CN116854555B - Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner - Google Patents
Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner Download PDFInfo
- Publication number
- CN116854555B CN116854555B CN202310836764.3A CN202310836764A CN116854555B CN 116854555 B CN116854555 B CN 116854555B CN 202310836764 A CN202310836764 A CN 202310836764A CN 116854555 B CN116854555 B CN 116854555B
- Authority
- CN
- China
- Prior art keywords
- reaction
- pressure
- derivative
- octahydronaphthalene
- cycloolefin
- 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
- POPHMOPNVVKGRW-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7-octahydronaphthalene Chemical compound C1CCC2CCCCC2=C1 POPHMOPNVVKGRW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 39
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 230000001502 supplementing effect Effects 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- -1 cyclic olefin Chemical class 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 claims description 2
- VTWPBVSOSWNXAX-UHFFFAOYSA-N 5-decylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCCCC)CC1C=C2 VTWPBVSOSWNXAX-UHFFFAOYSA-N 0.000 claims description 2
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 claims description 2
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-UHFFFAOYSA-N 0.000 claims description 2
- GOLQZWYZZWIBCA-UHFFFAOYSA-N 5-octylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCC)CC1C=C2 GOLQZWYZZWIBCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 42
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 36
- 238000005698 Diels-Alder reaction Methods 0.000 abstract description 10
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 47
- 230000001965 increasing effect Effects 0.000 description 25
- 238000004821 distillation Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002848 norbornenes Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- KIAPWMKFHIKQOZ-UHFFFAOYSA-N 2-[[(4-fluorophenyl)-oxomethyl]amino]benzoic acid methyl ester Chemical compound COC(=O)C1=CC=CC=C1NC(=O)C1=CC=C(F)C=C1 KIAPWMKFHIKQOZ-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- VKNXYLFKIOFLJG-UHFFFAOYSA-N 4,4-dimethyl-2,3,6,7,8,8a-hexahydro-1H-naphthalene Chemical compound CC1(C)CCCC2CCCC=C12 VKNXYLFKIOFLJG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07C2/50—Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/52—Ortho- or ortho- and peri-condensed systems containing five condensed rings
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (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 provides a preparation method of dimethylbridge octahydronaphthalene or a derivative thereof and gradient pressurization, belonging to the technical field of preparation of macrocyclic olefins, wherein the preparation method comprises the following steps: introducing protective gas into a reaction kettle, adding dicyclopentadiene and cycloolefin, carrying out initial pressurization by the protective gas, then heating the system to 190-220 ℃ for heat preservation reaction, carrying out reaction for 8-12 h by a method of indirectly supplementing pressure according to pressure drop along with the reaction, and separating according to the boiling point of a target component to obtain a corresponding product. The distribution of cyclopentadiene (main existing form after dicyclopentadiene cracking-cyclopentadiene) in gas-liquid two phases is regulated by pressure change to keep the dynamic high feeding ratio of cycloolefin and cyclopentadiene which actually participate in Diels-Alder reaction, thereby realizing high yield of target monomer, and the monomer conversion rate can reach more than 90% under the lower original feeding ratio of cycloolefin and dicyclopentadiene.
Description
Technical Field
The invention belongs to the technical field of preparation of macrocyclic olefins, and particularly relates to a preparation method of dimethylbridge octahydronaphthalene or a derivative thereof and gradient pressurization.
Background
Cycloolefin polymers have received extensive attention in recent years as a class of high-performance thermoplastic resins based on the polymerization of cyclic olefin monomers. Compared with the traditional optical high molecular materials such as polymethyl methacrylate (PMMA), polycarbonate (PC) and the like, the cycloolefin polymer has more excellent properties such as good transparency, lower density, higher thermal stability, lower shrinkage, water absorption, double refraction index and the like. Therefore, the cycloolefin copolymer can be widely applied to the fields of high added value industries such as optics, information, electric appliances, medical use and the like.
A number of performance parameters are used for evaluating cycloolefin polymers, the glass transition temperature (T g ) Is an extremely important index for the application. T (T) g The thermal stability of the cycloolefin polymer material and the use of the final product, such as poor heat resistance, are directly determined, and the dimensional stability of the material is directly affected, which ultimately results in deterioration of the properties of the product, such as optical properties and mechanical properties. Therefore, improving the heat resistance of the cycloolefin polymer greatly increases the range of use of the cycloolefin copolymer. In general, the highly sterically hindered cycloolefins are capable of significantly increasing the T of cycloolefin polymers or copolymers g . To increase T of cycloolefin polymer g Scientists have synthesized some macrocyclic cycloolefins for the preparation of high T g Cycloolefin polymers of (C) a), for example, dimethyloctahydronaphthalene, tricyclopentadiene, exo-1, 4a, 9a, 10-hexahydro-9, 10 (1 ', 2') -desmethylidene-1, 4-desmethylidene anthracene, etc. However, the existing synthesis of the macrocyclic norbornene derivative monomer often has the problems of low reaction conversion rate, more byproducts (such as trimers and oligomers) and the like.
Currently, for this problem, such as CN 11478156A, CN 105541529A, etc., two ways are often adopted: firstly, diluting a reaction component by adding a solvent to reduce the generation of a polymer; secondly, the purpose is achieved by adding a polymerization inhibitor, however, the addition of the polymerization inhibitor still cannot inhibit the formation of oligomers such as trimerization, tetramerization and the like. The synthesis of macrocyclic olefins, which is a kind of diels-alder reaction, has the property of reversible progress, and has important practical significance in providing a process for forward progress of the reaction under proper conditions to improve the conversion rate of cycloolefins, and reduce the cost and energy consumption of separation and purification.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing dimethylbridge octahydronaphthalene or a derivative thereof by gradient pressurization, which can inhibit the formation of by-products and can synthesize dimethylbridge octahydronaphthalene or a derivative thereof in high yield.
A dimethylbridge octahydronaphthalene or derivative thereof having the structural formula:
r is H or C1-C10 alkyl.
Further, the structural formula of the dimethylbridge octahydronaphthalene or the derivative thereof is as follows:
the cycloolefin monomer structures and boiling points used for the above listed two-bridge octahydronaphthalene or its derivatives are shown below:
the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof comprises the following steps:
introducing protective gas into a reaction device (preferably a reaction kettle or a stainless steel autoclave), adding dicyclopentadiene and cycloolefin to initially boost pressure by the protective gas, heating the system to 190-220 ℃ to perform heat preservation reaction, and performing indirect pressure supplementing method according to pressure drop along with the reaction for 8-12 h (preferably 10-12 h), and separating according to the boiling point of a target component to obtain a corresponding product.
The invention regulates Diels-Alder reaction to prepare the dimethylbridge octahydronaphthalene and the substituted dimethylbridge octahydronaphthalene compound by gradient pressure change. The invention regulates and controls the distribution of cyclopentadiene (main existing form after dicyclopentadiene is cracked-cyclopentadiene) in gas-liquid two phases through pressure change so as to keep the dynamic high feeding ratio of cycloolefin and cyclopentadiene which actually participate in Diels-Alder reaction, thereby realizing high yield of target monomer, and the monomer conversion rate can reach more than 90% under the lower original feeding ratio of cycloolefin and dicyclopentadiene. Meanwhile, the macrocyclic olefin derivative can prepare the cycloolefin copolymer with high glass transition temperature and high mechanical property through coordination polymerization and ring-opening metathesis reaction under the condition of small introduction.
Further, dicyclopentadiene and cycloolefin are used as raw materials to be mixed, diels-Alder reaction is carried out under the heating condition, a target product is obtained through separation, and a reaction route diagram of the gradient pressurizing preparation method of the alpha-octahydronaphthalene and the derivative thereof is as follows:
r is H or C1-C10 alkyl.
Further, in the gradient pressurizing preparation method of the dimethylbridged octahydronaphthalene or the derivative thereof, the cycloolefin is excessively added.
Further, in the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof, the molar ratio of the cycloolefin to the dicyclopentadiene is 4:1-8:1.
Further, in the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof, the cycloolefin is a derivative of norbornene with the 5-position being monosubstituted by an alkyl chain.
Further, in the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof, the cycloolefin is at least one of norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene and norbornene derivatives.
Further, in the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof, the pressure after the protective gas is introduced is 1.5-3.5 MPa, and the protective gas pressure which is 3-10 times of the pressure drop is intermittently supplemented for a plurality of times in the reaction process according to the value of the pressure drop.
Further, in the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof, the reaction pressure is 3-6 MPa when the thermal insulation reaction is carried out.
Further, in the gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof, the shielding gas is not particularly limited, and a gas which does not participate in Diels-Alder reaction, such as nitrogen or argon, preferably nitrogen, which is relatively low in price and easy to obtain can be selected.
The pressure during the reaction of the invention mainly comes from the pressure of protective gas filled before the reaction and the supplementary pressure during the reaction, and the inventor discovers that the initial filling pressure can effectively ensure that the cycloolefin is not easy to gasify in a large quantity at the reaction temperature, and always ensures that the cycloolefin at the bottom of the reaction kettle is in far excess of dicyclopentadiene and the amount of cyclopentadiene (the cracked cyclopentadiene is taken as a main body) which is a cracking product thereof at the reaction temperature, and the cyclopentadiene is continuously consumed along with the progress of the reaction. At this time, after pressurizing, the concentration of cyclopentadiene in the gas phase in the reaction kettle is further reduced, the utilization rate of dicyclopentadiene can be effectively improved, and the yield of a target product is increased. Taking norbornene (atmospheric boiling point 96 ℃) having the lowest boiling point used in monomer 1 of formula II as an example, the predicted boiling point is higher than 200 ℃ when the reaction pressure is 2 MPa; thus, for cycloolefins having an atmospheric boiling point above 96℃the cycloolefins remain liquid at 200℃and an absolute excess of cycloolefins in the liquid phase of the reaction substrate is ensured. The dicyclo is basically and completely cracked into cyclopentadiene (the normal pressure boiling point is 41 ℃) at the reaction temperature of 200 ℃, when the reaction pressure is 2MPa, the boiling point of cyclopentadiene is about 160-180 ℃, and the amount of cyclopentadiene in the gas phase can be realized by changing the pressure (namely, the actual feeding ratio of cycloolefin and cyclopentadiene in the liquid phase can be realized by changing the pressure). The corresponding boiling point can be referred to for the relevant theoretical calculation (chemical report, 1954 (12): 553-556.; chemical industry handbook, chemical industry Press 2008). According to theoretical values and requirements of a reaction device, the initial pressurizing pressure is 1.5-3.5 MPa, preferably more than 2MPa, according to the pressure drop, the pressure is increased by 3-10 times, and the highest pressure is controlled below 6MPa.
The reaction temperature of the invention is 190-220 ℃, and the inventor discovers that the conversion rate of the monomer is obviously accelerated along with the rise of the temperature. However, when the temperature is increased to 220 ℃ or higher, by-products such as trimer, oligomer and the like are significantly increased. Therefore, the heating temperature is preferably 190 to 220 ℃, more preferably 200 to 220 ℃.
The inventor finds that the reaction time is controlled to be 8-12 h, the pressure compensation operation is not carried out within 3h of the initial reaction, the pressure compensation operation is carried out after 3h, the first pressure compensation is carried out for 4-6 h, the pressure is maintained until the reaction is finished after the second pressure compensation is carried out for 6-8 h, and the purpose of the pressure compensation is to change the distribution content of cyclopentadiene in the gas phase and the liquid phase so as to regulate the actual feeding ratio of cycloolefin and cyclopentadiene in the liquid phase.
In the present invention, the inventors found that when the feed ratio of cycloolefin to dicyclopentadiene is greater than 2:1 (molar ratio), the monomer conversion of dicyclopentadiene is continuously increased as the feed ratio is further increased. However, too much cycloolefin is in excess, which further increases the cost of separation and purification. And according to the calculation result, the feeding ratio of the cycloolefin to the cyclopentadiene actually participating in the Diels-Alder reaction in the liquid phase can be correspondingly increased by changing the pressure and the pressure supplementing operation in the process (the feeding ratio of the actual cycloolefin in the liquid phase is far higher than that of the initial cycloolefin and dicyclopentadiene). Therefore, the ratio of cycloolefin to dicyclopentadiene is preferably 4:1 to 8:1 (molar ratio).
Compared with the prior art, the invention has the following advantages and technical effects:
1. under the condition that no catalyst exists, the molar ratio of the cycloolefin to the cyclopentadiene which actually participates in the Diels-Alder reaction of the liquid phase system is increased only through initial pressurization and pressure compensation in the reaction process under the condition that the original feeding ratio of the cycloolefin to the dicyclopentadiene is not improved, the utilization rate of the dicyclopentadiene and the yield of a target product are effectively improved, the generation of byproducts is restrained, and the energy consumption for separation and purification is reduced.
2. Under the condition of relatively low feeding ratio of original cycloolefin and dicyclopentadiene, the efficient utilization of dicyclopentadiene is realized, the requirements on reaction temperature and pressure are moderate, the use requirement on equipment is reduced, and meanwhile, the reaction efficiency is improved by short reaction time.
3. The production process is simple, intermittent reaction is adopted, the device is simple, the cost is low, and the high-purity separation of the target product can be realized through atmospheric distillation and vacuum distillation.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the product obtained in example 1 of the present invention;
FIG. 2 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product obtained in example 3 of the present invention;
FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product obtained in example 4 of the present invention;
FIG. 4 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 5 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the product obtained in example 6 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The structural formula of the dimethylbridged octahydronaphthalene or the derivative thereof in the following examples is as follows:
the cycloolefin monomer structures and boiling points used for the above listed two-bridge octahydronaphthalene or its derivatives are shown below:
example 1
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-1 (i.e., 1 in formula II, the same applies hereinafter) and dicyclopentadiene were added to a reaction vessel in a molar ratio of 4:1 by means of a metering pump, and 2, 6-t-butyl-p-methylphenol (BHT), an antioxidant, was mixed in an amount of 0.2wt% based on the total amount of the reaction mixture, in the reaction raw material. After the charging is completed, vacuumizing, introducing nitrogen for three times, introducing nitrogen for 2MPa into the reaction kettle, and setting the temperature of the reactor to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.42MPa, the pressure in the system is reduced to 3.28MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 0.6MPa and 0.6MPa in 4-6 hours and 6-8 hours. After reacting for 12 hours under this condition, heating was stopped. The crude product was taken out, excess II-1 monomer was removed by atmospheric distillation, and the target product was collected by secondary distillation under reduced pressure, yielding a target product of 86%.
And (3) performing nuclear magnetic resonance hydrogen spectrum detection on the obtained product, wherein the detection result is shown in figure 1. As can be seen from FIG. 1, the product obtained in example 1 of the present invention is a monomer represented by formula I-1 (i.e., 1 in formula I, hereinafter the same applies).
Comparative example 1
The monomer synthesis of this example was carried out at the same feed ratio, the same monomer and the same reaction temperature as in example 1 without the initial pressurization protection of the system, and after the reaction was completed, the same separation was adopted to measure the yield of the target product as 35%.
Comparative example 2
The monomer synthesis of this example was carried out at the same feed ratio, the same monomer and the same reaction temperature as in example 1, and the system was subjected to only initial pressurization to protect 1MPa without the pressure compensation operation during the reaction, and after the reaction was completed, the same separation method was adopted to measure the yield of the objective product as 43%.
Comparative example 3
The monomer synthesis of this example was carried out at the same feed ratio, the same monomer and the same reaction temperature as in example 1, and the system was subjected to only initial pressurization to protect 2MPa without the pressure compensation operation in the reaction process, and after the reaction was completed, the same separation method was adopted to measure the yield of the objective product as 65%.
Example 2
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-1 and dicyclopentadiene are added into a reaction kettle by a metering pump according to the mol ratio of 6:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, vacuumizing, introducing nitrogen for three times, introducing nitrogen for 2MPa into the reaction kettle, and setting the temperature of the reactor to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.65MPa, the pressure in the system is reduced to 3.43MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 0.6MPa and 1.5MPa in 4-6 hours and 6-8 hours. After reacting for 10 hours under this condition, heating was stopped. The crude product was taken out, excess II-1 monomer was removed by atmospheric distillation, and the target product was collected by secondary distillation under reduced pressure, yielding a target product of 95%.
The product obtained in example 2 of the present invention is a monomer represented by formula I-1 (i.e., 1 in formula I).
Example 3
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-2 and dicyclopentadiene are added into a reaction kettle by a metering pump according to the mol ratio of 6:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, vacuumizing, introducing nitrogen for three times, introducing nitrogen for 2MPa into the reaction kettle, and setting the temperature of the reactor to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.35MPa, the pressure in the system is reduced to 3.23MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 0.6MPa and 1MPa in 4-6 hours and 6-8 hours. After reacting for 10 hours under this condition, heating was stopped. The crude product was taken out, excess II-2 monomer was removed by atmospheric distillation, and the target product was collected by distillation under reduced pressure twice, yielding 94% of the target product.
And (3) performing nuclear magnetic resonance hydrogen spectrum detection on the obtained product, wherein the detection result is shown in figure 2. As can be seen from FIG. 2, the product obtained in example 3 of the present invention is a monomer represented by formula I-2.
Example 4
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-3 and dicyclopentadiene are added into a reaction kettle by a metering pump according to the mol ratio of 6:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, vacuumizing, introducing nitrogen for three times, introducing nitrogen for 2MPa into the reaction kettle, and setting the temperature of the reactor to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.31MPa, the pressure in the system is reduced to 3.17MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 0.6MPa and 1.5MPa in 4-6 hours and 6-8 hours. After reacting for 10 hours under this condition, heating was stopped. The crude product was taken out, excess II-3 monomer was removed by atmospheric distillation, and the target product was collected by distillation under reduced pressure twice, and the yield of the target product was found to be 93%.
And (3) performing nuclear magnetic resonance hydrogen spectrum detection on the obtained product, wherein the detection result is shown in figure 3. As can be seen from FIG. 3, the product obtained in example 4 of the present invention is a monomer represented by formula I-3.
Example 5
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-4 and dicyclopentadiene are added into a reaction kettle by a metering pump according to the mol ratio of 6:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, vacuumizing, introducing nitrogen for three times, introducing nitrogen for 2MPa into the reaction kettle, and setting the temperature of the reactor to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.30MPa, the pressure in the system is reduced to 3.15MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 0.8MPa and 1.5MPa in 4-6 hours and 6-8 hours. After reacting for 10 hours under this condition, heating was stopped. The crude product was taken out, excess II-4 monomer was removed by atmospheric distillation, and the target product was collected by distillation under reduced pressure twice, yielding 94% of the target product.
And (4) performing nuclear magnetic resonance hydrogen spectrum detection on the obtained product, wherein the detection result is shown in figure 4. As can be seen from FIG. 4, the product obtained in example 5 of the present invention is a monomer represented by formula I-4.
Example 6
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-5 and dicyclopentadiene are added into a reaction kettle by a metering pump according to the mol ratio of 6:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, vacuumizing, introducing nitrogen for three times, introducing nitrogen for 2MPa into the reaction kettle, and setting the temperature of the reactor to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.23MPa, the pressure in the system is reduced to 3.04MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 0.6MPa and 0.6MPa in 4-6 hours and 6-8 hours. After reacting for 12 hours under this condition, heating was stopped. The crude product was taken out, excess II-5 monomer was removed by atmospheric distillation, and the target product was collected by secondary distillation under reduced pressure, yielding a target product of 90%.
And (5) performing nuclear magnetic resonance hydrogen spectrum detection on the obtained product, wherein the detection result is shown in figure 5. As can be seen from FIG. 5, the product obtained in example 6 of the present invention is a monomer represented by formula I-5.
Example 7
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-5 and dicyclopentadiene are added into a reaction kettle by a metering pump according to the mol ratio of 6:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, the vacuum pumping and nitrogen introducing are carried out for three times, nitrogen is filled into the reaction kettle for 2.5MPa, and the temperature of the reactor is set to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 3.92MPa, the pressure in the system is reduced to 3.75MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 1MPa and 2MPa in 4-6 hours and 6-8 hours. After reacting for 10 hours under this condition, heating was stopped. The crude product was taken out, excess II-5 monomer was removed by atmospheric distillation, and the target product was collected by secondary distillation under reduced pressure, yielding a target product of 95%.
The product obtained in example 7 of the present invention is a monomer of formula I-5.
Example 8
The stainless steel autoclave was heated to 150 ℃, evacuated by a vacuum pump for 8h, and filled with nitrogen. The monomer of formula II-5 and dicyclopentadiene are added into a reaction kettle by a metering pump according to a mol ratio of 8:1, and an antioxidant BHT accounting for 0.2 weight percent of the total material amount is mixed in the reaction raw materials. After the charging is completed, the vacuum pumping and nitrogen introducing are carried out for three times, nitrogen is filled into the reaction kettle for 2.5MPa, and the temperature of the reactor is set to be 200 ℃. After the temperature reaches the set temperature, the pressure in the kettle reaches 4.23MPa, the pressure in the system is reduced to 4.20MPa after the reaction is carried out for 3 hours, and then the pressure is respectively increased to 1MPa and 2MPa in 4-6 hours and 6-8 hours. After reacting for 10 hours under this condition, heating was stopped. The crude product was taken out, excess II-5 monomer was removed by atmospheric distillation, and the target product was collected by secondary distillation under reduced pressure, yielding a target product of 98%.
The product obtained in example 8 of the present invention is a monomer of formula I-5.
It can be seen from example 1 and comparative examples 1, 2 and 3 of the present invention that under the same charging mode and reaction temperature, the target monomer yields of 1MPa and 2MPa are gradually increased without initial pressurization, and the conversion rate of dicyclopentadiene is further improved to improve the target product yield by performing the pressure compensation operation in the reaction process, so that the molar ratio of cycloolefin and cyclopentadiene actually participating in diels-alder reaction in the liquid phase system is increased by initial pressurization and pressure compensation in the reaction process, and the utilization rate of dicyclopentadiene and the yield of the target product are effectively improved. It can be seen from examples 1 and 2 that the same yield increasing effect can be achieved by increasing the feed ratio of the original cycloolefin and dicyclopentadiene under the condition of the same initial pressurization and the same compensation pressure, and the synergistic effect can be achieved. In comparison between example 6 and example 7, the initial pressurization increased to 2.5MPa and the additional pressurization increased without changing other conditions also increased the yield of the target product. From the comparison of example 7 and example 8, the complete conversion of dicyclopentadiene can be achieved almost without changing the other conditions by increasing the initial charge ratio to 8:1. Under the condition of a certain optimized temperature, the effective synergistic effect can be realized by controlling the initial feeding ratio, the pressurizing and the process pressure supplementing, and the effective utilization of the raw materials is realized to the greatest extent. Meanwhile, the actual content of each component in the gas phase in the reaction system (the ratio of cycloolefin to cyclopentadiene actually participating in the Diels-Alder reaction) can be regulated by changing the pressure, so that the reaction is carried out in a favorable direction.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (7)
1. The gradient pressurizing preparation method of the dimethylbridge octahydronaphthalene or the derivative thereof is characterized by comprising the following steps of:
introducing protective gas into a reaction device, adding dicyclopentadiene and cycloolefin, carrying out initial pressure rise on the protective gas, then heating the system to 190-220 ℃ for heat preservation reaction, carrying out reaction for 8-12 h according to a method of indirectly supplementing pressure according to pressure drop along with the reaction, and separating according to the boiling point of a target component to obtain a corresponding product;
the pressure of the protective gas after being introduced is 1.5-3.5 MPa, and the protective gas pressure which is 3-10 times of the pressure drop is intermittently supplemented for a plurality of times in the reaction process according to the value of the pressure drop;
the structural formula of the dimethylbridge octahydronaphthalene or the derivative thereof is as follows:
r is H or C1-C10 alkyl.
2. The method for preparing dimethylbridged octahydronaphthalene or a derivative thereof according to claim 1, wherein the cycloolefin is added in excess.
3. The gradient pressurizing preparation method of dimethylbridge octahydronaphthalene or a derivative thereof according to claim 2, wherein the molar ratio of cycloolefin to dicyclopentadiene is 4:1-8:1.
4. The method for preparing dimethylbridged octahydronaphthalene or a derivative thereof according to claim 3, wherein the cyclic olefin is norbornene or a derivative thereof having a single position 5 substituted with an alkyl chain.
5. The method for preparing dimethylbridged octahydronaphthalene or a derivative thereof according to claim 4, wherein the cycloolefin is at least one of norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene and 5-decyl-2-norbornene.
6. The gradient pressurizing preparation method of dimethylbridge octahydronaphthalene or a derivative thereof according to claim 1, wherein the reaction pressure is 3-6 MPa when the thermal insulation reaction is performed.
7. The method for preparing dimethylbridge octahydronaphthalene or a derivative thereof according to claim 1, wherein the protective gas is nitrogen or argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310836764.3A CN116854555B (en) | 2023-07-10 | 2023-07-10 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310836764.3A CN116854555B (en) | 2023-07-10 | 2023-07-10 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116854555A CN116854555A (en) | 2023-10-10 |
| CN116854555B true CN116854555B (en) | 2024-02-06 |
Family
ID=88235370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310836764.3A Active CN116854555B (en) | 2023-07-10 | 2023-07-10 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116854555B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891456A (en) * | 1987-07-06 | 1990-01-02 | Nippon Oil Co., Ltd. | Method for preparing norbornene structure compound |
| JP2000026332A (en) * | 1998-07-06 | 2000-01-25 | Nippon Petrochem Co Ltd | COMPOSITION FOR POLYMERIZING 2-ETHYL-1,4,5,8-DIMETHANO-1,2,3,4,4 a,5,8,8a-OCTAHYDRONAPHTHALENE |
| JP2000026333A (en) * | 1998-07-06 | 2000-01-25 | Nippon Petrochem Co Ltd | PRODUCTION OF 2-ETHYL-1,4,5,8-DIMETHANO-1,2,3,4,4a,5,8,8a- OCTAHYDRONAPHTHALENE |
| JP2001055350A (en) * | 1999-06-10 | 2001-02-27 | Nippon Petrochem Co Ltd | Production of tetracyclododecene derivative |
| JP2004059508A (en) * | 2002-07-29 | 2004-02-26 | Nippon Zeon Co Ltd | Method for producing tetracyclododecene derivative |
| CN112592248A (en) * | 2020-12-21 | 2021-04-02 | 无锡阿科力科技股份有限公司 | Preparation method and application of tetracyclododecene compound |
| CN113286830A (en) * | 2018-10-03 | 2021-08-20 | 马特里亚公司 | Polymers for special applications |
| CN113336613A (en) * | 2021-05-19 | 2021-09-03 | 拓烯科技(衢州)有限公司 | Preparation method of tetracyclododecene compound |
| CN115385769A (en) * | 2022-09-06 | 2022-11-25 | 杭州睿丰融创科技有限公司 | Method for reducing byproducts in process of synthesizing tetracyclododecene compound |
| CN115433053A (en) * | 2022-09-06 | 2022-12-06 | 杭州睿丰融创科技有限公司 | Co-production method of tetracyclododecene and norbornene |
| CN116535283A (en) * | 2023-05-04 | 2023-08-04 | 杭州睿丰融创科技有限公司 | Preparation method of tetracyclododecene and derivatives thereof |
-
2023
- 2023-07-10 CN CN202310836764.3A patent/CN116854555B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891456A (en) * | 1987-07-06 | 1990-01-02 | Nippon Oil Co., Ltd. | Method for preparing norbornene structure compound |
| JP2000026332A (en) * | 1998-07-06 | 2000-01-25 | Nippon Petrochem Co Ltd | COMPOSITION FOR POLYMERIZING 2-ETHYL-1,4,5,8-DIMETHANO-1,2,3,4,4 a,5,8,8a-OCTAHYDRONAPHTHALENE |
| JP2000026333A (en) * | 1998-07-06 | 2000-01-25 | Nippon Petrochem Co Ltd | PRODUCTION OF 2-ETHYL-1,4,5,8-DIMETHANO-1,2,3,4,4a,5,8,8a- OCTAHYDRONAPHTHALENE |
| JP2001055350A (en) * | 1999-06-10 | 2001-02-27 | Nippon Petrochem Co Ltd | Production of tetracyclododecene derivative |
| JP2004059508A (en) * | 2002-07-29 | 2004-02-26 | Nippon Zeon Co Ltd | Method for producing tetracyclododecene derivative |
| CN113286830A (en) * | 2018-10-03 | 2021-08-20 | 马特里亚公司 | Polymers for special applications |
| CN112592248A (en) * | 2020-12-21 | 2021-04-02 | 无锡阿科力科技股份有限公司 | Preparation method and application of tetracyclododecene compound |
| CN113336613A (en) * | 2021-05-19 | 2021-09-03 | 拓烯科技(衢州)有限公司 | Preparation method of tetracyclododecene compound |
| CN115385769A (en) * | 2022-09-06 | 2022-11-25 | 杭州睿丰融创科技有限公司 | Method for reducing byproducts in process of synthesizing tetracyclododecene compound |
| CN115433053A (en) * | 2022-09-06 | 2022-12-06 | 杭州睿丰融创科技有限公司 | Co-production method of tetracyclododecene and norbornene |
| CN116535283A (en) * | 2023-05-04 | 2023-08-04 | 杭州睿丰融创科技有限公司 | Preparation method of tetracyclododecene and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116854555A (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wegner | Solid-state polymerization mechanisms | |
| EP2098542A1 (en) | Process for production of -olefin low polymers | |
| CN104710401A (en) | High-purity lactide and preparation method thereof | |
| CN116854555B (en) | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner | |
| CN112592248A (en) | Preparation method and application of tetracyclododecene compound | |
| Yang et al. | Synthesis of cyclic olefin polymers with high glass transition temperature by ring‐opening metathesis copolymerization and subsequent hydrogenation | |
| CN111548246A (en) | Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction | |
| CN113387921B (en) | Method for synthesizing glycolide | |
| Fang et al. | Synthesis and characterization of a novel functional monomer containing two allylphenoxy groups and one S-triazine ring and the properties of its copolymer with 4, 4′-bismaleimidodiphenylmethane (BMDPM) | |
| CN110628449A (en) | Method for preparing spinning-grade synthetic mesophase pitch | |
| CN112679297A (en) | Preparation method of high-purity dicyclopentadiene | |
| Bai et al. | Ring-opening metathesis polymerization of cyclopropene derivatives towards polyolefin elastomer analogues | |
| CA1049192A (en) | Ethylene polymerization process | |
| Cui et al. | Synthesis of cyclic olefin polymers with high glass transition temperature and high transparency using tungsten-based catalyst system | |
| CN110563867B (en) | Preparation method of high molecular weight high cis content polybutylene maleate | |
| CN108101728B (en) | Preparation method of p-menthane | |
| KR100831631B1 (en) | Method of preparation norbornene derivatives | |
| US4219688A (en) | Process for producing vinylnorbornene and/or tetrahydroindene | |
| CN106588555A (en) | Method for preparing cyclopentadiene and methylcyclopentadiene | |
| CN114478156A (en) | Synthesis method of polycyclic norbornene derivative | |
| CN110963990A (en) | Preparation method of musk C-14 | |
| JP3259498B2 (en) | Norbornene derivative compositions for metathesis ring-opening polymerization | |
| WO2024139679A1 (en) | Production process for norbornene | |
| CN117624562A (en) | Cycloolefin polymer containing thiophene group and preparation method and application thereof | |
| KR102004517B1 (en) | Continuous production method of norbornene derivative |
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 |