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CN-122010663-A - Cyclic olefin compound and preparation method and application thereof

CN122010663ACN 122010663 ACN122010663 ACN 122010663ACN-122010663-A

Abstract

The invention relates to the field of organic synthesis, in particular to a cyclic olefin compound, a preparation method and application thereof. According to the invention, a cyclic olefin compound and cyclopentadiene are used as raw materials, diels-Alder reaction is carried out under the liquid phase condition at 100-200 ℃ and 1-5 MPa, the molar ratio of the two is controlled to be (1-2): 1, the reaction can be carried out in a tubular, kettle-type or combined reactor in an intermittent, semi-continuous or continuous mode, and compound II can be supplemented during the reaction to ensure the constant molar ratio of the raw materials. The method omits the dicyclopentadiene high-temperature cracking step in the traditional process, has low reaction temperature and few byproducts, improves the utilization rate of raw materials and the environment-friendly performance of the device, and reduces the energy consumption and the dangers. The cyclic olefin compound prepared by the method is used for ring-opening metathesis polymerization, and the hydrogenated ring-opening metathesis polymer obtained after hydrogenation has excellent elongation at break and is suitable for downstream processing application.

Inventors

  • LIAO HENG
  • XU LEITING
  • GONG ZHAOLONG

Assignees

  • 广东特聚新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1. A process for producing a cyclic olefin compound, comprising the steps of: Adding the compound I and the compound II into a reactor, and generating Diels-Alder reaction at 100-200 ℃ and 1-5 MPa to generate a compound III cyclic olefin compound; Wherein the structural formula of the compound I, the compound II and the compound III is as follows: ; In the formula I, R 1 and R 2 are independently one of H, C 1 -C 4 alkyl groups, or R 1 and R 2 are connected to form a cyclic structure with 5-10 carbon atoms, wherein n=1-4; the molar ratio of the compound I to the compound II is (1-2) 1; the reaction time of the Diels-Alder reaction is 1-5 h.
  2. 2. The process for preparing a cyclic olefin compound according to claim 1, wherein the compound I and the compound II are mixed with a solvent to form a solution before being fed into the reactor.
  3. 3. The method for producing a cyclic olefin compound according to claim 1, wherein the solvent comprises one of n-hexane, cyclohexane, toluene or xylene.
  4. 4. The method for producing a cyclic olefin compound according to claim 1, wherein the Diels-Alder reaction is carried out by one of batch reaction, semi-continuous reaction and continuous reaction.
  5. 5. The method for producing a cyclic olefin compound according to claim 1, wherein the reactor comprises a tubular reactor and/or a tank reactor.
  6. 6. A cyclic olefin compound produced by the process for producing a cyclic olefin compound according to any one of claims 1 to 5.
  7. 7. Use of a cyclic olefin compound according to claim 6 for hydrogenated ring-opening metathesis polymer synthesis.
  8. 8. Use of a cyclic olefin compound according to claim 7, characterized in that the synthesis of the hydrogenated ring-opening metathesis polymer comprises the steps of: mixing a cyclic olefin compound and a ring-opening metathesis catalyst for polymerization reaction to obtain a ring-opening metathesis polymer, and mixing the ring-opening metathesis polymer and a hydrogenation catalyst for hydrogenation reaction to obtain the hydrogenated ring-opening metathesis polymer.
  9. 9. The use of a cyclic olefin compound according to claim 8, wherein the polymerization reaction temperature is 30-100 ℃.
  10. 10. The use of a cyclic olefin compound according to claim 8, wherein the hydrogenation reaction is carried out at a temperature of 100 to 200 ℃.

Description

Cyclic olefin compound and preparation method and application thereof Technical Field The invention relates to the field of organic synthesis, in particular to a cyclic olefin compound, a preparation method and application thereof. Background The cyclic olefin monomer takes an important place in the chemical industry by virtue of the unique chemical structure and physical properties, and particularly the cyclic olefin compound containing a norbornene structure is a key material in a plurality of high-end fields such as biological medicine, organic synthesis, high-molecular synthesis and the like. In the field of high-molecular polymers, the compound is used as a core monomer of rubber and optical materials, and the prepared polymer has excellent heat resistance, light transmittance and mechanical stability, has high value-added application potential in the manufacture of high-end products such as precise instruments, electronic devices, medical devices and the like, and becomes an important material foundation for promoting the upgrade of related industries. Conventional synthesis of cyclic olefin compounds, particularly those containing norbornene structures, is generally synthesized by a Diels-Alder reaction of dicyclopentadiene with an olefin under high temperature and high pressure conditions. U.S. patent No. 4168282a discloses a method for synthesizing norbornene from b.f. goodrich, which uses halogenated hydrocarbon as a solvent and dicyclopentadiene and ethylene as raw materials, and performs a reaction at 240 to 280 ℃. DuPont discloses a method for preparing norbornene, which uses an inert aliphatic solvent such as heptane and the like, to prepare norbornene at 250-290 ℃. Chinese patent application CN117602998a discloses a process for the preparation of norbornene and tetracyclododecene, produced by reacting ethylene with dicyclopentadiene at a temperature of 220-280 ℃. Chinese patent application CN112592248a discloses a method for preparing tetracyclododecene compounds, which performs an addition reaction at 230-260 ℃ to prepare corresponding cycloolefin compounds. These high temperature conditions promote the cracking of dicyclopentadiene to cyclopentadiene and the addition reaction with olefins, but also present a number of problems. The high-temperature environment not only can cause side reactions of cyclopentadiene and dicyclopentadiene to generate various invalid byproducts to cause serious waste of raw materials, but also can increase energy consumption and safety risk in the production process, and the generated waste also causes additional pressure to the environment. In addition, in order to inhibit side reactions, the existing technology generally needs to greatly excess olefin monomers, which further reduces the overall utilization rate of raw materials and increases the production cost and the difficulty of subsequent separation and purification. Therefore, the development of milder reaction conditions, the reduction of side reactions and the improvement of the utilization rate of raw materials are realized, the efficient green synthesis of the cyclic olefin compounds is an urgent requirement for the development of the current industry, and the method has important significance for promoting the energy conservation, the greenization and the economic transformation of industrial production. Disclosure of Invention In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing a cyclic olefin compound, comprising the steps of: Adding the compound I and the compound II into a reactor, and generating Diels-Alder reaction at 100-200 ℃ and 1-5 MPa to generate a compound III cyclic olefin compound; Wherein the structural formula of the compound I, the compound II and the compound III is as follows: ; In the formula I, R 1 and R 2 are independently one of H, C 1-C4 alkyl groups or R 1 and R 2 are connected to form a cyclic structure with 5-10 carbon atoms, and n=1-4. As one practical example, the molar ratio of the compound I to the compound II is (1-2): 1. According to the synthesis scheme, through specific reaction conditions and raw material structural design, the core pain points that the traditional preparation of the cyclic olefin compound depends on dicyclopentadiene as a raw material and needs 220-290 ℃ high-temperature pyrolysis, so that the energy consumption is high, the danger is high, side reactions are easily caused, the raw material utilization rate is low due to the fact that olefin monomers are required to be greatly excessive, the waste is serious, and the purity of the product and the subsequent polymerization application performance are influenced due to the fact that byproducts are increased due to unbalance of the high temperature and the raw material proportion are solved. The method directly takes the cyclic olefin compound (compound I) as a raw material to omit a high-temperature cracking step, controls the react