)
1. A method of preparing pentamethylindane comprising the steps of: the method comprises the steps of preparing pentamethylindane by condensation reaction of alpha-methylstyrene and isoamylene as raw materials; taking fluoro carboxylic acid as a catalyst and ammonium acid as an auxiliary agent, and catalyzing condensation reaction under high pressure; the fluoro carboxylic acid is trifluoroacetic acid and/or pentafluoropropionic acid; the ammonium acid is one or more of ammonium acetate, ammonium sulfate, ammonium carbonate and ammonium nitrate.
2. The method according to claim 1, wherein the molar ratio of alpha-methylstyrene to isoamylene is from 1:2 to 2:1.
3. The method according to claim 1, wherein the molar ratio of alpha-methylstyrene to isoamylene is from 1:1.1 to 1:1.5.
4. The method according to claim 1, wherein the condensation reaction temperature is 30 to 80 ℃.
5. The method according to claim 1, wherein the condensation reaction temperature is 40 to 50 ℃.
6. The method according to claim 1, wherein the condensation reaction time is 2 to 12 hours.
7. The method according to claim 1, wherein the condensation reaction time is 3 to 5 hours.
8. The process of claim 1 wherein the catalyst is present in an amount of from 10% to 50% of the molar amount of α -methylstyrene, based on the molar amount of the fluorocarboxylic acid.
9. The method of claim 1, wherein the condensation reaction pressure is 0.2 to 3.0MPaG.
10. The method of claim 1, wherein the condensation reaction pressure is 0.5 to 2.0MPaG.
11. The method of claim 1, wherein the molar ratio of trifluoroacetic acid to ammonium acid is from 1:1 to 10:1.
12. The method according to claim 1, wherein the molar ratio of pentafluoropropionic acid to ammonium acid is from 5:1 to 20:1.
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