CN115385769A - Method for reducing byproducts in process of synthesizing tetracyclododecene compound - Google Patents
Method for reducing byproducts in process of synthesizing tetracyclododecene compound Download PDFInfo
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- CN115385769A CN115385769A CN202211083036.1A CN202211083036A CN115385769A CN 115385769 A CN115385769 A CN 115385769A CN 202211083036 A CN202211083036 A CN 202211083036A CN 115385769 A CN115385769 A CN 115385769A
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Abstract
The invention provides a method for synthesizing tetracyclododecene. The invention circularly adds dicyclopentadiene dropwise and introduces a small amount of ethylene. The operation of the circular dripping mode can effectively reduce the by-products. The invention can effectively inhibit the decomposition of the norbornene into cyclopentadiene and ethylene in the reaction process due to the introduction of the ethylene. Meanwhile, the introduced ethylene can react with part of dicyclopentadiene to generate norbornene, so that the cost for synthesizing norbornene in the production process is effectively reduced.
Description
Technical Field
The invention belongs to the technical field of synthesis of tetracyclododecene compounds, relates to a synthesis method of tetracyclododecene, and particularly relates to a method for reducing byproducts in the process of synthesizing tetracyclododecene compounds.
Background
Tetracyclododecene Compounds (TCD) are commonly used as polymerized monomers to prepare Cyclic Olefin Copolymers (COC), and the cyclic olefin copolymers are mainly used for manufacturing products such as optical lenses, medical packaging materials and the like. Therefore, in order to achieve better COC product properties, it is a primary task to develop efficient processes for preparing cycloolefin monomers.
Corresponding research schemes are also disclosed in the prior art, for example, U.S. Pat. No. 8,8978,8978,8978 discloses the preparation of norbornene/tetracyclododecene and its derivatives from olefins, norbornene and cyclopentadiene. Then distilling and separating to recover partial norbornene and separating to obtain target product tetracyclododecene, but cyclopentadiene trimer and other side products are easy to produce in the reaction process. By increasing the molar ratio of the olefin or increasing the reaction temperature, the trimer by-product content can be reduced, but increasing the molar ratio reduces the proportion of tetracyclododecene in the product, and increasing the temperature leads to an increase in other by-products, resulting in a decrease in the yield of tetracyclododecene. In addition, patent CN112592248 also reports a method for preparing tetracyclododecene compounds by using norbornene and cyclopentadiene or dicyclopentadiene as raw materials, wherein the purity of the tetracyclododecene compounds after distillation and purification can reach more than 98%, but the reaction generates many byproducts.
Therefore, how to find a more suitable reaction mode to solve the above problems in the existing synthesis of tetracyclododecene compounds has become one of the technical problems to be solved by many front-line researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for synthesizing tetracyclododecene, and in particular, to a method for reducing byproducts in the process of synthesizing tetracyclododecene compounds.
The invention provides a method for synthesizing tetracyclododecene, which comprises the following steps:
1) Introducing a raw material system comprising a dicyclopentadiene solution, a norbornene solution and liquid ethylene into a tubular reactor for reaction to obtain a reaction solution;
2) And returning the reaction liquid obtained in the step to a raw material system, and continuously entering a tubular reactor along with the raw material system of the dicyclopentadiene solution, the norbornene solution and the liquid ethylene for circular reaction to obtain the tetracyclododecene.
Preferably, the solvent of the dicyclopentadiene solution comprises one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane;
the mass concentration of the dicyclopentadiene solution is 0.01-90%.
Preferably, the solvent of the norbornene solution comprises one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane;
the mass concentration of the norbornene solution is 10-90%.
Preferably, in the step 1), the molar ratio of the dicyclopentadiene to the norbornene is 1: (1-20);
in the step 1), the molar ratio of the dicyclopentadiene to the liquid ethylene is (1-10): (10-1);
preferably, the reaction temperature is 180-270 ℃;
the reaction time is 0.1-6 h.
Preferably, the reaction solution returning raw material system specifically comprises:
and returning the reaction liquid to the norbornene solution raw material in the raw material system, mixing the reaction liquid with the norbornene solution raw material to obtain a mixed liquid, and continuously feeding the dicyclopentadiene solution, the mixed liquid and the liquid ethylene raw material system into the tubular reactor for circular reaction.
Preferably, in the step 1), the flow ratio of the dicyclopentadiene solution to the norbornene solution is (1-5): (20-1);
the flow ratio of the dicyclopentadiene solution to the mixed solution is (1-5): (20-1).
Preferably, the number of the cyclic reaction is 2 to 4;
the retention time of the raw material system in the reaction system is 1-12 h.
Preferably, the circulating reaction further comprises an atmospheric distillation step and a vacuum distillation step.
Preferably, after the normal pressure rectification, norbornene can be obtained;
and continuing vacuum distillation after the normal pressure rectification to obtain the tetracyclododecene.
The invention provides a method for synthesizing tetracyclododecene, which comprises the following steps of firstly introducing a raw material system comprising dicyclopentadiene solution, norbornene solution and liquid ethylene into a tubular reactor for reaction to obtain reaction liquid; and then returning the reaction liquid obtained in the step to a raw material system, and continuously entering a tubular reactor along with the raw material system of the dicyclopentadiene solution, the norbornene solution and the liquid ethylene for circular reaction to obtain the tetracyclododecene. Compared with the prior art, the invention is based on the research that the prior scheme for synthesizing the Tetracyclododecene (TCD) generates more heavy components, such as Tricyclopentadiene (TCPD) and the like, and higher temperature is often required in the preparation process of the Tetracyclododecene (TCD), so that the decomposition of Norbornene (NB) is easily caused.
Based on the method, the invention creatively designs a method for synthesizing the tetracyclododecene, which is a method for reducing byproducts in the process of synthesizing the tetracyclododecene compound. Aiming at the condition that the by-product is high in the process of synthesizing Tetracyclododecene (TCD) in the prior art, particularly, dicyclopentadiene (DCPD) raw material liquid is circularly dripped, the dripped dicyclopentadiene (DCPD) is consumed immediately, the norbornene and dicyclopentadiene are maintained at a high molar ratio, the content of the by-product HCD can be effectively reduced, and the content of cyclopentadiene Trimer (TCPD) can be effectively reduced. A small amount of ethylene is introduced into the system, so that not only can the decomposition of Norbornene (NB) be inhibited, but also the generation of byproducts can be effectively inhibited. Meanwhile, ethylene can react with part of dicyclopentadiene (DCPD) to generate Norbornene (NB), so that the production cost is saved.
According to the invention, by means of cyclic dropwise addition and ethylene introduction, the generation of by-products can be reduced, the decomposition of Norbornene (NB) can be inhibited, and the high-purity tetracyclododecene compound can be prepared.
Experimental results show that by adopting the synthetic method of the tetracyclododecene provided by the invention, the concentration of the by-product is reduced to 1.44% and the by-product/TCD is 0.06 by means of cyclic dropwise addition and ethylene introduction, namely, fewer by-products and fewer Norbornenes (NB) are generated in unit mass of product production, and the TCD with the purity of more than 99% is obtained by reduced pressure distillation.
Drawings
FIG. 1 is a schematic process flow diagram of a reaction system for synthesizing Tetracyclododecene (TCD) according to the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs analytical purity or conventional purity used in the art of tetracyclododecene synthesis.
All the raw materials of the invention, the marks or the abbreviations thereof belong to the conventional marks or the abbreviations in the field, and are clear and definite in the field of related applications, and the raw materials can be purchased from the market or prepared by the conventional method according to the marks or the abbreviations by the technical personnel in the field.
The invention provides a method for synthesizing tetracyclododecene, which comprises the following steps:
1) Introducing a raw material system comprising a dicyclopentadiene solution, a norbornene solution and liquid ethylene into a tubular reactor for reaction to obtain a reaction solution;
2) And returning the reaction liquid obtained in the step to a raw material system, and continuously entering a tubular reactor along with the raw material system of the dicyclopentadiene solution, the norbornene solution and the liquid ethylene for circular reaction to obtain the tetracyclododecene.
The method comprises the steps of firstly introducing a raw material system comprising a dicyclopentadiene solution, a norbornene solution and liquid ethylene into a tubular reactor for reaction to obtain a reaction solution.
In the present invention, the solvent of the dicyclopentadiene solution preferably includes one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane, and more preferably cyclohexane, toluene, xylene, n-pentane or n-hexane.
In the present invention, the mass concentration of the dicyclopentadiene solution is preferably 0.01% to 90%, more preferably 0.1% to 80%, more preferably 1% to 60%, more preferably 5% to 50%, more preferably 10% to 30%.
In the present invention, the solvent of the norbornene solution preferably includes one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane, and more preferably cyclohexane, toluene, xylene, n-pentane or n-hexane.
In the present invention, the norbornene solution preferably has a mass concentration of 10% to 90%, more preferably 30% to 80%, and still more preferably 50% to 60%.
In the present invention, in the step 1), the molar ratio of the dicyclopentadiene to the norbornene is preferably 1: (1 to 20), more preferably 1: (5 to 16), more preferably 1: (11 to 12).
In the present invention, in the step 1), the molar ratio of the dicyclopentadiene to the liquid ethylene is preferably (1 to 10): (10-1), more preferably (3-8): (10-1), more preferably (5-6): (10-1), more preferably (1-10): (8 to 3), more preferably (1 to 10): (6-5).
In the present invention, the temperature of the reaction is preferably 180 to 270 ℃, more preferably 200 to 250 ℃, and still more preferably 220 to 230 ℃.
In the present invention, the reaction time is preferably 0.1 to 6 hours, more preferably 1 to 5 hours, and still more preferably 2 to 4 hours. Specifically, the reaction time is the reaction time in the tubular reactor during the synthesis process of the present invention.
In the present invention, in the step 1), the flow ratio of the dicyclopentadiene solution to the norbornene solution is preferably (1 to 5): (20-1), more preferably (2-4): (20-1), more preferably (1-5): (15 to 6).
In the present invention, the flow ratio of the dicyclopentadiene solution to the mixed solution is preferably (1 to 5): (20-1), more preferably (2-4): (20-1), more preferably (1-5): (15 to 6).
In the present invention, the flow ratio set for carrying out the first reaction of step 1) is constant, and when the reaction solution in step 2) is circulated into the NB solution, the mixed solution can be fed into the reaction system under the same flow conditions or can be finely adjusted. Therefore, the flow ratio in the invention can reflect the dosage relation and proportion of the materials.
The reaction solution obtained in the step is returned to the raw material system, and then continuously enters the tubular reactor along with the raw material system of the dicyclopentadiene solution, the norbornene solution and the liquid ethylene for circular reaction to obtain the tetracyclododecene.
In the present invention, the reaction solution is preferably returned to the raw material system:
and returning the reaction liquid to the norbornene solution raw material in the raw material system, mixing the reaction liquid with the norbornene solution raw material to obtain a mixed liquid, and continuously feeding the dicyclopentadiene solution, the mixed liquid and the liquid ethylene raw material system into the tubular reactor for circular reaction.
In the present invention, the number of the cyclic reaction is preferably 2 to 4.
In the present invention, the residence time of the raw material system in the reaction system is preferably 1 to 12 hours, more preferably 3 to 10 hours, and still more preferably 5 to 8 hours. Specifically, the residence time is preferably the total time of the raw material system in the whole reaction system.
In the present invention, the recycling reaction preferably further comprises an atmospheric distillation step and a vacuum distillation step.
In the present invention, it is preferable that norbornene can be obtained after the atmospheric distillation.
In the present invention, the distillation under reduced pressure is continued after the atmospheric distillation, and preferably tetracyclododecene is obtained.
The invention is a complete and refined integral synthesis process, better reduces by-products and inhibits the decomposition of NB, and the synthesis method of the tetracyclododecene specifically comprises the following steps:
the invention provides a continuous synthesis method of Tetracyclododecene (TCD), which adopts a continuous synthesis mode to circularly drop, and part of ethylene is introduced to inhibit byproducts.
Specifically, the structural formula of the tetracyclododecene compound is shown as the formula (I):
specifically, the raw materials of the feeding device are a DCPD solution and an NB solution. Among them, one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane are used as a solvent, and cyclohexane is preferable.
Specifically, the reaction solution from the tubular reactor is recycled to the NB solution storage tank. Wherein, the circulation is carried out for 2 to 4 times. Based on NB.
Specifically, the reaction temperature is preferably 180 to 270 ℃, more preferably 220 to 250 ℃.
Specifically, the molar ratio of the total NB to the total DCPD is preferably 1:1-20, more preferably 5:1-12.
Specifically, the molar ratio of the DCPD to ethylene is preferably 1.
Specifically, the reaction time of the raw materials in the reactor is preferably 1 to 12 hours, more preferably 2 to 4 hours.
In the present invention, tetracyclododecene (TCD) is a monomer polymerized to prepare a cycloolefin copolymer having the formula C 12 H 16 The structural formula is shown as the formula (I):
the main reaction is as follows:
the side reactions are as follows:
the invention provides a complete and refined integral synthesis process, better reduces by-products and inhibits the decomposition of NB, and also provides a synthesis device of the tetracyclododecene, which specifically comprises the following structure and composition:
referring to FIG. 1, FIG. 1 is a schematic process flow diagram of a reaction system for synthesizing Tetracyclododecene (TCD) according to the present invention.
As shown in fig. 1, the reactor is a reactant feeding device, a tubular reactor, an air cooling zone, a product detection zone and a circulating pipeline from left to right. (one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane, preferably cyclohexane) is used as a solvent to prepare a DCPD solution and an NB solution according to a certain molar ratio, the DCPD solution, the NB solution and liquefied ethylene are pumped into a tubular reactor by a liquid phase metering pump according to a certain flow rate (the flow rate is calculated according to the reactor volume and the retention time by using Aspen software simulation), and a reaction liquid discharged from the tubular reactor is recycled into an NB solution storage tank. Circulating for 2-4 times, wherein the reaction temperature is 180-270 ℃, the molar ratio of the total NB to the total DCPD is 1:1-20, the retention time of the raw materials in the reactor is 1-12 h, and the pressure in the reactor is adjusted by a back pressure valve. Sampling after the reaction system is stable, and detecting the content of each component in the crude product by using gas chromatography. And (3) rectifying the TCD reaction solution at normal pressure to obtain NB with the purity of more than 99%, and continuing to rectify under reduced pressure to obtain TCD with the purity of more than 99%.
The invention provides a method for reducing byproducts in the process of synthesizing tetracyclododecene compounds. According to the invention, through circularly dripping the dicyclopentadiene (DCPD) raw material liquid, the dripped dicyclopentadiene (DCPD) can be consumed immediately, the norbornene and dicyclopentadiene are maintained at a higher molar ratio, the content of the byproduct HCD can be effectively reduced, and the content of cyclopentadiene Trimer (TCPD) can be effectively reduced. A small amount of ethylene is introduced into the system, so that not only can the decomposition of Norbornene (NB) be inhibited, but also the generation of byproducts can be effectively inhibited. Meanwhile, ethylene reacts with part of dicyclopentadiene (DCPD) to generate Norbornene (NB), so that the production cost is saved.
According to the invention, by means of cyclic dropwise addition and ethylene introduction, the generation of by-products can be reduced, the decomposition of Norbornene (NB) can be inhibited, and the high-purity tetracyclododecene compound can be prepared.
Experimental results show that by adopting the synthetic method of the tetracyclododecene provided by the invention, the concentration of the by-product is reduced to 1.44% and the by-product/TCD is 0.06 by means of cyclic dropwise addition and ethylene introduction, that is, fewer by-products are generated and Norbornene (NB) is consumed in unit mass of product production, and the TCD with the purity of more than 99% is obtained by reduced pressure rectification.
For further illustration of the present invention, the following will describe in detail a method for synthesizing tetracyclododecene provided by the present invention with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Preparing NB cyclohexane solution with a mass fraction of 60%, preparing DCPD cyclohexane solution according to a molar ratio NB: DCPD =8:1, and calculating the flow rate according to 4 cycle times and reaction time. Introducing ethylene gas into a thermostatic bath at the temperature of minus 5 ℃ to change into a liquid phase, and mixing the ethylene gas: DCPD =1:5 molar ratio determines the desired flow rate of ethylene. And (3) feeding the NB cyclohexane solution, the DCPD cyclohexane solution and the ethylene into a tubular reactor by using a liquid phase metering pump. The reaction temperature is 240 ℃, the raw materials stay in the reactor for 4 hours, the pressure in the reactor is adjusted to 10MPa by a back pressure valve, the reaction liquid is circulated back to the NB cyclohexane solution storage tank, and after the reaction is finished, a sample is taken and the gas chromatography is used for detecting the content of each component in the crude product. And (3) rectifying the crude product at normal pressure to obtain NB with the purity of more than 99%, and continuing to rectify under reduced pressure to obtain TCD with the purity of more than 99%.
Example 2
NB cyclohexane solution was prepared at a mass fraction of 50%, DCPD cyclohexane solution was prepared at a molar ratio of NB: DCPD =4:1, and the flow rate was calculated at 4 cycles and reaction time. Introducing ethylene gas into a thermostatic bath at the temperature of minus 5 ℃ to change into a liquid phase, and mixing the ethylene gas: DCPD =1:1 molar ratio determines the desired flow rate of ethylene. And (3) feeding the NB cyclohexane solution, the DCPD cyclohexane solution and the ethylene into a tubular reactor by using a liquid phase metering pump. The reaction temperature is 240 ℃, the raw materials stay in the reactor for 4 hours, the pressure in the reactor is adjusted to be 10MPa by a back pressure valve, the reaction liquid is circulated back to the NB cyclohexane solution storage tank, and after the reaction is finished, a sample is taken and the gas chromatography is used for detecting the content of each component in the crude product. And (3) rectifying the crude product at normal pressure to obtain NB with the purity of more than 99%, and continuing to rectify under reduced pressure to obtain TCD with the purity of more than 99%.
Comparative example 1
Ethylene was not fed and the other conditions were kept the same as in example 1.
Comparative example 2
The mass of NB and DCPD to be added, and the amount of cyclohexane to be added were calculated as NB (NB: DCPD = 8:1) by mass fraction 60%. The preparation mass was 60% NB (NB: DCPD = 8:1) in cyclohexane solution, and the flow rate was calculated in terms of the residence time. Introducing ethylene gas into a thermostatic bath at the temperature of minus 5 ℃ to change into a liquid phase, and mixing the ethylene gas: DCPD =1:5 molar ratio determines the desired flow rate of ethylene. And (3) pumping the prepared solution and ethylene into the tubular reactor by using a liquid-phase metering pump. The reaction temperature is 240 ℃, the raw materials stay in the reactor for 4 hours, the pressure in the reactor is adjusted to 10MPa by a back pressure valve, and after the reaction system is stable, a sample is taken and the gas chromatography is used for detecting the content of each component in the crude product.
Referring to table 1, table 1 shows the results of gas chromatography tests on crude products prepared in examples of the present invention and comparative examples.
TABLE 1
| Main component | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| NB | 45.02％ | 28.30％ | 37.01％ | 44.89％ |
| TCD | 23.86％ | 34.33％ | 26.53％ | 20.84％ |
| Cyclohexane | 29.47％ | 32.45％ | 28.47％ | 29.46％ |
| Cyclopentadiene | 0.05％ | 0.04％ | 0.09％ | 0.18％ |
| DCPD | 0.23％ | 0.87％ | 0.47％ | 0.23％ |
| TCPD | 0.24％ | 0.65％ | 1.21％ | 2.24％ |
| Polymer and method of producing the same | 1.13％ | 3.36％ | 6.22％ | 2.16％ |
| Total by-products | 1.44％ | 4.05％ | 7.43％ | 4.58％ |
| by-product/TCD | 0.06 | 0.12 | 0.28 | 0.22 |
The foregoing detailed description of the method for reducing by-products during the synthesis of tetracyclododecenes according to the present invention has been presented and the principles and embodiments of the present invention are described herein with reference to specific examples, which are intended to be included as an aid in understanding the principles of the present invention and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for synthesizing tetracyclododecene is characterized by comprising the following steps:
1) Introducing a raw material system comprising a dicyclopentadiene solution, a norbornene solution and liquid ethylene into a tubular reactor for reaction to obtain a reaction solution;
2) And returning the reaction liquid obtained in the step to a raw material system, and continuously entering a tubular reactor along with the raw material system of the dicyclopentadiene solution, the norbornene solution and the liquid ethylene for circular reaction to obtain the tetracyclododecene.
2. The synthesis method according to claim 1, wherein the solvent of the dicyclopentadiene solution comprises one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane;
the mass concentration of the dicyclopentadiene solution is 0.01-90%.
3. The method of claim 1, wherein the solvent of the norbornene solution comprises one or more of cyclohexane, toluene, xylene, n-pentane, and n-hexane;
the mass concentration of the norbornene solution is 10-90%.
4. The synthesis method according to claim 1, wherein in the step 1), the molar ratio of the dicyclopentadiene to the norbornene is 1: (1-20);
in the step 1), the molar ratio of the dicyclopentadiene to the liquid ethylene is (1-10): (10-1);
5. the synthesis method according to claim 1, wherein the reaction temperature is 180-270 ℃;
the reaction time is 0.1-6 h.
6. The synthesis method according to claim 1, wherein the reaction solution return raw material system is specifically:
and returning the reaction liquid to the norbornene solution raw material in the raw material system, mixing the reaction liquid with the norbornene solution raw material to obtain a mixed liquid, and continuously feeding the dicyclopentadiene solution, the mixed liquid and the liquid ethylene raw material system into the tubular reactor for circular reaction.
7. The synthesis method according to claim 6, wherein in the step 1), the flow ratio of the dicyclopentadiene solution to the norbornene solution is (1-5): (20-1);
the flow ratio of the dicyclopentadiene solution to the mixed solution is (1-5): (20-1).
8. The synthesis method according to claim 1, wherein the number of the cyclic reactions is 2 to 4;
the retention time of the raw material system in the reaction system is 1-12 h.
9. The synthesis method according to claim 1, characterized in that the cyclic reaction is followed by an atmospheric distillation step and a vacuum distillation step.
10. The synthesis method according to claim 9, characterized in that norbornene can be obtained after the atmospheric distillation;
and continuing vacuum distillation after the normal pressure rectification to obtain the tetracyclododecene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115806460A (en) * | 2022-12-09 | 2023-03-17 | 杭州睿丰融创科技有限公司 | Method for reducing by-products in production process of tetracyclododecene |
| CN115838314A (en) * | 2022-11-30 | 2023-03-24 | 天津大学 | Method for dynamically synthesizing tetracyclododecene through oscillation heating |
| CN116854555A (en) * | 2023-07-10 | 2023-10-10 | 天津大学 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115838314A (en) * | 2022-11-30 | 2023-03-24 | 天津大学 | Method for dynamically synthesizing tetracyclododecene through oscillation heating |
| CN115806460A (en) * | 2022-12-09 | 2023-03-17 | 杭州睿丰融创科技有限公司 | Method for reducing by-products in production process of tetracyclododecene |
| CN115806460B (en) * | 2022-12-09 | 2024-03-08 | 杭州睿丰融创科技有限公司 | Method for reducing byproducts in tetracyclododecene production process |
| CN116854555A (en) * | 2023-07-10 | 2023-10-10 | 天津大学 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
| CN116854555B (en) * | 2023-07-10 | 2024-02-06 | 天津大学 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
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