Cycloolefin block copolymer and preparation method thereof
By using catalysts with specific structures to prepare cyclic olefin block copolymers with hard and soft segments, the thermal stability and brittleness problems of cyclic olefin polymers are solved, and copolymers with high thermal stability and good toughness are achieved. The high thermal stability and good toughness transparency are also achieved, solving the problems of poor thermal stability and brittleness in the prior art. Cyclic olefin block copolymers with high glass transition temperature and high elongation at break are prepared.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- PETROCHINA SHANGHAI ADVANCED MATERIALS RESEARCH INSTITUTE CO LTD
- Filing Date
- 2024-11-05
- Publication Date
- 2026-05-08
AI Technical Summary
Existing cyclic olefin polymers have problems with thermal stability and brittleness. Too low an insertion rate leads to a decrease in glass transition temperature, while too high an insertion rate leads to a decrease in toughness. In addition, existing catalysts are expensive, which limits their industrial applications.
Using catalysts I and II with specific structures, cyclic olefin block copolymers with hard and soft segments are prepared through ring-opening polymerization and hydrogenation. The insertion rate of rigid cyclic olefins is controlled, and the segment connection is adjusted using a co-catalyst, combined with suitable reaction conditions and hydrogenation treatment.
A cyclic olefin block copolymer with good thermal stability, high elongation at break, and high glass transition temperature was prepared, which also has excellent transparency and processing performance, and reduced costs.
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Figure CN121991322A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of block copolymer technology, and in particular to a cyclic olefin block copolymer and its preparation method. Background Technology
[0002] Cyclic olefin polymers, or COPs for short, are a class of non-crystalline polyolefin materials with good transparency and water vapor barrier properties, and have broad application prospects in fields such as optics and medical packaging.
[0003] In the process of preparing cyclic olefin copolymers, the insertion rate of cyclic olefins with rigid structures directly affects the thermal stability and mechanical strength of the cyclic olefin copolymers. Too low an insertion rate will lead to a decrease in glass transition temperature and a decrease in thermal stability; too high an insertion rate will result in poor toughness of the finished product and make it easy to break.
[0004] Non-patent literature 1 discloses a method for alternating copolymerization of norbornene with cyclopentene or cyclooctene. This method can improve the flexibility of the polymer and reduce the processing difficulty. However, this method uses expensive ruthenium-based catalysts, which limits its industrial application.
[0005] In summary, those skilled in the art urgently need to find catalysts with specific structures to solve the problems of poor thermal stability and brittleness of COP materials.
[0006] [Non-Patent Literature 1] Kong Yong, Yang Xiaohua, Wang Lin, et al. Research progress on ring-opening translocation polymerization [J]. Science Technology and Engineering, 2015, 15(30): 71-78 Summary of the Invention
[0007] The purpose of this invention is to provide a cyclic olefin block copolymer and its preparation method, which obtains a cyclic olefin block copolymer with higher elongation at break, higher glass transition temperature, and good thermal stability and toughness by selecting a catalyst with a specific structure.
[0008] The object of this invention is to provide a cyclic olefin block copolymer that simultaneously has hard segments and soft segments.
[0009] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:
[0010] This invention provides a method for preparing cyclic olefin block copolymers, comprising the following steps:
[0011] S1, a monocyclic olefin, a cyclic olefin with a rigid structure, an inert solvent, a molecular weight regulator and a co-catalyst are added to a reaction vessel in sequence and mixed to obtain a mixture. Then, solutions of catalyst I and catalyst II in an inert solvent are added at the same time to carry out a ring-opening polymerization reaction.
[0012] S2. After the reaction is complete, catalyst I and catalyst II are removed, the supernatant is filtered and a hydrogen source is introduced into it and a hydrogenation catalyst is added to carry out the hydrogenation reaction. After the reaction is complete, the mixture is filtered and separated to obtain the cyclic olefin block copolymer.
[0013] The structural formulas of catalyst I and catalyst II are shown below:
[0014]
[0015] In the formula, M is tungsten, molybdenum, nickel, or palladium; X is independently selected from halogens, C 1～30 Aliphatic alkanes, substituted or unsubstituted C 1～20 The aryl group; wherein the substituent is a group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom;
[0016] Ra1 to Ra2 are independently selected from hydrogen atoms and C atoms. 1～30 Aliphatic alkanes, substituted or unsubstituted C 1～20 The aryl group; Ra3 to Ra8 are independently selected from hydrogen atoms, C 1～30 Aliphatic alkanes, substituted or unsubstituted C 1～20 The aryl group; wherein the substituent is a group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom;
[0017] M' is tungsten, molybdenum, nickel, or palladium;
[0018] L is independently selected from halogens, C 1～30 Aliphatic alkyl groups, C 1～30 Alicyclic alkyl, substituted or unsubstituted C 1～20 The aryl group; wherein the substituents are isopropoxy, ethoxy, bromomethoxy, or formamido;
[0019] Rb1 to Rb2 are independently selected from hydrogen atoms, C atoms 1～30 Aliphatic alkanes, substituted C 1～20 The aryl group; Rb3 to Rb4 are neutral dielectron donors;
[0020] n is an integer from 0 to 6.
[0021] The method for preparing the cyclic olefin block copolymer as described above, wherein the cyclic olefin containing the rigid structure has the structural formula shown in Formula III below:
[0022]
[0023] Formula III
[0024] In the formula, R1 to R10 each independently represent a hydrogen atom, a C1 to 30 alkyl group, or a substituted or unsubstituted C6 to 20 aryl group, wherein the substituent is a group containing a silicon atom, a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom; R1 and R4 are combined with each other to form a ring;
[0025] m takes the integer between 0 and 3.
[0026] In the preparation method of the cyclic olefin block copolymer as described above, the molar ratio of catalyst I, catalyst II, monocyclic olefin, and cyclic olefin containing a rigid structure is 1:2-5:(100-4000):(100-4000).
[0027] The method for preparing the cyclic olefin block copolymer as described above, wherein the total mass fraction of the monocyclic olefin and the cyclic olefin containing the rigid structure in the inert solvent is 1 wt% to 50 wt%, and the mass ratio of the monocyclic olefin to the cyclic olefin containing the rigid structure is 1:(0.1-10).
[0028] In the method for preparing the cyclic olefin block copolymer as described above, the reaction temperature of the ring-opening polymerization is 20–300°C, and the reaction temperature of the hydrogenation reaction is -10–200°C.
[0029] In the preparation method of the cyclic olefin block copolymer as described above, the molecular weight regulator is selected as one or more compounds containing carbon-carbon double bonds of C3 to 30, and the molar ratio of the total amount of the monocyclic olefin and the cyclic olefin containing the rigid structure to the molecular weight regulator is (10 to 1000): 1.
[0030] In the preparation method of the cyclic olefin block copolymer as described above, the co-catalyst is one or more of alkyllithium, alkylzinc, alkylaluminum, and alkylmagnesium.
[0031] In the preparation method of the cyclic olefin block copolymer as described above, the hydrogen source is hydrogen or a hydrazine compound.
[0032] The method for preparing the cyclic olefin block copolymer as described above, wherein the cyclic olefin containing a rigid structure includes one or more of norbornene, 2-phenyl-5-norbornene, tetracyclododecene, 2-benzoyl-5-norbornene, 5-norbornene-2,3-dicarboximide, 5-norbornene-2,3-dicarboxylic anhydride, and methyl-5-norbornene-2,3-dicarboxylic anhydride.
[0033] The present invention also provides a cyclic olefin block copolymer, wherein it is prepared by any of the preparation methods described above.
[0034] Compared with the prior art, the advantages of the present invention are as follows:
[0035] This invention provides a cyclic olefin block copolymer and its preparation method. By selecting a catalyst with a specific structure, a cyclic olefin block copolymer with hard and soft segments is prepared, which solves the problems of poor thermal stability and brittleness of COP materials. The obtained cyclic olefin block copolymer has better thermal stability, higher elongation at break, higher glass transition temperature, good transparency and excellent processing performance. Attached Figure Description
[0036] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.
[0037] Figure 1 The image shows the DSC spectrum of the cyclic olefin block copolymer prepared in Example 1 of this invention. Detailed Implementation
[0038] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0039] On one hand, the present invention provides a method for preparing a cyclic olefin block copolymer, comprising the following steps:
[0040] S1, a monocyclic olefin, a cyclic olefin with a rigid structure, an inert solvent, a molecular weight regulator and a co-catalyst are added to a reaction vessel in sequence and mixed to obtain a mixture. Then, solutions of catalyst I and catalyst II in an inert solvent are added at the same time to carry out a ring-opening polymerization reaction.
[0041] The structural formulas of catalyst I and catalyst II are shown below:
[0042]
[0043] This invention prepares cyclic olefin block copolymers with hard and soft segments by selecting catalysts with specific structures. The resulting cyclic olefin block copolymers have better thermal stability and excellent processing performance, higher elongation at break, higher glass transition temperature, good transparency, and high light transmittance.
[0044] Catalyst I has a low insertion rate into rigid cyclic olefins, thus generating soft segments with poor rigidity. Catalyst II has a high insertion rate into rigid cyclic olefins, thus generating hard segments with strong rigidity. The two segments are linked together through chain transfer via a co-catalyst, thereby forming a block copolymer with both hard and soft segments.
[0045] In the formula, M is tungsten, molybdenum, nickel or palladium; X is independently selected from halogens, C1-30 aliphatic alkanes, substituted or unsubstituted C1-20 aryl groups; wherein the substituents are groups containing oxygen atoms, nitrogen atoms, sulfur atoms or silicon atoms;
[0046] Ra1 to Ra2 are independently selected from hydrogen atoms, C1 to 30 aliphatic alkanes, and substituted or unsubstituted C1 to 20 aryl groups; Ra3 to Ra8 are independently selected from hydrogen atoms, C1 to 30 aliphatic alkanes, and substituted or unsubstituted C1 to 20 aryl groups; wherein the substituents are groups containing oxygen atoms, nitrogen atoms, sulfur atoms, or silicon atoms.
[0047] M' is tungsten, molybdenum, nickel, or palladium;
[0048] L is independently selected from halogens, C1-30 aliphatic alkyl groups, C1-30 alicyclic alkyl groups, substituted or unsubstituted C1-20 aryl groups; wherein the substituents are isopropoxy, ethoxy, bromomethoxy, or formamido.
[0049] Rb1 to Rb2 are independently selected from hydrogen atoms, C1 to 30 aliphatic alkanes, and substituted C1 to 20 aryl groups; Rb3 to Rb4 are neutral two-electron donors;
[0050] n is an integer from 0 to 6.
[0051] S2. After the reaction is complete, catalyst I and catalyst II are removed, the supernatant is filtered and a hydrogen source is introduced into it and a hydrogenation catalyst is added to carry out the hydrogenation reaction. After the reaction is complete, the mixture is filtered and separated to obtain the cyclic olefin block copolymer.
[0052] In one specific embodiment, catalyst I, M is tungsten.
[0053] In one specific embodiment, catalyst I has n = 2.
[0054] Specifically, the structures of the compounds shown in Catalyst I are as follows: compounds I-1 to I-6:
[0055]
[0056] In one specific embodiment, M' in catalyst II is molybdenum.
[0057] In one specific embodiment, in the catalyst II formula, L is an oxygen-containing substituent such as methoxy or ethoxyisopropoxy.
[0058] In one specific embodiment, the L molecules in catalyst II can be linked together to form a ring.
[0059] Specifically, the structures of the compounds shown in Catalyst II are as follows: compounds II-1 to II-6:
[0060]
[0061] In one specific embodiment, catalyst I and catalyst II can be supported on a support to form a supported catalyst.
[0062] In one specific embodiment, the support for the supported catalyst includes, but is not limited to, activated carbon, silica gel, diatomaceous earth, and alumina.
[0063] In one specific embodiment, the molar ratio of catalyst I, catalyst II, monocyclic olefin, and cyclic olefin containing a rigid structure is 1:2-5:(100-4000):(100-4000).
[0064] In one specific embodiment, the molar ratio of catalyst I, catalyst II, monocyclic olefin, and cyclic olefin containing a rigid structure is 1:3-4.5:(500-2000):(500-2000).
[0065] The prepared cyclic olefin block copolymer maintained good optical properties and thermal stability, and was also easy to process. A higher proportion of catalyst I resulted in a greater proportion of soft segments in the copolymer, and vice versa.
[0066] In one specific embodiment, the structural formula of the cycloolefin containing the rigid structure is shown in Formula III below:
[0067]
[0068] Formula III
[0069] In the formula, R1 to R10 each independently represent a hydrogen atom, a C1 to 30 alkyl group, or a substituted or unsubstituted C6 to 20 aryl group, wherein the substituent is a group containing a silicon atom, a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom; R1 and R4 are combined with each other to form a ring;
[0070] m takes the integer between 0 and 3.
[0071] In one specific embodiment, the cyclic olefin containing a rigid structure includes one or more of norbornene, 2-phenyl-5-norbornene, tetracyclododecene, 2-benzoyl-5-norbornene, 5-norbornene-2,3-dicarboximide, 5-norbornene-2,3-dicarboxylic anhydride, and methyl-5-norbornene-2,3-dicarboxylic anhydride.
[0072] In one specific embodiment, the monocyclic olefin is selected as a substituted or unsubstituted C1-30 monocyclic olefin containing only one carbon-carbon double bond.
[0073] Specifically, monocyclic alkenes include, but are not limited to: cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methylcyclopentene, 1-ethylcyclooctene, 3-methyl-1-cyclohexene, 3-bromocyclohexene, 1,2-dichlorocyclopentene, cyclohexenol, cyclohexenic acid, 2-cyclohexen-1-one, 3-cyclohexen-1-one, 3-methyl-2-cyclohexen-1-one, cyclohexeneethylamine, and shikimic acid.
[0074] In one specific embodiment, the total mass fraction of monocyclic olefins and cyclic olefins containing rigid structures in the inert solvent is 1 wt% to 50 wt%, and the monocyclic olefins and cyclic olefins containing rigid structures are 1 wt% to 20 wt% and 1 wt% to 45 wt%, respectively.
[0075] In one specific embodiment, the total mass fraction of monocyclic olefins and cyclic olefins containing rigid structures in the inert solvent is 10% wt% to 30 wt%, and the monocyclic olefins and cyclic olefins containing rigid structures are 5 wt% to 15 wt% and 10 to 40 wt%, respectively.
[0076] In one specific embodiment, the reaction temperature for ring-opening polymerization is 20–300°C, and the reaction temperature for hydrogenation is -10–200°C.
[0077] In one specific embodiment, the reaction temperature for ring-opening polymerization is 40–100°C; further, the reaction temperature is 45–85°C.
[0078] In one specific embodiment, the reaction pressure for ring-opening polymerization is 0.1–5 MPa; further, the reaction pressure is 0.1–2 MPa.
[0079] In one specific embodiment, the reaction temperature of the hydrogenation reaction is -10 to 200°C; further, the reaction temperature is -5 to 190°C.
[0080] In one specific embodiment, the reaction temperature of the hydrogenation reaction is 25–180°C.
[0081] In one specific embodiment, the reaction pressure of the hydrogenation reaction is 0.06–14 MPa; further, the reaction pressure is 0.2–10 MPa.
[0082] In one specific embodiment, the reaction pressure of the hydrogenation reaction is 0.5–7 MPa.
[0083] In one specific embodiment, the molecular weight regulator is selected as one or more compounds containing carbon-carbon double bonds of C3 to 30, and the molar ratio of the total amount of monocyclic olefins and cyclic olefins containing rigid structures to the molecular weight regulator is (10 to 1000): 1.
[0084] In one specific embodiment, the molar ratio of the total amount of monocyclic olefins and cyclic olefins containing rigid structures to the amount of the molecular weight regulator is (100-1000):1.
[0085] By controlling the amount of molecular weight regulator, the molecular weight and distribution of the polymer can be adjusted, thereby obtaining a polymer with an appropriate molecular weight and a narrow molecular weight distribution.
[0086] In one specific embodiment, the molecular weight regulator is selected as at least one of aliphatic olefins and aromatic olefins.
[0087] Specifically, the molecular weight regulator may be selected from at least one of the following: 1-pentene, 2-pentene, 1-hexene, 2-hexene, 4-octene, 1-octene, 1-heptene; styrene, tristyrene, tetrastyrene, 4-phenyl-1-butene, 2-phenyl-2-butene, 6-phenyl-1-hexene; 4-bromo-1-butene, 2-bromo-2-butene, 6-bromo-1-hexene, 5,6-dibromo-1-hexene, 6-chloro-1-hexene, 6-chloro-2-hexene, 8-chloro-1-octene; allyl acetate, cinnamon acetate, ethyl oleate, allyl hexanoate, vinyl octanoate, and 1,4-diacetoxy-2-butene.
[0088] In one specific embodiment, the co-catalyst is at least one selected from alkyllithium, alkylzinc, alkylaluminum, and alkylmagnesium.
[0089] In one specific embodiment, the co-catalyst is at least one selected from lithium methyl, lithium ethyl, lithium propyl, lithium isopropyl, lithium n-butyl, lithium sec-butyl, lithium tert-butyl, lithium pentyl, lithium hexyl, lithium cyclohexyl, lithium tert-octyl, lithium n-eicosyl, lithium phenyl, lithium methylphenyl, lithium butylphenyl, lithium naphthyl, and lithium butylcyclohexyl.
[0090] In one specific embodiment, the co-catalyst is at least one selected from dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, dipentyl zinc, dihexyl zinc, dicyclohexyl zinc, di-tert-octyl zinc, diphenyl zinc, and dimethylphenyl zinc.
[0091] In one specific embodiment, the co-catalyst is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, trihexylaluminum, tricyclohexylaluminum, tritert-octylaluminum, triphenylaluminum, and trimethylphenylaluminum.
[0092] In one specific embodiment, the co-catalyst is at least one selected from dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, di-n-butyl magnesium, dipentyl magnesium, dihexyl magnesium, dicyclohexyl magnesium, ditert-octyl magnesium, diphenyl magnesium, dimethylphenyl magnesium, dibutylphenyl magnesium, dinaphthyl magnesium, and dibutylcyclohexyl magnesium.
[0093] In one specific embodiment, the hydrogen source is hydrogen gas or a hydrazine compound.
[0094] In one specific embodiment, the hydrazine compounds include, but are not limited to: hydrazine, phenylhydrazine, formylhydrazine, butyrylhydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, diphenylhydrazine, phenylmethanesulfonylhydrazine, and 4-methoxybenzenesulfonylhydrazine.
[0095] In one specific embodiment, the hydrogenation catalyst is a homogeneous catalyst or a heterogeneous catalyst.
[0096] In one specific embodiment, the hydrogenation catalyst is selected from catalysts consisting of a combination of transition metal compounds and organoaluminum compounds, catalysts consisting of metallocene compounds and organoalkali metal compounds, catalysts consisting of a combination of transition metal compounds and organomagnesium compounds, and noble metal carbene catalysts.
[0097] In one specific embodiment, the hydrogenation catalyst is a heterogeneous catalyst made by supporting metals such as nickel, palladium, platinum, rhodium, and ruthenium on a support.
[0098] In one specific embodiment, catalyst I and catalyst II are removed by adding an adsorbent and stirring.
[0099] In one specific embodiment, the adsorbent is an alkaline compound, including but not limited to: calcium hydroxide, calcium oxide, calcium chloride, barium chloride, and aluminum oxide.
[0100] In one specific embodiment, after the hydrogenation reaction is completed, the reaction solution is poured into a poor solvent for filtration and separation.
[0101] In one specific embodiment, the poor solvent is compatible with the ring-opening polymerization solvent and is immiscible with the cyclic olefin copolymer.
[0102] In one specific embodiment, the undesirable solvent is an alcohol solvent, an aldehyde or ketone solvent, or an ether solvent.
[0103] In one specific embodiment, the undesirable solvent is selected as methanol, ethanol, or isopropanol.
[0104] In one specific implementation, the pH value of a poor solvent can be adjusted by adding acidic or alkaline substances, thereby controlling the solubility of impurities in the solvent.
[0105] The present invention also provides a cyclic olefin block copolymer prepared by the above-described preparation method.
[0106] Specifically, the number average molecular weight of the cyclic olefin block copolymer is 2,000 to 30,000, and the weight average molecular weight is 10,000 to 500,000.
[0107] Specifically, the cyclic olefin block copolymer includes hard segments and soft segments, wherein the soft segments are composed of non-rigid cyclic olefin structures, and the weight ratio of hard segments is 20%-80%, preferably 40%-60%.
[0108] In one specific embodiment, the glass transition temperature of the cyclic olefin copolymer is 100–300°C.
[0109] In one specific embodiment, the glass transition temperature of the cyclic olefin copolymer is 100–200°C.
[0110] In one specific embodiment, the glass transition temperature of the cyclic olefin copolymer is 160–180°C.
[0111] Specifically, the hydrogenation rate of unsaturated bonds on the chain of the cyclic olefin copolymer is ≥95%.
[0112] Specifically, the hydrogenation rate of unsaturated bonds on the chain of the cyclic olefin copolymer is ≥97%.
[0113] By selecting the type of hydrogenation catalyst and adjusting the hydrogenation temperature and pressure, the hydrogenation rate can be increased, resulting in a more stable polymer structure.
[0114] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0115] The present invention will be further described below through specific embodiments and comparative examples. Unless otherwise specified, the reagents, materials and instruments used below are all conventional reagents, materials and instruments, all of which are commercially available, and the reagents and materials involved can also be synthesized by conventional synthetic methods.
[0116] In the following examples, catalyst a1, catalyst a2 and catalyst a3 refer to catalysts having the structures of formulas I-1, I-2 and I-6, respectively; catalyst b1, catalyst b2 and catalyst b3 refer to catalysts having the structures of formulas II-1, II-2 and II-5, respectively.
[0117] 1. The catalyst a1 of the present invention is prepared by the following method:
[0118] 4.7 g of tungsten hexachloride was dissolved in 80 mL of toluene to prepare a solution, which was then cooled to -78 °C. Separately, 9.72 g of 2,4,2',4'-tetratert-butyl-6,6'-biphenoxylithium was dissolved in 50 mL of toluene to prepare a solution, which was also cooled to -78 °C. The two solutions were mixed, and the temperature was slowly raised to room temperature. The reaction was allowed to proceed for 18 h. An equal volume of n-hexane was then added, and the mixture was cooled to -30 °C. After standing overnight, the solid product was collected by filtration.
[0119] The obtained solid product was dissolved in 85 mL of toluene, and 5 mL of a 10 wt% propyllithium toluene solution was added. The mixture was reacted at room temperature for 1 h, and the solution was cooled at -30 °C overnight. The precipitated solid was collected by filtration. The collected solid was dissolved in 70 mL of toluene to prepare a solution. Separately, 4.6 g of 5,6'-di-tert-butyl-3-phenoxylithium was dissolved in 60 mL of toluene to prepare a solution. The two solutions were mixed at -78 °C, and the mixture was gradually raised to room temperature and reacted for 6 h. An equal volume of n-hexane solution was added to the above mixed solution, and the mixture was recrystallized at -30 °C overnight. The solid obtained by filtration was catalyst a1.
[0120] 2. The catalyst a2 of the present invention is prepared by the following method:
[0121] 4.7 g of tungsten hexachloride was dissolved in 80 mL of toluene to prepare a solution, which was then cooled to -78 °C. Separately, 8.69 g of 2,4,2',4'-tetraisopropyl-6,6'-biphenoxylithium was dissolved in 60 mL of toluene to prepare a solution, which was also cooled to -78 °C. The two solutions were mixed, and the temperature was slowly raised to room temperature. The reaction was allowed to proceed for 15 h. An equal volume of n-hexane was then added, and the mixture was cooled to -30 °C. After standing overnight, the solid product was collected by filtration.
[0122] The obtained solid product was dissolved in 70 mL of toluene, and 7 mL of a 10 wt% tert-butyllithium toluene solution was added. The mixture was reacted at room temperature for 1 h, and the solution was cooled at -30 °C overnight. The precipitated solid was collected by filtration. The collected solid was dissolved in 70 mL of toluene to prepare a solution. Separately, 2.7 g of 3,5-di-tert-butyl-phenoxylithium was dissolved in 65 mL of toluene to prepare a solution. The two solutions were mixed at -78 °C, and the mixture was gradually raised to room temperature and reacted for 8 h. An equal volume of n-hexane solution was added to the above mixed solution, and the mixture was recrystallized at -30 °C overnight. The solid obtained by filtration was catalyst a2.
[0123] 3. The catalyst a3 of the present invention is prepared by the following method:
[0124] 4.7 g of tungsten hexachloride was dissolved in 80 mL of toluene to prepare a solution, which was then cooled to -78 °C. Separately, 9.72 g of 2,4,2',4'-tetraisopropyl-6,6'-biphenoxylithium was dissolved in 50 mL of toluene to prepare a solution, which was also cooled to -78 °C. The two solutions were mixed, and the temperature was slowly raised to room temperature. The reaction was allowed to proceed for 18 h. An equal volume of n-hexane was added, and the mixture was cooled to -30 °C. After standing overnight, the solid product was collected by filtration.
[0125] The obtained solid product was dissolved in 85 mL of toluene, and 3 mL of a 20 wt% benzyl magnesium chloride toluene solution was added. The mixture was reacted at room temperature for 1 h, and the solution was cooled at -30 °C overnight. The precipitated solid was collected by filtration. The collected solid was dissolved in 70 mL of toluene to prepare a solution. Separately, 5.4 g of 3,5-dimaleimide-phenoxylithium was dissolved in 60 mL of toluene to prepare a solution. The two solutions were mixed at -78 °C, and the mixture was gradually raised to room temperature and reacted for 10 h. An equal volume of n-hexane solution was added to the above mixed solution, and the mixture was recrystallized at -30 °C overnight. The solid obtained by filtration was catalyst a3.
[0126] 4. The catalyst b1 of the present invention is prepared by the following method:
[0127] Dissolve 7.4 g of (1,3-dimethylimidazole)molybdenum pentachloride in 80 mL of toluene, cool to -78 °C, add 4.5 mL of 20 wt% benzyl magnesium chloride toluene solution, react overnight at room temperature, add an equal volume of hexane to the above mixed solution, let stand overnight at -30 °C, filter, dissolve the obtained solid in 60 mL of toluene to prepare a solution, and dissolve 10.3 g of 3-bromopyridine in 45 mL of toluene to prepare a solution. Mix the two solutions at -78 °C and react at room temperature for 6 h, add an equal volume of cyclohexane to the solution, let stand overnight at -30 °C, filter, and the obtained solid is catalyst b1.
[0128] 5. The catalyst b2 of the present invention is prepared by the following method:
[0129] Dissolve 8.1 g of (1,3-diisopropylimidazolium)molybdenum pentachloride in 70 mL of toluene, cool to -78 °C, add 4.7 mL of 10 wt% propyllithium toluene solution, react overnight at room temperature, add an equal volume of hexane to the above mixed solution, let stand overnight at -30 °C, filter, dissolve the obtained solid in 75 mL of toluene to prepare a solution, separately dissolve 12.5 g of 3-bromopyridine in 50 mL of toluene to prepare a solution, mix the two solutions at -78 °C, and react at room temperature for 10 h, add an equal volume of cyclohexane to the solution, let stand overnight at -30 °C, filter, and the obtained solid is catalyst b2.
[0130] 6. The catalyst b3 of the present invention is prepared by the following method:
[0131] Dissolve 8.4 g of (1,3-di-tert-butylimidazolium) pentachloride in 75 mL of toluene, cool to -78 °C, add 5 mL of 20 wt% ethyl magnesium chloride toluene solution, react overnight at room temperature, add an equal volume of hexane to the above mixture, let stand overnight at -30 °C, filter, dissolve the obtained solid in 60 mL of toluene to prepare a solution, and dissolve 11 g of 3-bromopyridine in 45 mL of toluene to prepare a solution. Mix the two solutions at -78 °C, raise to room temperature and react overnight, add an equal volume of cyclohexane to the solution, let stand overnight at -30 °C, filter, and the obtained solid is catalyst b3.
[0132] Example 1
[0133] In a glove box, 100 mL each of a 0.1 mol / L toluene solution for catalyst a1 and a 0.1 mol / L toluene solution for catalyst b1 were prepared. 0.88 g of cyclopentene, 1.27 g of tetracyclododecene, 300 mL of toluene, 0.14 g of 1-octene, and 1.8 mL of a 0.2 M triisobutylaluminum hexane solution were added sequentially to a reactor purged with nitrogen three times. Then, 5 mL of toluene solution for catalyst a1 and 4.5 mL of toluene solution for catalyst b1 were added simultaneously. The mixture was stirred at 60 °C for 2 h under normal pressure. 10 g of calcium hydroxide was added, and the mixture was stirred for 0.5 h. After filtration, 0.2 g of 15% palladium-on-carbon catalyst was added to the supernatant, and hydrogen gas was introduced. The reaction was carried out at 160 °C and 0.9 MPa for 12 h. The palladium-on-carbon catalyst was separated by filtration, and the resulting reaction solution was poured into 3.5 L of ethanol. After filtration, the cyclic olefin block copolymer was obtained. The DSC spectrum of the cyclic olefin block copolymer is shown below. Figure 1 As shown.
[0134] Example 2
[0135] In a glove box, 100 mL each of 0.1 mol / L catalyst a2 toluene solution and 0.1 mol / L catalyst b1 toluene solution were prepared. 0.92 g cyclooctene, 1.55 g tetracyclododecene, 300 mL toluene, 0.2 g 1-hexene, and 2.2 mL triethylaluminum hexane solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 4.6 mL of catalyst a2 toluene solution and 5.1 mL of catalyst b1 toluene solution were added simultaneously. The mixture was stirred at atmospheric pressure and 50 °C for 1 h. 10 g calcium chloride was added, and the mixture was stirred for 0.5 h. The supernatant was filtered, and 0.2 g of 15% palladium on carbon catalyst was added, followed by hydrogen gas. The reaction was carried out at 180 °C and 1 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the resulting reaction solution was poured into 3.5 L of ethanol. After filtration, the cyclic olefin block copolymer was obtained.
[0136] Example 3
[0137] In a glove box, 100 mL each of 0.1 mol / L catalyst a3 toluene solution and 0.1 mol / L catalyst b2 toluene solution were prepared. 0.46 g cycloheptene, 1.65 g tetracyclododecene, 500 mL toluene, 0.15 g 1-octene, and 1.9 mL trimethylaluminum hexane solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 2.1 mL of catalyst a3 toluene solution and 3.3 mL of catalyst b2 toluene solution were added simultaneously. The mixture was stirred at atmospheric pressure and 70 °C for 2 h. 10 g calcium hydroxide was added to the reaction solution, and the mixture was stirred for 0.5 h. The supernatant was filtered, and 0.2 g of 15% palladium on carbon catalyst was added to it, followed by hydrogen gas. The reaction was carried out at 130 °C and 0.5 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the resulting reaction solution was poured into 3.5 L of ethanol. After filtration, the cyclic olefin block copolymer was obtained.
[0138] Example 4
[0139] In a glove box, 100 mL each of 0.1 mol / L catalyst a3 toluene solution and 0.1 mol / L catalyst b3 toluene solution were prepared. 0.73 g cyclopentene, 1.5 g 2-phenyl-5-norbornene, 260 mL toluene, 0.3 g 1-hexene, and 3 mL diethylaluminum hexane chloride solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 5.6 mL of catalyst a3 toluene solution and 6.0 mL of catalyst b3 toluene solution were added simultaneously. The mixture was stirred at 50 °C for 2 h under normal pressure. 10 g barium chloride was added, and the mixture was stirred for 0.5 h. The supernatant was filtered, and 0.2 g of 15% palladium on carbon catalyst was added. Hydrogen gas was introduced, and the reaction was carried out at 160 °C and 0.9 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the supernatant was poured into 3.5 L of ethanol. After filtration, the cycloolefin block copolymer was obtained.
[0140] Example 5
[0141] In a glove box, 100 mL each of 0.1 mol / L catalyst a2 toluene solution and 0.1 mol / L catalyst b1 toluene solution were prepared. 0.88 g cycloheptene, 1.27 g tetracyclododecene, 300 mL cyclohexane, 0.2 g 4-octene, and 2.2 mL diethylaluminum hexane chloride solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 4 mL of catalyst a2 toluene solution and 6.0 mL of catalyst b1 toluene solution were added simultaneously. The mixture was stirred at atmospheric pressure and 80 °C for 2 h. 15 g calcium hydroxide was added to the reaction solution, and the mixture was stirred for 0.5 h. The supernatant was filtered, and 0.2 g of 15% palladium on carbon catalyst was added. Hydrogen gas was introduced, and the reaction was carried out at 140 °C and 0.5 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the supernatant was poured into 3.5 L acetone. After filtration, the cyclic olefin block copolymer was obtained.
[0142] Example 6
[0143] In a glove box, 100 mL each of 0.1 mol / L catalyst a1 toluene solution and 0.1 mol / L catalyst b2 toluene solution were prepared. 1.71 g cyclooctene, 0.66 g 2-phenyl-5-norbornene, 300 mL cyclohexane, 0.3 g 1-hexene, and 2.5 mL diethylaluminum hexane chloride solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 3.3 mL of catalyst a1 toluene solution and 4.5 mL of catalyst b2 toluene solution were added simultaneously. The mixture was stirred at atmospheric pressure and 70 °C for 3 h. 10 g calcium hydroxide was added to the reaction solution, and the mixture was stirred for 0.5 h. The supernatant was filtered, and 0.2 g of 15% palladium on carbon catalyst was added to it, followed by hydrogen gas. The reaction was carried out at 170 °C and 0.9 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the supernatant was poured into 3.5 L acetone. After filtration, the cyclic olefin block copolymer was obtained.
[0144] Comparative Example 1
[0145] Prepare a 50 mL toluene solution of 0.1 mol / L ruthenium 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(dichlorobenzylmethyl)(tricyclohexylphosphine)ruthenium as the catalyst solution in a glove box. Add 0.88 g cyclopentene, 1.27 g tetracyclododecene, 300 mL toluene, 0.14 g 1-octene, and 7 mL of the above catalyst solution sequentially to a reactor purged with nitrogen three times. Stir at 60 °C for 2 h, add 10 g calcium hydroxide, stir for 0.5 h, filter, add 0.2 g of 15% palladium-on-carbon catalyst to the supernatant, and purge with hydrogen. React at 160 °C and 0.9 MPa for 12 h. Filter to separate the palladium-on-carbon catalyst, pour the resulting reaction solution into 3.5 L of ethanol, and filter to obtain a cyclic olefin block copolymer.
[0146] Comparative Example 2
[0147] Prepare a 50 mL toluene solution of 0.1 mol / L ruthenium 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(dichlorobenzylmethyl)(tricyclohexylphosphine)ruthenium as the catalyst solution in a glove box. Add 2.5 g of 2-phenyl-5-norbornene, 260 mL of toluene, 0.3 g of 1-hexene, and 8 mL of the above catalyst solution sequentially to a reactor purged with nitrogen three times. Stir at 50 °C for 2 h, add 10 g of barium chloride, stir for 0.5 h, filter, and collect the supernatant. Add 0.2 g of 15% palladium on carbon catalyst to the supernatant, purge with hydrogen, and react at 160 °C and 0.9 MPa for 12 h. Filter to separate the palladium on carbon catalyst, pour the supernatant into 3.5 L of ethanol, and filter to obtain a cyclic olefin block copolymer.
[0148] Comparative Example 3
[0149] 0.88 g of cyclopentene, 1.27 g of tetracyclododecene, 300 mL of toluene, 0.14 g of 1-octene, and 1.8 mL of triisobutylaluminum hexane solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 20 mL of 1 wt% di(2,6-dichlorophenol)tetrachlorotungsten oxide toluene solution was added. The mixture was stirred at 60 °C for 2 h. 10 g of calcium hydroxide was added, and the mixture was stirred for 0.5 h. After filtration, 0.2 g of 15% palladium on carbon catalyst was added to the supernatant, and hydrogen gas was introduced. The mixture was reacted at 160 °C and 0.9 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the resulting reaction solution was poured into 3.5 L of ethanol. After filtration, the cycloolefin block copolymer was obtained.
[0150] Comparative Example 4
[0151] 1.27 g of tetracyclododecene, 300 mL of toluene, 0.14 g of 1-octene, and 1.8 mL of triisobutylaluminum hexane solution (0.2 M) were added sequentially to a reactor purged with nitrogen three times. Then, 25 mL of 1.5 wt% di(2,4,6-trichlorophenol)tetrachlorotungsten oxide toluene solution was added, and the mixture was stirred at 60 °C for 1 h. Next, 0.88 g of cyclopentene was added, and the mixture was stirred for another 1 h. Then, 10 g of calcium hydroxide was added, and the mixture was stirred for 0.5 h. After filtration, 0.2 g of 15% palladium on carbon catalyst was added to the supernatant, and hydrogen gas was introduced. The mixture was reacted at 160 °C and 0.9 MPa for 12 h. The palladium on carbon catalyst was separated by filtration, and the resulting reaction solution was poured into 3.5 L of ethanol. After filtration, the cycloolefin block copolymer was obtained.
[0152] Test case
[0153] Performance tests were conducted on Examples 1-6 and Comparative Examples 1-4, using the following methods:
[0154] 1. The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI) of the cyclic olefin block copolymers were determined by high-temperature gel permeation chromatography, using 1,2,4-trichlorobenzene as the mobile phase and narrow-distribution polystyrene as the standard.
[0155] 2. The glass transition temperature of the cyclic olefin block copolymer was determined using a differential scanning calorimeter (DSC) at a heating rate of 10 °C / min.
[0156] 3. The hydrogenation rate of the cyclic olefin block copolymer was measured by H-NMR spectroscopy, with deuterated chloroform as the solvent.
[0157] 4. The transmittance of the cyclic olefin block copolymer was determined by spectrophotometer. The cyclic olefin copolymer was made into a 3 mm thick sheet, and the test wavelength was 430 nm.
[0158] 5. The method for testing elongation at break is as follows: The cyclic olefin block copolymer was prepared into dumbbell-shaped test pieces. Tensile tests were conducted on the obtained dumbbell-shaped test pieces under the following conditions: clamp spacing: 100 mm, tensile speed: 45 mm / s, mark spacing: 65 mm, temperature: 25℃, and the elongation at break was measured. The results are shown in Table 1.
[0159] Table 1
[0160]
[0161]
[0162] The present invention prepares cyclic olefin block copolymers containing hard and soft segments, which have better thermal stability, higher elongation at break, higher glass transition temperature, good transparency and excellent processing performance.
[0163] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing a cyclic olefin block copolymer, characterized in that, Includes the following steps: S1, a monocyclic olefin, a cyclic olefin with a rigid structure, an inert solvent, a molecular weight regulator and a co-catalyst are added to a reaction vessel in sequence and mixed to obtain a mixture. Then, solutions of catalyst I and catalyst II in an inert solvent are added at the same time to carry out a ring-opening polymerization reaction. S2. After the reaction is complete, catalyst I and catalyst II are removed, the supernatant is filtered and a hydrogen source is introduced into it and a hydrogenation catalyst is added to carry out the hydrogenation reaction. After the reaction is complete, the mixture is filtered and separated to obtain the cyclic olefin block copolymer. The structural formulas of catalyst I and catalyst II are shown below: In the formula, M is tungsten, molybdenum, nickel, or palladium; X is independently selected from halogens, C 1～30 Aliphatic alkanes, substituted or unsubstituted C 1～20 The aryl group; wherein the substituent is a group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom; Ra1 to Ra2 are independently selected from hydrogen atoms, C atoms 1～30 Aliphatic alkanes, substituted or unsubstituted C 1～20 The aryl group; Ra3 to Ra8 are independently selected from hydrogen atoms, C 1～30 Aliphatic alkanes, substituted or unsubstituted C 1～20 The aryl group; wherein the substituent is a group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom; M' is tungsten, molybdenum, nickel, or palladium; L is independently selected from halogens, C 1～30 Aliphatic alkyl groups, C 1～30 Alicyclic alkyl, substituted or unsubstituted C 1～20 The aryl group; wherein the substituents are isopropoxy, ethoxy, bromomethoxy, or formamido; Rb1 to Rb2 are independently selected from hydrogen atoms, C atoms 1～30 Aliphatic alkanes, substituted C 1～20 The aryl group; Rb3 to Rb4 are neutral dielectron donors; n is an integer from 0 to 6.
2. The method for preparing the cyclic olefin block copolymer according to claim 1, characterized in that, The structural formula of the cycloolefin containing a rigid structure is shown in Formula III below: Formula III In the formula, R1 to R10 each independently represent a hydrogen atom, a C1 to 30 alkyl group, or a substituted or unsubstituted C6 to 20 aryl group, wherein the substituent is a group containing a silicon atom, a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom; R1 and R4 are combined with each other to form a ring; m takes the integer between 0 and 3.
3. The method for preparing the cyclic olefin block copolymer according to claim 1 or 2, characterized in that, The molar ratio of catalyst I, catalyst II, monocyclic olefin, and cyclic olefin containing a rigid structure is 1:2-5:(100-4000):(100-4000).
4. The method for preparing the cyclic olefin block copolymer according to claim 1 or 2, characterized in that, The total mass fraction of the monocyclic olefin and the cyclic olefin containing a rigid structure in the inert solvent is 1 wt% to 50 wt%, and the mass ratio of the monocyclic olefin to the cyclic olefin containing a rigid structure is 1:(0.1-10).
5. The method for preparing the cyclic olefin block copolymer according to claim 1 or 2, characterized in that, The reaction temperature for the ring-opening polymerization is 20–300°C, and the reaction temperature for the hydrogenation reaction is -10–200°C.
6. The method for preparing the cyclic olefin block copolymer according to claim 1 or 2, characterized in that, The molecular weight regulator is selected from one or more compounds containing carbon-carbon double bonds with C3 to 30, and the molar ratio of the total amount of monocyclic olefins and cyclic olefins containing rigid structures to the molecular weight regulator is (10 to 1000):
1.
7. The method for preparing the cyclic olefin block copolymer according to claim 1 or 2, characterized in that, The co-catalyst is one or more of alkyllithium, alkylzinc, alkylaluminum, and alkylmagnesium.
8. The method for preparing the cyclic olefin block copolymer according to claim 1 or 2, characterized in that, The hydrogen source is hydrogen gas or a hydrazine compound.
9. The method for preparing the cyclic olefin block copolymer according to claim 2, characterized in that, The cyclic olefins containing rigid structures include one or more of norbornene, 2-phenyl-5-norbornene, tetracyclododecene, 2-benzoyl-5-norbornene, 5-norbornene-2,3-dicarboximide, 5-norbornene-2,3-dicarboxylic anhydride, and methyl-5-norbornene-2,3-dicarboxylic anhydride.
10. A cyclic olefin block copolymer, characterized in that, Prepared by the preparation method according to any one of claims 1 to 9.