CN113214040A - Preparation method of pentamethyl indane - Google Patents
Preparation method of pentamethyl indane Download PDFInfo
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- CN113214040A CN113214040A CN202110465811.9A CN202110465811A CN113214040A CN 113214040 A CN113214040 A CN 113214040A CN 202110465811 A CN202110465811 A CN 202110465811A CN 113214040 A CN113214040 A CN 113214040A
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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 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 claims abstract description 220
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical group O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 239000004793 Polystyrene Substances 0.000 claims description 72
- 229920002223 polystyrene Polymers 0.000 claims description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- ONKNPOPIGWHAQC-UHFFFAOYSA-N galaxolide Chemical compound C1OCC(C)C2=C1C=C1C(C)(C)C(C)C(C)(C)C1=C2 ONKNPOPIGWHAQC-UHFFFAOYSA-N 0.000 description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 241000402754 Erythranthe moschata Species 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- -1 astringent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical class CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008278 cosmetic cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
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- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- 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
- B01J2231/46—C-H or C-C activation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical product production, and particularly relates to a preparation method of pentamethyl indane, which comprises the following steps: s1, synthesizing a crude product of indan, namely uniformly mixing alpha-methyl styrene and isoamylene, dripping the mixture into a reaction kettle, adding a catalyst into the reaction kettle, and reacting to obtain pentamethyl indan, wherein the catalyst is phosphomolybdic acid; and S2, rectifying the crude indane product, and rectifying the crude indane product by using an indane rectifying unit to obtain a finished pentamethyl indane product. The invention has the beneficial effects that: the phosphomolybdic acid is used as a catalyst to catalyze the preparation reaction of the pentamethyl indane, and is protonic acid which is composed of octahedral metal oxide heteropolyanions as basic units, so that the phosphomolybdic acid has stronger acidity and oxidation-reduction property compared with common phosphoric acid, and therefore, the phosphomolybdic acid has more excellent catalytic performance and is beneficial to improving the yield of the pentamethyl indane.
Description
Technical Field
The invention belongs to the technical field of chemical product production, and particularly relates to a preparation method of pentamethyl indane.
Background
Galaxolide is the first synthetic musk developed successfully by international perfumery. The galaxolide has molecular weight of 258.4, boiling point of 129 deg.C (107Pa), and chemical name of 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethylcyclopenta-gamma-2-benzopyran.
The galaxolide has musk fragrance, elegant fragrance, sweet fragrance, excellent penetrating power and diffusion power, lasting fragrance and good stability, and is commonly used in cosmetic cream, astringent, soap, daily essence, tobacco essence and edible essence to prepare cosmetic essence and perfume fixative. The musk of the product has strong fragrance, good stability, no toxicity, can not be absorbed by human internal organs, can be taken orally, and has lower price, so the Jiale musk is deeply loved by a flavoring agent. Galaxolide has shown the potential of substituted musk xylols and nitromusks and is a promising species among polycyclic musks.
In the industrial process of preparing galaxolide, alpha-methyl styrene and isoamylene are first friedel-crafts alkylated to produce pentamethyl indan as the intermediate product, and this reaction is usually catalyzed with phosphoric acid or phosphorus pentoxide as catalyst.
The existing phosphoric acid or phosphorus pentoxide catalyst has low catalytic efficiency, and the yield of the prepared pentamethyl indane is usually less than 50%, so that the raw materials are greatly wasted in the production process.
Meanwhile, the pentamethyl indane contains a large amount of impurities such as isopentene dimer and the like, so that the purity is low, the low-purity pentamethyl indane is involved in the subsequent reaction, so that the problem of low synthesis yield of galaxolide is caused, and the impurities can influence the reaction effect, so that the pentamethyl indane needs to be subjected to subsequent treatment.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for producing pentamethyl indane, which can improve the yield and purity of pentamethyl indane.
The invention provides the following technical scheme:
a preparation method of pentamethyl indane comprises the following steps:
s1, synthesizing a crude product of indan, namely uniformly mixing alpha-methyl styrene and isoamylene, dripping the mixture into a reaction kettle, adding a catalyst into the reaction kettle, and reacting to obtain pentamethyl indan, wherein the catalyst is phosphomolybdic acid;
and S2, rectifying the crude indane product, and rectifying the crude indane product by using an indane rectifying unit to obtain a finished pentamethyl indane product.
Preferably, the phosphomolybdic acid is loaded before being put into use, and the loading method comprises the following steps: 1) dispersing the crosslinked polystyrene powder into boiling water, stirring uniformly, and adding phosphomolybdic acid; 2) the mixture was stirred vigorously at 100 ℃ until a sticky solid appeared; 3) and (3) drying the mixture in vacuum to obtain the crosslinked polystyrene supported phosphomolybdic acid catalyst.
Preferably, the crosslinking degree of the crosslinked polystyrene is controlled to be 5-8; the crosslinked polystyrene is activated before being put into use, and the activation method comprises the following steps: 1) firstly, carrying out lithium substitution treatment on crosslinked polystyrene to prepare lithium-substituted crosslinked polystyrene; 2) adding N, N-dimethylformamide into lithium polystyrene, stirring for 24h, centrifuging, and vacuum drying to obtain a dried substance; 3) adding triacetonamine and toluene into the dried product, stirring for 72h, centrifuging, and drying in vacuum to obtain the crosslinked polystyrene activator.
Preferably, the mass ratio of the lithium polystyrene to the N, N-dimethylformamide is 1: (0.2 to 0.4); the mass ratio of triacetonamine to toluene is 1: (12-14).
Preferably, the indan rectification unit comprises an indan rectification A1 tower bottom, an indan rectification A2 tower bottom, an indan rectification A3 tower bottom, an A3 tower top condenser, an A3 tower top reflux tank and a finished product indene full tank, the inlet end of the indan rectification A1 tower bottom is communicated with the outlet end of the indan crude product tank, the outlet end of the indan rectification A1 tower bottom is communicated with the inlet end of the indan rectification A2 tower bottom, the outlet end of the indan rectification A1 tower bottom is communicated with the inlet end of the indan rectification A3 tower bottom, the outlet end of the indan rectification A3 tower bottom is communicated with the inlet end of the A3 tower top condenser, the outlet end of the A3 tower top condenser is communicated with the inlet end of the A3 tower top reflux tank, and the outlet end of the A3 tower top reflux tank is communicated with the inlet end of the finished product indene full tank. .
Preferably, the tower comprises an A2 tower top condenser, an A2 tower top reflux tank, an isoamylene dimer storage tank and an A2 tower bottom pump, wherein the outlet end of the top of an indane rectification A2 tower bottom is communicated with the inlet end of the A2 tower top condenser, the outlet end of the A2 tower top condenser is communicated with the inlet end of the A2 tower top reflux tank, the outlet end of the A2 tower top reflux tank is communicated with the inlet end of the isoamylene dimer storage tank, the outlet end of the bottom of the indane rectification A2 tower bottom is communicated with the inlet end of the A2 tower bottom pump, and the outlet end of the A2 tower bottom pump is communicated with the inlet end of the indane A1 tower bottom pump.
Preferably, the system further comprises an indan rectification A4 tower kettle, an A4 tower condenser, an indan recovery front section groove, an indan recovery rear section groove and an indan finished product groove, wherein the inlet end of the indan rectification A4 tower kettle is communicated with the outlet end of the indan recovery groove, the outlet end of the top of the indan rectification A4 tower kettle is communicated with the inlet end of the A4 tower condenser, and the outlet end of the A4 tower condenser is respectively communicated with the inlet ends of the indan recovery front section groove, the indan recovery rear section groove and the indan finished product groove.
Preferably, the device further comprises an A3 tower concentrated drying kettle, wherein the inlet end of the A3 tower concentrated drying kettle is communicated with the outlet end of the bottom of the indane rectification A3 tower kettle, and the outlet end of the A3 tower concentrated drying kettle is communicated with the inlet end of the indane rectification A1 tower kettle.
The invention has the beneficial effects that:
1. the phosphomolybdic acid is protonic acid which is composed of octahedral metal oxide heteropolyanions as basic units, and acid radicals in the phosphomolybdic acid are coordinated by tetrahedrons which are formed by phosphorus atoms and oxygen ions positioned in the center and a plurality of coplanar and edge-sharing octahedrons which are formed by coordination atoms of molybdenum and oxygen atoms. Compared with common phosphoric acid, phosphomolybdic acid has stronger acidity and oxidation-reduction property due to the structure, so that phosphomolybdic acid has more excellent catalytic performance and is beneficial to improving the yield of pentamethyl indane.
2. The phosphomolybdic acid is immobilized on the crosslinked polystyrene, so that the influence caused by the defects of low specific surface area, poor thermal stability and easy loss of the phosphomolybdic acid is favorably reduced, and the catalytic effect and the recovery variability of the phosphomolybdic acid are improved.
3. The method controls the activation degree of the crosslinked polystyrene, thereby improving the crushing resistance and stability of the crosslinked polystyrene.
4. The method for activating the cross-linked polystyrene is beneficial to improving the stability of the cross-linked polystyrene, expanding the aperture of the cross-linked polystyrene and improving the load degree and load activity of phosphomolybdic acid.
5. The application has the following beneficial effects: according to the pentamethyl indan rectifying device, the pentamethyl indan is rectified by the rectifying unit, and the isoamylene dimer in the pentamethyl indan is separated, so that the purity of the pentamethyl indan is improved, and the subsequent efficiency of synthesizing galaxolide is improved. The pentamethyl indane separated in the rectification process of the galaxolide is recycled, impurities in the pentamethyl indane are separated through rectification operation, and the impurities are recycled, so that the utilization rate of the pentamethyl indane is improved, and the production cost is saved.
Drawings
FIG. 1 is a flow diagram of a process for rectifying pentamethyl indane discharged from a crude indane tank in an example of the present application;
FIG. 2 is a flow diagram of a rectification process for pentamethyl indane discharged from an indane finished product tank in an example of the application;
reference numerals: 1. an indane crude product tank; 2. indan rectification A1 tower bottom; 21. indan rectification A2 tower bottom; 211. a2 overhead condenser; 212. a2 overhead reflux drum; 213. an isoamylene dimer storage tank; 214. a2 bottom pump; 22. indan rectification A3 tower bottom; 221. a3 overhead condenser; 222. a3 overhead reflux drum; 223. a3 tower concentration dry kettle; 224. filling the finished product indene in the groove; 3. an indane recovery tank; 4. indan rectification A4 tower bottom; 41. a4 column condenser; 42. a front-stage tank for recovering indane; 43. an indane rear-section groove is recovered; 44. indan finished product tank.
Detailed Description
The present invention will be described in detail with reference to the following examples.
Example 1
A preparation method of pentamethyl indane comprises the following specific steps: mixing alpha-methyl styrene and isoamylene according to a molar ratio of 1: 0.75, uniformly mixing, then, dripping the mixed liquid into a reaction kettle for 20 hours, adding phosphomolybdic acid into the reaction kettle, keeping the molar ratio of phosphomolybdic acid to isoamylene at 1:0.85, keeping the pressure in the kettle at normal pressure, keeping the temperature at 30 ℃, keeping the temperature for reaction for 2 hours, reacting to obtain a pentamethyl indane crude product, and rectifying the indane crude product by using an indane rectification unit to obtain a pentamethyl indane finished product.
Example 2
A preparation method of pentamethyl indane comprises the following specific steps: mixing alpha-methyl styrene and isoamylene according to a molar ratio of 1: 0.75, uniformly mixing, then, dripping the mixed liquid into a reaction kettle for 20 hours, adding crosslinked polystyrene loaded phosphomolybdic acid into the reaction kettle, keeping the molar ratio of the crosslinked polystyrene loaded phosphomolybdic acid to the isoamylene at 1:0.85, keeping the temperature at 30 ℃ under normal pressure in the kettle, carrying out heat preservation reaction for 2 hours to obtain a pentamethyl indane crude product, and rectifying the indane crude product by using an indane rectification unit to obtain a pentamethyl indane finished product. (ii) a
The method for loading the cross-linked polystyrene loaded phosphomolybdic acid comprises the following steps: 1) dispersing crosslinked polystyrene powder with the crosslinking degree of 5 into boiling water, uniformly stirring, and adding phosphomolybdic acid, wherein the mass ratio of the polystyrene powder to the phosphomolybdic acid is 1: 1; 2) the mixture was stirred vigorously at 100 ℃ until a sticky solid appeared; 3) and (3) drying the mixture in vacuum at the temperature of 45 ℃ to obtain the crosslinked polystyrene supported phosphomolybdic acid catalyst.
Example 3 is different from example 2 in that,
the crosslinked polystyrene powder had a degree of crosslinking of 7.
Example 4 is different from example 2 in that,
the crosslinked polystyrene powder had a degree of crosslinking of 8.
Example 5
A preparation method of pentamethyl indane comprises the following specific steps: mixing alpha-methyl styrene and isoamylene according to a molar ratio of 1: 0.75, uniformly mixing, then, dripping the mixed liquid into a reaction kettle for 20 hours, adding crosslinked polystyrene loaded phosphomolybdic acid into the reaction kettle, keeping the molar ratio of the crosslinked polystyrene loaded phosphomolybdic acid to the isoamylene at 1:0.85, keeping the temperature at 30 ℃ under normal pressure in the kettle, carrying out heat preservation reaction for 2 hours to obtain a pentamethyl indane crude product, and rectifying the indane crude product by using an indane rectification unit to obtain a pentamethyl indane finished product.
The method for loading the cross-linked polystyrene loaded phosphomolybdic acid comprises the following steps: 1) dispersing crosslinked polystyrene powder with the crosslinking degree of 7 into boiling water, uniformly stirring, and adding phosphomolybdic acid, wherein the mass ratio of the polystyrene powder to the phosphomolybdic acid is 1: 1; 2) the mixture was stirred vigorously at 100 ℃ until a sticky solid appeared; 3) and (3) drying the mixture in vacuum at the temperature of 45 ℃ to obtain the crosslinked polystyrene supported phosphomolybdic acid catalyst.
The crosslinked polystyrene is activated before being put into use, and the activation method comprises the following steps: 1) firstly, carrying out lithium substitution treatment on crosslinked polystyrene to prepare lithium-substituted crosslinked polystyrene; 2) adding N, N-dimethylformamide into the lithium polystyrene, wherein the mass ratio of the lithium polystyrene to the N, N-dimethylformamide is 1: stirring at 90 deg.C for 24 hr, centrifuging, and vacuum drying at 60 deg.C to obtain dried substance; 3) adding triacetonamine and toluene into the dried substance, wherein the mass ratio of triacetonamine to toluene is 1: stirring for 72h at 12 and 60 ℃, centrifuging, and then carrying out vacuum drying at the temperature of 40 ℃ to obtain the crosslinked polystyrene activator.
Example 6
A preparation method of pentamethyl indane comprises the following specific steps: mixing alpha-methyl styrene and isoamylene according to a molar ratio of 1: 0.75, uniformly mixing, then, dripping the mixed liquid into a reaction kettle for 20 hours, adding crosslinked polystyrene loaded phosphomolybdic acid into the reaction kettle, keeping the molar ratio of the crosslinked polystyrene loaded phosphomolybdic acid to the isoamylene at 1:0.85, keeping the temperature at 30 ℃ under normal pressure in the kettle, carrying out heat preservation reaction for 2 hours to obtain a pentamethyl indane crude product, and rectifying the indane crude product by using an indane rectification unit to obtain a pentamethyl indane finished product. .
The method for loading the cross-linked polystyrene loaded phosphomolybdic acid comprises the following steps: 1) dispersing crosslinked polystyrene powder with the crosslinking degree of 7 into boiling water, uniformly stirring, and adding phosphomolybdic acid, wherein the mass ratio of the polystyrene powder to the phosphomolybdic acid is 1: 1; 2) the mixture was stirred vigorously at 100 ℃ until a sticky solid appeared; 3) and (3) drying the mixture in vacuum at the temperature of 45 ℃ to obtain the crosslinked polystyrene supported phosphomolybdic acid catalyst.
The crosslinked polystyrene is activated before being put into use, and the activation method comprises the following steps: 1) firstly, carrying out lithium substitution treatment on crosslinked polystyrene to prepare lithium-substituted crosslinked polystyrene; 2) adding N, N-dimethylformamide into the lithium polystyrene, wherein the mass ratio of the lithium polystyrene to the N, N-dimethylformamide is 1: stirring at 90 deg.C for 24 hr, centrifuging, and vacuum drying at 60 deg.C to obtain dried substance; 3) adding triacetonamine and toluene into the dried substance, wherein the mass ratio of triacetonamine to toluene is 1: 13, stirring for 72 hours at 60 ℃, centrifuging, and then carrying out vacuum drying at 40 ℃ to obtain the crosslinked polystyrene activator.
Example 7
A preparation method of pentamethyl indane comprises the following specific steps: mixing alpha-methyl styrene and isoamylene according to a molar ratio of 1: 0.75, uniformly mixing, then, dripping the mixed liquid into a reaction kettle for 20 hours, adding crosslinked polystyrene loaded phosphomolybdic acid into the reaction kettle, keeping the molar ratio of the crosslinked polystyrene loaded phosphomolybdic acid to the isoamylene at 1:0.85, keeping the temperature at 30 ℃ under normal pressure in the kettle, carrying out heat preservation reaction for 2 hours to obtain a pentamethyl indane crude product, and rectifying the indane crude product by using an indane rectification unit to obtain a pentamethyl indane finished product.
The method for loading the cross-linked polystyrene loaded phosphomolybdic acid comprises the following steps: 1) dispersing crosslinked polystyrene powder with the crosslinking degree of 7 into boiling water, uniformly stirring, and adding phosphomolybdic acid, wherein the mass ratio of the polystyrene powder to the phosphomolybdic acid is 1: 1; 2) the mixture was stirred vigorously at 100 ℃ until a sticky solid appeared; 3) and (3) drying the mixture in vacuum at the temperature of 45 ℃ to obtain the crosslinked polystyrene supported phosphomolybdic acid catalyst.
The crosslinked polystyrene is activated before being put into use, and the activation method comprises the following steps: 1) firstly, carrying out lithium substitution treatment on crosslinked polystyrene to prepare lithium-substituted crosslinked polystyrene; 2) adding N, N-dimethylformamide into the lithium polystyrene, wherein the mass ratio of the lithium polystyrene to the N, N-dimethylformamide is 1: stirring at 90 deg.C for 24 hr, centrifuging, and vacuum drying at 60 deg.C to obtain dried product; 3) adding triacetonamine and toluene into the dried substance, wherein the mass ratio of triacetonamine to toluene is 1: 14, stirring for 72 hours at 60 ℃, then centrifuging, and then carrying out vacuum drying at 40 ℃ to obtain the crosslinked polystyrene activator.
Comparative example 1, which is different from example 1 in that,
phosphorus pentoxide was used as the catalyst.
The rectifying units in embodiments 1 to 7 of the present invention are shown in fig. 1 and 2, and the pentamethyl indane rectifying unit includes an indane rectifying a1 tower bottom 2, an indane rectifying a2 tower bottom 21, an indane rectifying A3 tower bottom 22, an A3 tower top condenser 221, an A3 tower top reflux tank 222, an A3 tower concentrated drying kettle 223, a finished product indene full tank 224, an a2 tower top condenser 211, an a2 tower top reflux tank 212, an isoamylene dimer storage tank 213, an a2 tower bottom pump 214, an indane rectifying a4 tower bottom 4, an a4 tower condenser 41, an indane recovery front-stage tank 42, an indane recovery rear-stage tank 43, and an indane finished product tank 44.
The inlet end of an indane rectification A1 tower bottom 2 is communicated with the outlet end of an indane crude product tank 1, the outlet end of the top of an indane rectification A1 tower bottom 2 is communicated with the inlet end of an indane rectification A2 tower bottom 21, the outlet end of the bottom of an indane rectification A1 tower bottom 2 is communicated with the inlet end of an indane rectification A3 tower bottom 22, the outlet end of an indane rectification A3 tower bottom 22 is communicated with the inlet end of an A3 tower top condenser 221, the outlet end of an A3 tower top condenser 221 is communicated with the inlet end of an A3 tower top reflux tank 222, the outlet end of an A3 tower top reflux tank 222 is communicated with the inlet end of a finished product indene full tank 224, the inlet end of an A3 tower concentration drying kettle 223 is communicated with the outlet end of the bottom of an indane rectification A3 tower bottom 22, and the outlet end of an A3 tower concentration drying kettle 223 is communicated with the inlet end of an indane rectification A1 tower bottom 2.
An outlet end of the top of an indane rectification A2 tower bottom 21 is communicated with an inlet end of an A2 tower top condenser 211, an outlet end of the A2 tower top condenser 211 is communicated with an inlet end of an A2 tower top reflux tank 212, an outlet end of the A2 tower top reflux tank 212 is communicated with an inlet end of an isoamylene dimer storage tank 213, an outlet end of the bottom of an indane rectification A2 tower bottom 21 is communicated with an inlet end of an A2 tower bottom pump 214, and an outlet end of the A2 tower bottom pump 214 is communicated with an inlet end of an indane rectification A1 tower bottom 2.
The inlet end of a tower kettle 4 of the indan rectification A4 is communicated with the outlet end of the indan recovery tank 3, the outlet end of the top of the tower kettle 4 of the indan rectification A4 is communicated with the inlet end of a condenser 41 of the A4, and the outlet end of the condenser 41 of the A4 is respectively communicated with the inlet ends of a front indan recovery tank 42, a rear indan recovery tank 43 and an indan finished product tank 44.
Test detection
The yield of pentamethylindan in examples 1-7 and comparative example 1 was determined and the results are reported in the table below.
TABLE 1
From the experimental data in table 1 it can be seen that:
1. compared with the prior art that phosphorus pentoxide is used for catalyzing and preparing pentamethyl indane, the yield of pentamethyl indane is obviously improved by adopting phosphomolybdic acid for catalyzing and preparing pentamethyl indane;
2. after cross-linked polystyrene is used for loading phosphomolybdic acid, the yield improvement effect of the catalyst on pentamethyl indane is remarkably improved, which shows that the use of the cross-linked polystyrene has a positive promotion effect;
3. after the crosslinked polystyrene is activated, the yield of the pentamethyl indane is improved to a certain extent, which shows that the activation is beneficial to improving the catalytic activity of the crosslinked polystyrene.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of pentamethyl indane is characterized by comprising the following steps:
s1, synthesizing a crude product of indan, namely uniformly mixing alpha-methyl styrene and isoamylene, dripping the mixture into a reaction kettle, adding a catalyst into the reaction kettle, and reacting to obtain pentamethyl indan, wherein the catalyst is phosphomolybdic acid;
and S2, rectifying the crude indane product, and rectifying the crude indane product by using an indane rectifying unit to obtain a finished pentamethyl indane product.
2. The method for preparing pentamethyl indane according to claim 1, wherein phosphomolybdic acid is loaded before being put into use, and the loading method comprises the following steps: 1) dispersing the crosslinked polystyrene powder into boiling water, stirring uniformly, and adding phosphomolybdic acid; 2) the mixture was stirred vigorously at 100 ℃ until a sticky solid appeared; 3) and (3) drying the mixture in vacuum to obtain the crosslinked polystyrene supported phosphomolybdic acid catalyst.
3. The method for preparing pentamethyl indane according to claim 2, wherein the crosslinking degree of the crosslinked polystyrene is controlled to be 5-8; the crosslinked polystyrene is activated before being put into use, and the activation method comprises the following steps: 1) firstly, carrying out lithium substitution treatment on crosslinked polystyrene to prepare lithium-substituted crosslinked polystyrene; 2) adding N, N-dimethylformamide into lithium polystyrene, stirring for 24h, centrifuging, and vacuum drying to obtain a dried substance; 3) adding triacetonamine and toluene into the dried product, stirring for 72h, centrifuging, and drying in vacuum to obtain the crosslinked polystyrene activator.
4. The method according to claim 3, wherein the mass ratio of the lithium polystyrene to the N, N-dimethylformamide is 1: (0.2 to 0.4); the mass ratio of triacetonamine to toluene is 1: (12-14).
5. The method of claim 1, wherein the pentamethyl indane is obtained by reacting pentamethyl indane, the indan rectification unit comprises an indan rectification A1 tower bottom, an indan rectification A2 tower bottom, an indan rectification A3 tower bottom, an A3 tower top condenser, an A3 tower top reflux tank and a finished product indene full tank, the inlet end of the tower bottom of the indan rectification A1 is communicated with the outlet end of the indan crude product tank, the outlet end of the top of the tower bottom of the indan rectification A1 is communicated with the inlet end of the tower bottom of the indan rectification A2, the outlet end at the bottom of the tower bottom of the indan rectification A1 is communicated with the inlet end of the tower bottom of the indan rectification A3, the outlet end of the tower bottom of the indan rectification A3 is communicated with the inlet end of the condenser at the top of the A3 tower, the outlet end of the A3 overhead condenser is communicated with the inlet end of the A3 overhead reflux tank, and the outlet end of the A3 overhead reflux tank is communicated with the inlet end of the finished product indene full tank.
6. The method as claimed in claim 5, further comprising an A2 overhead condenser, an A2 overhead reflux drum, an isoamylene dimer storage tank, and an A2 bottoms pump, wherein the outlet of the top of the tower bottom of the indane rectification A2 is communicated with the inlet of the A2 overhead condenser, the outlet of the A2 overhead condenser is communicated with the inlet of the A2 overhead reflux drum, the outlet of the A2 overhead reflux drum is communicated with the inlet of the isoamylene dimer storage tank, the outlet of the bottom of the tower bottom of the indane rectification A2 is communicated with the inlet of the tower bottom pump of the A2, and the outlet of the bottom pump of the A2 is communicated with the inlet of the tower bottom of the indane rectification A1.
7. The method for preparing pentamethyl indane according to claim 5, further comprising an indane rectification A4 tower bottom, an A4 tower condenser, an indane recovery front section tank, an indane recovery rear section tank and an indane finished product tank, wherein the inlet end of the indane rectification A4 tower bottom is communicated with the outlet end of the indane recovery tank, the outlet end of the top of the indane rectification A4 tower bottom is communicated with the inlet end of the A4 tower condenser, and the outlet end of the A4 tower condenser is respectively communicated with the inlet ends of the indane recovery front section tank, the indane recovery rear section tank and the indane finished product tank.
8. The method as claimed in claim 5, further comprising a concentrated A3 tower drying still, wherein the inlet end of the concentrated A3 tower drying still is connected to the outlet end of the bottom of the A3 tower of indane rectification, and the outlet end is connected to the inlet end of the A1 tower bottom of the indane rectification.
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