Synthesis method of hexyl norbornene and application method of hexyl norbornene in polycycloolefin
Hexylnorbornene was synthesized by controlling the molar ratio of octene and dicyclopentadiene and adding a polymerization inhibitor. By combining ROMP polymerization and high-pressure hydrogenation, the toughness and solution stability problems of polycyclic olefin materials were solved, and the efficient preparation of polycyclic olefins was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 广东特聚新材料科技有限公司
- Filing Date
- 2026-02-06
- Publication Date
- 2026-05-15
AI Technical Summary
Existing polycyclic olefin materials are insufficient in terms of toughness and impact resistance, and have poor solution stability, which increases the difficulty of devolatilization and granulation.
Hexylnorbornene was synthesized by controlling the molar ratio of octene to dicyclopentadiene to (0.8-2):(0.5-1) and adding a polymerization inhibitor. Subsequently, hexylnorbornene was used as a raw material, and polycyclic olefins were prepared by combining ROMP polymerization and high-pressure hydrogenation reaction and adjusting the reaction conditions.
It improves the toughness and impact resistance of polycyclic olefins, enhances solution stability, reduces precipitation and gelation, and achieves mild reaction conditions and high conversion rate.
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Figure CN122036444A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer compounds, specifically to a method for synthesizing hexylnorbornene and its application in polycyclic olefins. Background Technology
[0002] Polycyclic olefins (PEOs) are highly transparent polyolefin materials with numerous superior properties, finding wide application in optical materials, pharmaceuticals, and vaccines. However, most PEOs are prepared by ring-opening polymerization of norbornene derivative monomers via ROMP followed by hydrogenation. This results in polymers with numerous cyclic structures, high rigidity, but insufficient toughness and impact resistance. Furthermore, PEO solutions exhibit low stability, readily precipitating out of the reaction solution, increasing the difficulty of devolatilization and granulation. Therefore, optimizing norbornene derivative monomers and developing a norbornene derivative with mild reaction conditions, short reaction time, and high conversion rate for application in PEO preparation is crucial for improving the toughness and impact resistance of PEOs.
[0003] Japanese Patent Application Publication No. 1-168724 discloses a ternary cyclic olefin polymer synthesized via ROMP ring-opening polymerization, exhibiting excellent light transmittance, low water absorption, and scratch resistance. However, this ternary cyclic olefin polymer generally has low mechanical strength, low impact strength, and poor toughness. Japanese Patent Application JP 2005-290232 A discloses that increasing the NB content in the polymerization process can improve the solution stability, impact resistance, and toughness of the cyclic olefin polymer; however, a high NB content will lower the glass transition temperature (Tg) of the polycyclic olefin material, affecting its processability. Summary of the Invention
[0004] In order to develop a norbornene derivative with mild reaction conditions, short reaction time and high conversion rate, the first aspect of the present invention provides a method for synthesizing hexyl norbornene, comprising the following steps: using octene and dicyclopentadiene as substrates, adding a polymerization inhibitor and solvent I, mixing and carrying out a Diels-Alder reaction to generate hexyl norbornene, wherein the molar ratio of octene to dicyclopentadiene is (0.8-2):(0.5-1).
[0005] This invention controls the molar ratio of octene to dicyclopentadiene to be (0.8-2):(0.5-1), making the reactant ratio more favorable for the Diels-Alder reaction. This can achieve a dicyclopentadiene conversion rate of over 55%, a byproduct (cyclopentadiene polymer) content of less than 1%, and a lower reaction temperature, shorter reaction time, and milder reaction conditions.
[0006] In one embodiment, the molar ratio of octene to dicyclopentadiene is (1-2):(0.5-0.8).
[0007] In one embodiment, the molar ratio of octene to dicyclopentadiene is (1.3-2):(0.5-0.6).
[0008] In one embodiment, the polymerization inhibitor accounts for 0.01%-0.5% of the total mass of the raw materials for preparing hexylnorbornene.
[0009] In one embodiment, the polymerization inhibitor accounts for 0.1%-0.5% of the total mass of the raw materials for preparing hexylnorbornene.
[0010] In one embodiment, the polymerization inhibitor accounts for 0.1%-0.3% of the total mass of the raw materials for preparing hexylnorbornene.
[0011] In one embodiment, the solvent is a low-polarity solvent, which includes, but is not limited to, at least one of petroleum ether, carbon tetrachloride, cyclohexane, n-hexane, octane, benzene, toluene, or xylene.
[0012] In one embodiment, the solvent includes at least one of octane, cyclohexane, benzene, toluene, or xylene.
[0013] In one embodiment, the solvent includes at least one of cyclohexane, toluene, or xylene.
[0014] In one embodiment, the polymerization inhibitor includes at least one of phenolic, quinone, and amine polymerization inhibitors.
[0015] In one embodiment, the polymerization inhibitor includes at least one of hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, p-benzoquinone, methyl-p-benzoquinone, N-nitrosodiphenylamine, or phenothiazine.
[0016] In one embodiment, the polymerization inhibitor includes at least one of p-tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, p-benzoquinone, or methyl-p-benzoquinone.
[0017] In one embodiment, the polymerization inhibitor includes at least one of p-tert-butylcatechol (TBC) or 2,6-di-tert-butyl-p-cresol.
[0018] In one embodiment, the concentration of dicyclopentadiene in solution A is 55-95 wt%.
[0019] In one embodiment, the concentration of dicyclopentadiene in solution A is 85-95 wt%.
[0020] In one embodiment, the reaction temperature is 150-300°C and the reaction time is 1-5 hours.
[0021] In one embodiment, the reaction temperature is 150-250°C; the reaction temperature is 180-220°C.
[0022] As one embodiment, the method for synthesizing hexylnorbornene specifically includes the following steps: Prepare solution A: Mix dicyclopentadiene with solvent one, heat to 120°C and keep warm for later use; Preparation of Solution B: Mix octene, solvent one, and polymerization inhibitor to obtain solution B; Heat solution B to 150-300℃ and hold at that temperature for 10 min. Add solution A dropwise to carry out the reaction, controlling the dropwise addition time to 0.5-4.5 h. Keep warm for 0.5 h. Use gas chromatography to detect the bicyclic conversion rate and the formation of byproducts. Obtain hexylnorbornene with a purity >99% by vacuum distillation.
[0023] This invention avoids side reactions caused by excessively high local concentrations by adding liquid A to liquid B and controlling the dropping rate; the polymerization inhibitor can effectively suppress the self-polymerization reaction of dicyclopentadiene and reduce the formation of by-products.
[0024] A second aspect of the present invention provides a hexylnorbornene synthesized using the above-described hexylnorbornene synthesis method, wherein the purity of the hexylnorbornene is >99% and the by-product rate is ≤0.3%.
[0025] A third aspect of the present invention provides a method for preparing a polycyclic olefin, using the aforementioned hexylnorbornene as a raw material.
[0026] In one embodiment, the raw materials for preparing the polycyclic olefin include, by weight, 110-130 parts of monomer mixture, 450-550 parts of solvent, 0.5-1 parts of molecular weight regulator, 0.1-0.5 parts of reaction regulator, and 0.5-1 parts of catalyst.
[0027] In one embodiment, the raw materials for preparing the polycyclic olefin include, by weight, 120 parts of monomer mixture, 500 parts of solvent, 0.6 parts of molecular weight regulator, 0.38 parts of reaction regulator, and 0.72 parts of catalyst.
[0028] In one embodiment, the high-pressure hydrogenation reaction comprises 5-15 parts by weight of polycyclic olefin intermediate, 80-100 parts by weight of solvent, and 0.3-0.8 parts by weight of hydrogenation catalyst.
[0029] In one embodiment, the high-pressure hydrogenation reaction comprises 10 parts by weight of polycyclic olefin intermediate, 90 parts by weight of solvent, and 0.5 parts by weight of hydrogenation catalyst.
[0030] As one embodiment, the method for preparing the polycyclic olefin includes the following steps: The monomer mixture containing the hexylnorbornene, solvent II, molecular weight regulator, reaction regulator, and catalyst are stirred and mixed, and the temperature is raised to carry out ROMP polymerization. After the reaction is completed, the polycyclic olefin intermediate is quenched and precipitated. The polycyclic olefin intermediate was dried at low temperature, and then hydrogenation catalyst and solvent III were added to carry out a high-pressure hydrogenation reaction. After filtering the hydrogenation catalyst, the polycyclic olefin was obtained.
[0031] In one embodiment, the mixing temperature is 25-40°C.
[0032] In one embodiment, the monomer mixture further includes at least one of norbornene, dicyclopentadiene, tetracyclododecene, methyl norbornene, vinyl norbornene, or cyclopentadiene polymer.
[0033] In one embodiment, the monomer mixture comprises the hexylnorbornene, tetracyclododecene, and dicyclopentadiene; the molar ratio of the tetracyclododecene, dicyclopentadiene, and hexylnorbornene is (10-90):(5-80):(5-50).
[0034] In one embodiment, the solvent two includes at least one of cyclohexane, carbon tetrachloride, toluene, xylene, n-hexane, and benzene.
[0035] In one embodiment, the catalyst includes a main catalyst and a co-catalyst.
[0036] In one embodiment, the weight ratio of the main catalyst to the co-catalyst is (0.1-0.3):(0.3-0.7).
[0037] In one embodiment, the weight ratio of the main catalyst to the co-catalyst is 0.24:0.48.
[0038] In one embodiment, the main catalyst is a chloride of a transition metal; the main catalyst includes at least one of tungsten hexachloride, rhenium pentachloride, titanium tetrachloride, or molybdenum tetrachloride.
[0039] In one embodiment, the co-catalyst includes at least one of trimethylaluminum, triethylaluminum, diethylaluminum chloride, triisobutylaluminum, dichloroethylaluminum, sesquiethylaluminum chloride, or tri-n-butylaluminum.
[0040] In one embodiment, the reaction modifier includes, but is not limited to, at least one of ethanol, propanol, butanol, sec-butanol, diethyl ether, dibutyl ether, diphenyl ether, ethyl acetate, ethyl propionate, benzyl acetate, or ethyl benzoate.
[0041] In one embodiment, the molecular weight regulator is a monoolefin compound, including but not limited to at least one of ethylene, propylene, butene, hexene, octene, pentene, cyclohexene, cyclopentene, or methpropylene.
[0042] In one embodiment, the molecular weight regulator includes at least one of pentene, hexene, octene, cyclohexene, cyclopentene, or methpropylene.
[0043] In one embodiment, the molecular weight regulator includes at least one of pentene, hexene, or octene.
[0044] In one embodiment, the quenching is alcohol quenching, wherein the alcohol includes at least one of methanol, ethanol, propanol or isopropanol.
[0045] In one embodiment, the solvent three is a non-polar solvent or a low-polar solvent, and the solvent three includes, but is not limited to, at least one of petroleum ether, carbon tetrachloride, cyclohexane, n-hexane, octane, benzene, toluene, or xylene.
[0046] In one embodiment, the solvent three includes at least one of cyclohexane, n-hexane, octane, or toluene.
[0047] In one embodiment, the solvent three includes at least one of cyclohexane or octane.
[0048] In one embodiment, the hydrogenation catalyst includes at least one of a supported nickel catalyst, a Raney nickel catalyst, a Raney cobalt catalyst, or a Pd / C catalyst.
[0049] In one implementation, the hydrogenation rate after the high-pressure hydrogenation reaction is >99.5%.
[0050] In one embodiment, the reaction temperature of the ROMP polymerization reaction is 50-75°C, and the reaction time is 1-3 hours.
[0051] In one embodiment, the high-pressure hydrogenation reaction is carried out at a temperature of 80-180°C, a pressure of 3-6 MPa, and a time of 1-4 hours.
[0052] In one embodiment, the high-pressure hydrogenation reaction is carried out at a reaction temperature of 170°C, a reaction pressure of 3.5 MPa, and a reaction time of 4 h.
[0053] Compared with the prior art, the present invention has the following beneficial effects; (1) The method for synthesizing hexylnorbornene described in this invention controls the molar ratio of octene to dicyclopentadiene to be (0.8-2): (0.5-1), which can achieve a dicyclopentadiene conversion rate of up to 55% or more, a byproduct (cyclopentadiene polymer) content of less than 1%, and a lower reaction temperature, a shorter reaction time, and milder reaction conditions.
[0054] (2) The synthesis method of hexylnorbornene described in this invention controls the reaction temperature to 150-300℃, which can improve the conversion rate of DCPD, and with the addition of a polymerization inhibitor, the occurrence of side reactions is further reduced.
[0055] (3) The hexylnorbornene described in this invention is used to prepare polycyclic olefins. A mixture of hexylnorbornene, tetracyclododecene and dicyclopentadiene monomers is used to significantly reduce the crystallinity of polycyclic olefins, improve the toughness and impact resistance of polycyclic olefins, enhance solution stability, and reduce precipitation and gelation phenomena.
[0056] (4) The hexylnorbornene described in this invention is used to prepare polycyclic olefins. The molar ratio of hexylnorbornene, tetracyclododecene and dicyclopentadiene is (10-90): (5-80): (5-50), which can achieve a balance between tensile elongation at break and impact strength, and reduce crystallinity while achieving a balance with other properties.
[0057] (5) The hexylnorbornene described in this invention is used to prepare polycyclic olefins. The reaction conditions of high-pressure hydrogenation are controlled at a temperature of 80-180℃, a reaction pressure of 3-6MPa, and a reaction time of 1-4h. This can significantly improve the toughness and impact resistance of polycyclic olefin materials and improve the solution stability of hydrogenated liquid. Attached Figure Description
[0058] Figure 1 This is a diagram illustrating the experimental mechanism of the present invention.
[0059] Figure 2 The polycyclic olefins in the application examples and comparative examples are shown after standing for one week.
[0060] Figure 3 The images show the infrared spectra of the polycyclic olefin intermediate and the polycyclic olefin prepared in Example 1. The upper part of the image shows the polycyclic olefin intermediate, and the lower part shows the polycyclic olefin. Detailed Implementation
[0061] Example 1 A method for synthesizing hexylnorbornene specifically includes the following steps: Prepare solution A: Mix dicyclopentadiene with solvent one, heat to 120°C and keep warm for later use; Preparation of Solution B: Mix octene, solvent one, and polymerization inhibitor to obtain solution B; Solution B was heated to 170℃ and held at that temperature for 10 min. Solution A was then added dropwise to initiate the reaction. The dropwise addition time was controlled to be 5 h, and the temperature was maintained for 0.5 h. Gas chromatography was used to detect the bicyclic conversion rate and the formation of byproducts. Hexylnorbornene with a purity >99% was obtained by vacuum distillation.
[0062] The solvent is cyclohexane. The polymerization inhibitor is p-tert-butylcatechol.
[0063] The concentration of dicyclopentadiene in solution A is 90 wt%.
[0064] The molar ratio of octene to dicyclopentadiene is 2:1.
[0065] The solvent in solution B accounts for 10% of the mass of octene.
[0066] The polymerization inhibitor accounts for 0.2% of the total mass of the raw materials used in the preparation of hexylnorbornene.
[0067] The parameters and corresponding elution times of the gas chromatogram are shown in Table 1.
[0068] The mechanism diagram of Example 1 is shown below. Figure 1 .
[0069] Example 2 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 1, except that the polymerization inhibitor accounts for 0.5% of the total mass of the raw materials for preparing hexylnorbornene.
[0070] Example 3 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 1, the difference being that the temperature of solution B is raised to 180°C, held at the temperature for 10 min, solution A is added dropwise to carry out the reaction, the dropwise addition time is controlled to be 5 h, and the temperature is maintained for 0.5 h. The bicyclic conversion rate and the generation of by-products are detected by gas chromatography, and hexylnorbornene with a purity >99% is obtained by vacuum distillation.
[0071] Example 4 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 3, except that the molar ratio of octene and dicyclopentadiene is 2:0.8.
[0072] Example 5 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 4, the difference being that the temperature of solution B is raised to 190°C, held at the temperature for 10 min, solution A is added dropwise to carry out the reaction, the dropwise addition time is controlled to be 5 h, and the temperature is maintained for 0.5 h. The bicyclic conversion rate and the generation of by-products are detected by gas chromatography, and hexylnorbornene with a purity >99% is obtained by vacuum distillation.
[0073] Example 6 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 5, except that the molar ratio of octene and dicyclopentadiene is 2:0.5.
[0074] The solution B is heated to 200℃ and held at that temperature for 10 minutes. Solution A is then added dropwise to carry out the reaction. The dropwise addition time is controlled to be 5 hours, and the temperature is maintained for 0.5 hours. The bicyclic conversion rate and the formation of by-products are detected by gas chromatography. Hexylnorbornene with a purity >99% is obtained by vacuum distillation.
[0075] Example 7 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 5, except that the molar ratio of octene and dicyclopentadiene is 1.5:1.
[0076] Example 8 A method for synthesizing hexylnorbornene, the specific implementation method is the same as in Example 7, except that the polymerization inhibitor accounts for 0% of the total mass of the raw materials for preparing hexylnorbornene.
[0077] Application Example 1 A polycyclic olefin, the raw materials for preparation include, by weight, 120 parts of a monomer mixture, 500 parts of solvent, 0.6 parts of molecular weight regulator, 0.38 parts of reaction regulator, and 0.72 parts of catalyst.
[0078] The monomer mixture includes hexylnorbornene, tetracyclododecene, and dicyclopentadiene prepared in Example 6; the molar ratio of tetracyclododecene, dicyclopentadiene, and hexylnorbornene is 17:80:3.
[0079] The second solvent is dehydrated toluene. The molecular weight regulator is 1-hexene.
[0080] The reaction regulator is a combination of dipropyl ether and isopropanol in a weight ratio of 0.2:0.18.
[0081] The catalyst comprises a main catalyst and a co-catalyst in a weight ratio of 0.24:0.48.
[0082] The main catalyst is 40 parts by weight of toluene containing 0.6 wt% tungsten hexachloride.
[0083] The co-catalyst is diisobutylaluminum chloride.
[0084] A method for preparing a polycyclic olefin includes the following steps: The monomer mixture, solvent II, molecular weight regulator, reaction regulator and co-catalyst were stirred and mixed at 35°C for 10 min. The main catalyst was added dropwise over 30 min. After stirring evenly, the temperature was raised to 60°C for ROMP polymerization reaction for 2 h. The conversion rate of monomers in the polymerization reaction solution was determined by gas chromatography and was 100%. After the reaction was completed, polycyclic olefin intermediates were quenched and precipitated. 10 parts by weight of polycyclic olefin intermediate were dried at 50°C, 0.5 parts by weight of hydrogenation catalyst and 90 parts by weight of solvent were added, and a high-pressure hydrogenation reaction was carried out. After filtering the hydrogenation catalyst, a colorless clear liquid was obtained, and the polycyclic olefin was obtained.
[0085] The quenching is alcohol quenching, and the alcohol is ethanol.
[0086] The solvent three is cyclohexane.
[0087] The hydrogenation catalyst is a supported nickel catalyst, purchased from Shanghai Xunkai Catalysis Technology Co., Ltd., with the grade 8800.
[0088] The high-pressure hydrogenation reaction is carried out at a temperature of 170°C, a pressure of 3.5 MPa, and a time of 4 hours.
[0089] The hydrogenation rate was measured to be >99.5% by an infrared spectrometer after the high-pressure hydrogenation reaction.
[0090] The infrared spectra of the prepared polycyclic olefin intermediates and polycyclic olefins are shown in the figure. Figure 3 .
[0091] Application Example 2 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 1, except that the molar ratio of tetracyclododecene, dicyclopentadiene and hexylnorbornene is 49:50:1.
[0092] Application Example 3 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 1, except that the molar ratio of tetracyclododecene, dicyclopentadiene and hexylnorbornene is 45:50:5.
[0093] Application Example 4 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 1, except that the reaction temperature of the high-pressure hydrogenation reaction is 150°C, the reaction pressure is 3.5 MPa, and the reaction time is 4 h.
[0094] Application Example 5 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 3, except that the reaction temperature of the high-pressure hydrogenation reaction is 150°C, the reaction pressure is 3.5 MPa, and the reaction time is 4 h.
[0095] Application Example 6 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 1, except that the reaction temperature of the high-pressure hydrogenation reaction is 130°C, the reaction pressure is 5 MPa, and the reaction time is 4 h.
[0096] Application Example 7 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 3, except that the reaction temperature of the high-pressure hydrogenation reaction is 130°C, the reaction pressure is 5 MPa, and the reaction time is 4 h.
[0097] Application Comparative Example 1 A polycyclic olefin and its preparation method are disclosed. The specific implementation method is the same as that in Application Example 1, except that the monomer mixture includes tetracyclododecene and dicyclopentadiene; the molar ratio of tetracyclododecene to dicyclopentadiene is 50:50.
[0098] Application Comparative Example 2 A polycyclic olefin and its preparation method are disclosed. The specific implementation method is the same as that in Application Example 1, except that the monomer mixture includes norbornene, tetracyclododecene and dicyclopentadiene; the molar ratio of tetracyclododecene, dicyclopentadiene and norbornene is 17:80:3.
[0099] Application Comparative Example 3 A polycyclic olefin and its preparation method are described. The specific implementation method is the same as that in Application Example 3, except that the monomer mixture includes norbornene, tetracyclododecene and dicyclopentadiene; the molar ratio of tetracyclododecene, dicyclopentadiene and norbornene is 17:80:3.
[0100] Performance testing 1. Dicyclopentadiene conversion rate: The dicyclopentadiene conversion rates of Examples 1-8 were tested using gas chromatography, and the test results are shown in Table 2.
[0101] 2. Byproduct rate: The byproduct rates of Examples 1-8 were tested using gas chromatography, and the test results are shown in Table 2.
[0102] 3. Stability: The colorless, clear polycyclic olefin solutions obtained in the application examples and comparative examples were stored at 40°C for 1, 3, 5, 7, 9, and 11 days to observe the solution stability. The test results are shown in Table 3. Images after 7 days of storage are shown below. Figure 2 From left to right, these are application examples 1-7 and application comparative examples 1-3.
[0103] 4. Mechanical property test: The test results are shown in Table 4.
[0104] Table 1
[0105] Table 2
[0106] The test results in Table 2 show that as the reaction temperature increases, the conversion rate of dicyclopentadiene increases, but at the same time, the amount of by-products (cyclopentadiene polymers) also increases. Increasing the amount of octene added is beneficial to increasing the conversion rate of dicyclopentadiene while reducing the formation of by-products. The introduction of polymerization inhibitors is beneficial to reducing side reactions in the reaction, but the effect no longer increases after the amount added reaches a certain level.
[0107] Table 3
[0108] The test results in Table 3 show that: comparing the results of Application Example 2, Application Example 3, and Application Comparative Example 1, it can be found that adding hexylnorbornene during polymerization helps reduce the crystallinity of the hydrogenated liquid and improves the solution stability; the higher the amount added, the better the stability. Comparing the solution stability of the hydrogenated liquids of Application Example 1, Application Comparative Example 2, Application Example 3, and Application Comparative Example 3 when stored at a constant temperature of 40°C, it can be found that, at the same molar addition amount, hexylnorbornene has higher solution stability than norbornene. Comparing the results of Application Example 1, Application Example 4, Application Example 6, Application Example 3, Application Example 5, and Application Example 7, it can be found that the hydrogenated liquid with high-temperature hydrogenation has better stability.
[0109] Table 4
[0110] The test results in Table 4 show that the addition of hexylnorbornene is beneficial to improving the tensile elongation at break and impact strength of polycyclic olefin materials, and both tensile elongation at break and impact strength increase with increasing addition amount. Comparing Application Example 1 with Comparative Example 2, and Application Example 3 with Comparative Example 3, it can be found that hexylnorbornene has a better modification effect on the toughness and impact resistance of polycyclic olefin materials than norbornene. Comparing the results of Application Example 1, Application Example 4, and Application Example 6 with Application Example 5, Application Example 7, it can be found that the higher the hydrogenation temperature (130℃-170℃), the better the toughness and impact resistance of the polycyclic olefin materials, possibly due to ring-opening hydrogenation during high-temperature hydrogenation.
Claims
1. A method for synthesizing hexylnorbornene, characterized in that, Includes the following steps: Octene and dicyclopentadiene were used as substrates, and a polymerization inhibitor and solvent were added to carry out a Diels-Alder reaction to generate hexylnorbornene. The molar ratio of octene to dicyclopentadiene was (0.8-2):(0.5-1).
2. The method for synthesizing hexylnorbornene according to claim 1, characterized in that, The polymerization inhibitor accounts for 0.01%-0.5% of the total mass of the raw materials used to prepare hexylnorbornene.
3. The method for synthesizing hexylnorbornene according to claim 1, characterized in that, The reaction temperature is 150-300℃, and the reaction time is 1-5h.
4. A hexylnorbornene, characterized in that, The hexylnorbornene was synthesized using the method described in any one of claims 1-3, wherein the purity of the hexylnorbornene is >99% and the byproduct rate is ≤0.3%.
5. A method for preparing polycyclic olefins, characterized in that, It is prepared using hexylnorbornene as described in claim 4 as a raw material.
6. The method for preparing polycyclic olefins according to claim 5, characterized in that, Includes the following steps: The monomer mixture containing the hexylnorbornene, solvent II, molecular weight regulator, reaction regulator, and catalyst are stirred and mixed, and the temperature is raised to carry out ROMP polymerization. After the reaction is completed, the polycyclic olefin intermediate is quenched and precipitated. The polycyclic olefin intermediate was dried at low temperature, and then hydrogenation catalyst and solvent III were added to carry out a high-pressure hydrogenation reaction. After filtering the hydrogenation catalyst, the polycyclic olefin was obtained.
7. The method for preparing polycyclic olefins according to claim 6, characterized in that, The monomer mixture further includes at least one of norbornene, dicyclopentadiene, tetracyclododecene, methyl norbornene, vinyl norbornene, or cyclopentadiene.
8. The method for preparing polycyclic olefins according to claim 7, characterized in that, The monomer mixture comprises hexylnorbornene, tetracyclododecene, and dicyclopentadiene; the molar ratio of tetracyclododecene, dicyclopentadiene, and hexylnorbornene is (10-90):(5-80):(5-50).
9. The method for preparing polycyclic olefins according to claim 6, characterized in that, The reaction temperature for the ROMP polymerization reaction is 50-75℃, and the reaction time is 1-3h.
10. The method for preparing polycyclic olefins according to claim 6, characterized in that, The high-pressure hydrogenation reaction has a reaction temperature of 80-180℃, a reaction pressure of 3-6MPa, and a reaction time of 1-4h.