A cyclic olefin ring-opening alternating copolymer, its preparation method and application

Abstract

This application discloses a cyclic olefin ring-opening alternating copolymer, its preparation method, and its applications. The cyclic olefin ring-opening alternating copolymer of this application is synthesized by alternating 1:1 ring-opening substitutions of any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene. The cyclic olefin ring-opening alternating copolymer of this application possesses a precise 1:1 alternating insertion copolymer structure with high alternation degree, high molecular weight, narrow distribution, and excellent thermodynamic properties, laying the foundation for the preparation of high-performance elastomers, optical films, and biomedical materials.

Description

Technical Field

[0001] This application relates to the field of cyclic olefin ring-opening metastasis alternating copolymerization technology, and in particular to a cyclic olefin ring-opening metastasis alternating copolymer, its preparation method and application. Background Technology

[0002] Olefin ring-opening metathesis polymerization (ROMP) is an important method for constructing high molecular weight olefin polymers. Alternating cyclic olefin copolymerization, in particular, has become a research hotspot in polymer synthesis because it can precisely control the polymer backbone sequence structure, endowing materials with excellent mechanical, thermal, and functional properties. High-strain cyclic olefins such as norbornene (NBE), cyclobutene (CBE), and cyclopropylene (CPE) are commonly used monomers in ROMP. When cyclic olefins undergo alternating copolymerization, the resulting copolymers, namely alternating cyclic olefin ring-opening metathesis copolymers, combine the structural advantages of both monomers and have significant application value in the field of high-performance materials. However, existing technologies for alternating copolymerization sequences of cyclic olefins still face several bottlenecks: 1) High-strain cyclic olefin monomers have a significant tendency to self-polymerize, and traditional catalysts struggle to achieve precise and uniform alternating copolymerization of the two monomers, easily generating random copolymers or block copolymers; 2) Existing Ru-based catalysts cannot simultaneously achieve selective recognition of monomers with different steric hindrances and ring strains; 3) Some catalytic systems require excess monomers to achieve low-degree alternating copolymerization, resulting in low atom economy and low molecular weight and wide distribution of the obtained copolymers, lacking practical application value; 4) Existing catalysts for alternating copolymerization of cyclic olefins exhibit poor catalytic selectivity and universality.

[0003] While existing Grubbs-type ruthenium catalysts are widely used in olefin metathesis, they struggle to distinguish between different monomers, making it impossible to achieve alternating copolymerization of high-strain cyclic olefins. Although some asymmetric NHC carbene-modified ruthenium catalysts can improve the degree of alternation, they still suffer from low cis-structure content and high glass transition temperatures. Therefore, achieving efficient and precise alternating copolymerization of high-strain cyclic olefins through ring-opening metathesis remains a pressing technical problem to be solved in this field. Summary of the Invention

[0004] The purpose of this application is to provide a novel cyclic olefin ring-opening alternating copolymer, as well as a method for preparing the cyclic olefin ring-opening alternating copolymer and its applications.

[0005] To achieve the above objectives, this application adopts the following technical solution:

[0006] This application discloses a cyclic olefin ring-opening alternating copolymer, which is formed by alternating copolymerization of any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene in a 1:1 ratio.

[0007] In this process, any two cyclic olefin monomers can be two differently substituted cyclopropylenes, two differently substituted cyclobutenes, two differently substituted norbornenes, a substituted or unsubstituted cyclopropylene and a substituted or unsubstituted cyclobutene, a substituted or unsubstituted cyclopropylene and a substituted or unsubstituted norbornene, or a substituted or unsubstituted cyclobutene and a substituted or unsubstituted norbornene. A 1:1 alternating copolymerization refers to the uniform alternating copolymerization of two cyclic olefin monomers in a 1:1 molar ratio, for example, a substituted or unsubstituted cyclopropylene A and a substituted or unsubstituted cyclobutene B, which are copolymerized in an alternating ABABABABABAB… pattern.

[0008] It should be noted that the cyclic olefin ring-opening alternating copolymer of this application, compared with existing alternating copolymers, has a precise 1:1 alternating insertion copolymer structure, high degree of alternation, high molecular weight, narrow distribution, and excellent thermodynamic properties. In some implementations, the cyclic olefin ring-opening alternating copolymer of this application has a number-average molecular weight of up to 490 kDa, PDI < 1.9, an adjustable glass transition temperature of 40~170 ℃, a main chain thermal decomposition temperature as high as 360 ℃, tensile strength ≥ 12 MPa, elastic modulus ≥ 350 MPa, and toughness ≥ 17 MJ·m. -3 It is better suited for high-performance elastomers, optical films, biomedical materials and other fields.

[0009] In one implementation of this application, the substituted cyclopropylene has the structure shown in Formula A, the substituted cyclobutene has the structure shown in Formula B, and the substituted norbornene has the structure shown in Formula C.

[0010] , , ,

[0011] Ring-opening metathesis 1:1 alternating copolymerization reactions occur between cyclopropenes with different substituents, between cyclobutenes with different substituents, between norbornene with different substituents, between cyclopropene and cyclobutene, between cyclopropene and norbornene, or between cyclobutene and norbornene.

[0012] In one implementation of this application, the substituted cyclopropylene is at least one of the structures shown in A1, A2, A3, A4, and A5.

[0013] ;

[0014] Wherein, x is at least one of Cl, Br, and F;

[0015] The groups attached to the 2nd, 3rd, and 4th carbons of the Ar group are at least one of H, F, Cl, Br, CF3, OMe, Me, iPr, tBu, NO2, CN, NH2, OH, and COOMe, and / or the groups attached to the 2nd, 4th, and 6th carbons of the Ar group are at least one of F, Br, CF3, OMe, Me, and Et, and / or the groups attached to the 3rd and 5th carbons of the Ar group are at least one of F, Br, CF3, OMe, Me, and Et;

[0016] R1 is selected from Me, Et, iPr, tBu, OH, OMe, NH2, NMe2 or COOMe, and R2 is selected from H, Me, Et, iPr or tBu.

[0017] In one implementation of this application, the substituted cyclobutene is at least one of the structures shown in B1, B2, B3, B4, and B5.

[0018] ;

[0019] Where x is O or SO2, and n is 1, 2 or 3;

[0020] R3 and R5 can be repeatedly selected from COCH3, COCl3, COCF3, Ts, Boc, Cbz, Me, Et, iPr, tBu, Ph or Hex;

[0021] R4 is selected from F, Cl, Br, OH, OMe, OTBS, COOMe, Bn, CH2OH, CH2OBn, CH2OBz, CH2NH, CH2NMe2, CH2tBu, or CH2OBoc.

[0022] In one implementation of this application, the substituted or unsubstituted norbornene is at least one of the structures shown in C1, C2, C3, C4, and C5.

[0023] ;

[0024] Where x is O, S, NMe, CH2, CMe2, CHBr, or CPE;

[0025] The groups attached to the 2nd and 3rd carbons of the Ar group are at least one of F, Cl, Br, CF3, OMe, Me, Et, iPr, tBu, NO2, CN, NH2, OH, OEt, and COOMe.

[0026] R6 is selected from H, Me, CHO, CN, COCH3, OCOCH3, COOH, Boc, COOEt, CH2NH2, CH2Br, Vinyl, or Ethylidene;

[0027] R7 is selected from Me, H, Ph, COCH3, OCOCH3, COOH, COOEt, CH2NH2, CH2Br, Bn, or OMe.

[0028] This application also discloses a method for preparing the cyclic olefin ring-opening alternating copolymer of this application, which includes using any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene as raw materials, and using a chiral ruthenium catalyst to perform a 1:1 alternating copolymerization reaction of the two cyclic olefin monomers to generate the cyclic olefin ring-opening alternating copolymer of this application.

[0029] The chiral ruthenium catalyst has the structure shown in formula (1).

[0030] Equation (1) ,

[0031] In formula (1), R1 is phenyl, R2 is isopropyl, R3 isopropyl, R4 is hydrogen, R5 is tert-butyl, and R6 isopropyl.

[0032] It should be noted that the chiral ruthenium catalyst used in the preparation method of this application is a cyclic metallized Ru stereocenter complex with dual active centers. Its active centers can dynamically switch between out-of-plane and in-plane conformations: the out-of-plane conformation is a crowded cavity structure, which preferentially binds monomers with low steric hindrance and low ring strain through the steric hindrance screening effect, achieving kinetically controlled selective insertion; the in-plane conformation is an open cavity structure, which preferentially binds monomers with high ring strain through the ring strain thermodynamic driving effect, achieving thermodynamically controlled selective insertion. Therefore, the chiral ruthenium catalyst used in the preparation method of this application, through a dual regulation mechanism of "steric hindrance screening-ring strain driving," can achieve precise 1:1 alternating insertion polymerization between high-strain cyclic olefins, such as cyclopropylene, cyclobutene, and norbornene, effectively suppressing the tendency of monomer self-polymerization. Furthermore, the alternating copolymers prepared using the chiral ruthenium catalyst in this application possess high molecular weight, narrow distribution, and excellent thermodynamic properties. In one embodiment of this application, the prepared alternating copolymers have a number-average molecular weight of up to 490 kDa, PDI < 1.9, an adjustable glass transition temperature between 40 and 170 °C, a main chain thermal decomposition temperature as high as 360 °C, tensile strength ≥ 12 MPa, elastic modulus ≥ 350 MPa, and toughness ≥ 17 MJ·m. -3 This makes the prepared alternating copolymers promising for applications in high-performance elastomers, optical films, and biomedical materials.

[0033] In one implementation of this application, the reaction temperature of the alternating copolymerization reaction is -10℃ to 50℃.

[0034] In one implementation of this application, the alternating copolymerization reaction is carried out under an inert gas protection.

[0035] In one implementation of this application, the molar ratio of the two cyclic olefin monomers is 1:1.

[0036] In one implementation of this application, the molar ratio of chiral ruthenium catalyst to monomer is 1:(200~1000).

[0037] In one implementation of this application, the alternating copolymerization reaction is carried out in a solvent.

[0038] In one implementation of this application, the solvent is at least one selected from dichloromethane, toluene, n-hexane, haloalkanes, aromatic hydrocarbons, and aliphatic hydrocarbons.

[0039] It should be noted that the use of solvent is a preferred condition, but not a necessity; under certain conditions, solvent may not be used, that is, the reactants may be dissolved or melted, or the reactants may be directly mixed and then reacted under heating, grinding, or gas-phase conditions; or supercritical carbon dioxide may be used as the reaction medium.

[0040] In one implementation of this application, the alternating copolymerization reaction time is 10~60 min.

[0041] This application also discloses the application of the cyclic olefin ring-opening alternating copolymer of this application in the preparation of elastomer materials, film materials, biomedical materials or functional coating materials.

[0042] It should be noted that the cyclic olefin ring-opening alternating copolymer of this application, as an elastomer material, can be used in high-end sealing, shock absorption, and fatigue-resistant components; as a film material, it is suitable for high-barrier, high-transparency, and dimensionally stable optical films and packaging films; as a biomedical material, it can be used to manufacture medical devices, in vitro diagnostic consumables, drug carriers, and implantation aids, meeting sterilization and biosafety requirements; as a functional coating material, it can be used to prepare wear-resistant, weather-resistant, corrosion-resistant, insulating, and surface-protective coatings, improving the service life and functionality of the substrate. In summary, the cyclic olefin ring-opening alternating copolymer of this application provides a new high-performance solution for the field of high-end polymer materials.

[0043] Due to the adoption of the above technical solutions, the beneficial effects of this application are as follows:

[0044] The cyclic olefin ring-opening alternating copolymer of this application has a precise 1:1 alternating insertion copolymer structure with high degree of alternation, high molecular weight, narrow distribution and excellent thermodynamic properties, laying the foundation for the preparation of high-performance elastomers, optical films, biomedical materials and the like. Attached Figure Description

[0045] Figure 1 This is a schematic diagram of the catalyst structure in the embodiments of this application;

[0046] Figures 2 to 7 These are the GPC spectra of the six alternating copolymers synthesized in the embodiments of this application;

[0047] Figure 8 This is the DSC spectrum of the alternating copolymer synthesized in the embodiments of this application;

[0048] Figure 9 This is the TGA spectrum of the alternating copolymer synthesized in the embodiments of this application;

[0049] Figure 10 This is a graph showing the mechanical properties of the alternating copolymers synthesized in the embodiments of this application;

[0050] Figure 11 This is a curve showing the real-time conversion rate of the monomer monitored by coarse NMR spectroscopy during the synthesis of poly(B4-2-alt-C1-1) in the embodiments of this application.

[0051] Figure 12 This is the linear fitting curve of poly(B4-2-alt-C1-1) against polychlorinated chloride in the embodiments of this application. Detailed Implementation

[0052] To address the problems of high-strength monomer self-polymerization, random copolymer structure, and poor performance in existing cyclic olefin ring-opening metastasis alternating copolymers, this application develops a novel cyclic olefin ring-opening metastasis alternating copolymer, which is formed by alternating copolymerization of any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene in a 1:1 ratio.

[0053] In some implementations, the substituted cyclopropene has the structure shown in Formula A, the substituted cyclobutene has the structure shown in Formula B, and the substituted norbornene has the structure shown in Formula C.

[0054] , , ,

[0055] Ring-opening metathesis 1:1 alternating copolymerization reactions occur between cyclopropenes with different substituents, between cyclobutenes with different substituents, between norbornene with different substituents, between cyclopropene and cyclobutene, between cyclopropene and norbornene, or between cyclobutene and norbornene.

[0056] The specific reaction formula is as follows:

[0057]

[0058] In some implementations, the chiral ruthenium catalyst used to prepare the cyclic olefin ring-opening metathesis alternating copolymer of this application has dual active centers, which can achieve dual regulation of steric hindrance and ring strain through conformational dynamic switching, and accurately identify and selectively insert cyclic olefin monomers.

[0059] The chiral ruthenium catalyst used in this application has the structure shown in formula (1).

[0060] Equation (1) ,

[0061] Wherein, R1 is selected from phenyl, R2 from isopropyl, R3 from isopropyl, R4 from hydrogen, R5 from tert-butyl, and R6 from isopropyl.

[0062] The chiral ruthenium catalyst of this application is a cyclometalated Ru stereocenter complex with dual active centers. Its active centers can dynamically switch between out-of-plane and in-plane conformations: the out-of-plane conformation is a crowded cavity structure, which preferentially binds monomers with low steric hindrance and low ring strain through the steric hindrance screening effect, achieving kinetically controlled selective insertion; the in-plane conformation is an open cavity structure, which preferentially binds monomers with high ring strain through the ring strain thermodynamic driving effect, achieving thermodynamically controlled selective insertion.

[0063] The synthetic route for this chiral ruthenium catalyst precisely controls regio / stereoselectivity and functional group compatibility. The specific synthetic steps include:

[0064] 1. Hydroxyl protection and introduction of Ad substituents: Stereoselective hydroxyl protection was achieved by using α-phenyl-β-hydroxy-amine as a raw material and a diethyl azodicarbonate / triphenylphosphine catalytic system via the Mitsunobu reaction; then the Boc protecting group was selectively cleaved by trichloroacetic acid, and the silver salt reacted with the bromide to generate an Ad carbocation intermediate, which was then introduced with the action of potassium carbonate.

[0065] 2. Construction of five-membered nitrogen-containing heterocyclic ligands: After the hydroxyl protection of hydrazine hydrate was removed by hydrazine dehydrogenation, it was subjected to Buchwald-Hartwig amination with 2,6-diisopropylbromobenzene under the catalysis of Pd2(dba)3; subsequently, under the co-catalysis of ammonium tetrachloroborate / formic acid, it underwent intramolecular cyclization with triethyl orthoformate to directionally construct five-membered nitrogen-containing heterocyclic ligands.

[0066] 3. Ru complex formation and CH bond activation: After deprotonation treatment with potassium carbonate, Ru metal precursor is formed into Ru complex intermediate through ligand substitution; finally, under the action of sodium terpentate, stereoselective CH bond activation reaction of Ad is achieved, and the chiral ruthenium catalyst is prepared efficiently.

[0067] In some implementations, the synthetic route of the chiral ruthenium catalyst in this application is as follows:

[0068]

[0069] Based on the above chiral ruthenium catalyst, the preparation method of the cyclic olefin ring-opening alternating copolymer of this application includes using any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene as raw materials, and using a chiral ruthenium catalyst to perform a 1:1 alternating ring-opening alternating copolymerization reaction of the two cyclic olefin monomers to generate the cyclic olefin ring-opening alternating copolymer of this application.

[0070] Using the chiral ruthenium catalyst as the main catalyst, cyclic olefin monomers undergo 1:1 alternating copolymerization through ring-opening metathesis to generate structurally regular alternating cyclic olefin copolymers. The core catalytic mechanism involves the chiral ruthenium catalyst achieving precise alternating copolymerization through a dynamic catalytic cycle regulated by both steric hindrance and ring strain. The specific process (taking CBE and NBE as examples) is as follows:

[0071] 1. The Ru oxygen bond of the catalyst breaks and dissociates to form an out-of-plane conformation active center (i.e., a crowded cavity). Through steric hindrance screening, it preferentially recognizes CBE with small steric hindrance and low ring strain, driving it to undergo a kinetically controlled [2+2] cycloaddition reaction to generate Ru heterocyclic butane intermediate;

[0072] 2. Ru heterocyclic butane intermediates migrate to in-plane conformational active centers (i.e., open cavities) through conformational inversion mechanisms and undergo ring-opening regeneration into new active species. At this point, ring strain becomes the dominant factor. NBEs with high ring strain preferentially undergo ring metathesis due to thermodynamic advantages, forming new Ru heterocyclic butane intermediates.

[0073] 3. The new Ru heterocyclic butane intermediate undergoes a conformational flip back to the out-of-plane conformation, completing the catalytic cycle reset and continuously achieving the alternating insertion of CBE and NBE monomers, ultimately forming a strictly alternating 1:1 copolymer backbone.

[0074] Therefore, the cyclic olefin ring-opening metastasis alternating copolymer of this application achieves 1:1 strict alternating copolymerization, overcoming the problem of high-strength monomer self-polymerization. Furthermore, the copolymer has the characteristics of high molecular weight, narrow distribution, and regular structure, and has excellent thermal and mechanical properties, showing broad application prospects.

[0075] In some embodiments, the substituted cyclopropylene is at least one of the structures shown in A1, A2, A3, A4, and A5.

[0076] Specifically, the structure shown in A1 includes A1-1 to A1-3, namely A1-1, A1-2, and A1-3, which are chlorine-, bromine-, and fluorine-substituted cyclopropenes, respectively, with the specific structures as follows:

[0077]

[0078] The structure shown in A2 specifically includes 37 compounds, A2-1 to A2-37, namely phenylmethylcyclopropene, phenylethylcyclopropene, phenylisopropylcyclopropene, phenyl tert-butylcyclopropene, phenylhydroxy-substituted cyclopropene, phenylmethoxy-substituted cyclopropene, phenyldimethylamino-substituted cyclopropene, phenylmethyl ester-substituted cyclopropene, 4-fluorophenylmethylcyclopropene, 4-chlorophenylmethylcyclopropene, 4-bromophenylmethylcyclopropene, 4-trifluoromethylphenylmethylcyclopropene, 4-nitrophenylmethylcyclopropene, 4-methoxyphenylmethylcyclopropene, 4-cyanophenylmethylcyclopropene, 4-methylphenylmethylcyclopropene, 4-isopropylphenylmethylcyclopropene, 4-tert-butylphenylmethylcyclopropene, 4-aminophenylmethylcyclopropene, 4-hydroxyphenylmethylcyclopropene, 4- Methyl phenylmethylcyclopropene, 3-nitrophenylmethylcyclopropene, 3-methoxyphenylmethylcyclopropene, 2-nitrophenylmethylcyclopropene, 2-methoxyphenylmethylcyclopropene, 3,5-difluorosubstituted phenylmethylcyclopropene, 3,5-dibromophenylmethylcyclopropene, 3,5-ditrifluoromethylphenylmethylcyclopropene, 3,5-dimethoxyphenylmethylcyclopropene, 3,5-dimethylphenylmethylcyclopropene, 3,5-diethylphenylmethylcyclopropene, 2,4,6-trifluorophenylmethylcyclopropene, 2,4,6-tribromophenylmethylcyclopropene, 2,4,6-tritrifluoromethylphenylmethylcyclopropene, 2,4,6-trimethoxyphenylmethylcyclopropene, 2,4,6-trimethylphenylmethylcyclopropene, 2,4,6-triethylphenylmethylcyclopropene.

[0079] The structural formulas for A2-1 to A2-37 are as follows:

[0080]

[0081] The structure shown in A3 specifically includes compounds A3-1 to A3-25, a total of 25 compounds, namely 2-methylphenyltrifluoromethylcyclopropene, 3-methylphenyltrifluoromethylcyclopropene, 4-fluorophenyltrifluoromethylcyclopropene, 4-chlorophenyltrifluoromethylcyclopropene, 4-bromophenyltrifluoromethylcyclopropene, 4-trifluoromethylphenyltrifluoromethylcyclopropene, 4-nitrophenyltrifluoromethylcyclopropene, 4-methoxyphenyltrifluoromethylcyclopropene, 4-cyanophenyltrifluoromethylcyclopropene, 4-methylphenyltrifluoromethylcyclopropene, 4-isopropylphenyltrifluoromethylcyclopropene, 4-tert-butylphenyltrifluoromethylcyclopropene, 4-amino 4-Hydroxyphenyltrifluoromethylcyclopropene, 4-methyl phenyltrifluoromethylcyclopropene, 3-nitrophenyltrifluoromethylcyclopropene, 3-methoxyphenyltrifluoromethylcyclopropene, 2-nitrophenyltrifluoromethylcyclopropene, 2-methoxyphenyltrifluoromethylcyclopropene, 3,5-difluorosubstituted phenyltrifluoromethylcyclopropene, 3,5-dibromophenyltrifluoromethylcyclopropene, 3,5-ditrifluoromethylphenyltrifluoromethylcyclopropene, 3,5-dimethoxyphenyltrifluoromethylcyclopropene, 3,5-dimethylphenyltrifluoromethylcyclopropene, 2,4,6-trimethylphenyltrifluoromethylcyclopropene.

[0082] The structural formulas for A3-1~25 are as follows:

[0083]

[0084] The structure shown in A4 specifically includes 37 compounds, A4-1 to A4-37, namely: phenyl methyl ester substituted cyclopropene, phenyl ethyl ester substituted cyclopropene, phenyl isopropyl ester substituted cyclopropene, phenylformic acid substituted cyclopropene, phenyl tert-butyl ester substituted cyclopropene, phenyl propyl ester substituted cyclopropene, phenyl butyl ester substituted cyclopropene, phenyl isopropyl ester substituted cyclopropene, 4-fluorophenyl methyl ester substituted cyclopropene, 4-chlorophenyl methyl ester substituted cyclopropene, 4-bromophenyl methyl ester substituted cyclopropene, 4-trifluoromethyl substituted phenyl methyl ester substituted cyclopropene, 4-nitrophenyl methyl ester substituted cyclopropene, 4-methoxyphenyl methyl ester substituted cyclopropene, 4-cyanophenyl methyl ester substituted cyclopropene, 4-methylphenyl methyl ester substituted cyclopropene, 4-isopropylphenyl methyl ester substituted cyclopropene, 4-tert-butylphenyl methyl ester substituted cyclopropene, 4-aminophenyl methyl ester substituted cyclopropene, 4-hydroxyphenyl methyl ester substituted cyclopropene, and 4-methyl ester benzene. 3-Nitrophenylmethyl ester substituted with cyclopropene, 3-Methoxyphenylmethyl ester substituted with cyclopropene, 2-Nitrophenylmethyl ester substituted with cyclopropene, 2-Methoxyphenylmethyl ester substituted with cyclopropene, 3,5-Di(trifluorophenyl)methyl ester substituted with cyclopropene, 3,5-Di(bromophenyl)methyl ester substituted with cyclopropene, 3,5-Dimethyl ester substituted with phenylmethyl ester substituted with cyclopropene, 3,5-Dimethoxyphenylmethyl ester substituted with cyclopropene, 3,5-Dimethylphenylmethyl ester substituted with cyclopropene, 3,5-Diethylphenylmethyl ester substituted with cyclopropene, 2,4,6-Trifluorophenylmethyl ester substituted with cyclopropene, 2,4,6-Tribromophenylmethyl ester substituted with cyclopropene, 2,4,6-Trimethyl ester substituted with phenylmethyl ester substituted with cyclopropene, 2,4,6-Trimethoxyphenylmethyl ester substituted with cyclopropene, 2,4,6-Trimethylphenylmethyl ester substituted with cyclopropene, 2,4,6-Triethylphenylmethyl ester substituted with cyclopropene.

[0085] The structural formulas for A4-1~37 are as follows:

[0086]

[0087] The structure shown in A5 specifically includes 24 compounds, A5-1 to A5-24, namely, bis(4-fluorophenyl)-substituted cyclopropene, bis(4-chlorophenyl)-substituted cyclopropene, bis(4-bromophenyl)-substituted cyclopropene, bis(4-trifluoromethyl)-substituted phenyl-substituted cyclopropene, bis(4-methoxyphenyl)-substituted cyclopropene, bis(4-cyanophenyl)-substituted cyclopropene, bis(4-methylphenyl)-substituted cyclopropene, bis(4-isopropylphenyl)-substituted cyclopropene, bis(4-tert-butylphenyl)-substituted cyclopropene, bis(4-aminophenyl)-substituted cyclopropene, bis(4-hydroxyphenyl)-substituted cyclopropene, and bis(4-phenyl)-substituted cyclopropene. Alkenes, bis(3-nitrophenyl)-substituted cyclopropene, bis(3-methoxyphenyl)-substituted cyclopropene, bis(2-nitrophenyl)-substituted cyclopropene, bis(2-methoxyphenyl)-substituted cyclopropene, bis(3,5-di-trifluorophenyl)-substituted cyclopropene, bis(3,5-dibromophenyl)-substituted cyclopropene, bis(3,5-disubstituted phenyl)-substituted cyclopropene, bis(3,5-dimethoxyphenyl)-substituted cyclopropene, bis(3,5-dimethylphenyl)-substituted cyclopropene, bis(3,5-diethylphenyl)-substituted cyclopropene, bis(2,4,6-trimethylphenyl)-substituted cyclopropene, bis(2,4,6-trifluorophenyl)-substituted cyclopropene.

[0088] The structural formulas for A5-1~24 are as follows:

[0089]

[0090] In some embodiments, the substituted cyclobutene is at least one of the structures shown in B1, B2, B3, B4, and B5.

[0091] Specifically, the structure shown in B1 includes B1-1~2, namely B1-1 and B1-2, which are 3-sulfonyl-3-azabicyclo[3.2.0]hept-6-ene and 3-hydroxy-3-azabicyclo[3.2.0]hept-6-ene-2,4-dione, respectively, with the following specific structures:

[0092]

[0093] The structure shown in B2 specifically includes B2-1 to 18, a total of 18 compounds, namely 3-acetyl-3-azabicyclo[3.2.0]hept-6-ene, 3-trichloroacetyl-3-azabicyclo[3.2.0]hept-6-ene, 3-trifluoroacetyl-3-azabicyclo[3.2.0]hept-6-ene, 3-p-toluenesulfonyl-3-azabicyclo[3.2.0]hept-6-ene, 3-Boc-3-azabicyclo[3.2.0]hept-6-ene, 3-Cbz-3-azabicyclo[3.2.0]hept-6-ene, 3-methyl-3-azabicyclo[3.2.0]hept-6-ene, 3-ethyl-3-azabicyclo[3.2.0]hept-6-ene, 3-isopropyl-3-azabicyclo[3.2.0]hept-6-ene, 3 -tert-butyl-3-azabicyclo[3.2.0]hept-6-ene, 3-phenyl-3-azabicyclo[3.2.0]hept-6-ene, 3-n-hexyl-3-azabicyclo[3.2.0]hept-6-ene, 3-methyl-3-azabicyclo[3.2.0]hept-6-ene-2,4-dione, 3-ethyl-3-azabicyclo[3.2.0]hept-6-ene-2,4-dione -Diketone, 3-isopropyl-3-azabicyclo[3.2.0]hept-6-en-2,4-dione, 3-tert-butyl-3-azabicyclo[3.2.0]hept-6-en-2,4-dione, 3-phenyl-3-azabicyclo[3.2.0]hept-6-en-2,4-dione, 3-n-hexyl-3-azabicyclo[3.2.0]hept-6-en-2,4-dione

[0094] The structural formulas for B2-1~18 are as follows:

[0095]

[0096] The structure shown in B3 specifically includes three compounds, B3-1 to B3-3: bicyclo[4.2.0]oct-1(8)-ene, bicyclo[5.2.0]non-1(9)-ene, and bicyclo[6.2.0]dec-1(10)-ene, with the following specific structural formulas:

[0097]

[0098] The structure shown in B4 specifically includes B4-1 to B4-15, a total of 15 compounds, namely 3,4-difluoro-substituted cyclobutene, 3,4-dichloro-substituted cyclobutene, 3,4-dibromo-substituted cyclobutene, 3,4-dihydroxy-substituted cyclobutene, 3,4-dimethoxy-substituted cyclobutene, 3,4-diOTBS-substituted cyclobutene, 3,4-dimethyl ester-substituted cyclobutene, 3,4-dibenzyl-substituted cyclobutene, 3,4-dihydroxymethyl-substituted cyclobutene, 3,4-dibenzyloxymethyl-substituted cyclobutene, 3,4-dibenzoylmethyl-substituted cyclobutene, 3,4-diaminomethyl-substituted cyclobutene, 3,4-dimethylaminomethyl-substituted cyclobutene, 3,4-di-tert-butylmethyl-substituted cyclobutene, and 3,4-bisBoc-methyl-substituted cyclobutene.

[0099] The structural formulas for B4-1~15 are as follows:

[0100]

[0101] The structure shown in B5 specifically includes compounds B5-1 to B5-18, totaling 18 compounds, namely 4-acetyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-trichloroacetyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-trifluoroacetyl-4-azatricyclo[5.2.1.0]deca-8-ene, and 4-p-toluenesulfonyl-4-azatricyclo[5.2.1.0] Deca-8-ene, 4-Boc-4-azatricyclo[5.2.1.0]deca-8-ene, 4-Cbz-4-azatricyclo[5.2.1.0]deca-8-ene, 4-methyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-ethyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-isopropyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4 -tert-butyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-phenyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-n-hexyl-4-azatricyclo[5.2.1.0]deca-8-ene, 4-methyl-4-azatricyclo[5.2.1.0]deca-8-ene-2,4-dione, 4-ethyl-4-azatricyclo[5.2.1.0]deca-8-ene-2, 4-Diketone, 4-isopropyl-4-azatricyclo[5.2.1.0]dec-8-en-2,4-dione, 4-tert-butyl-4-azatricyclo[5.2.1.0]dec-8-en-2,4-dione, 4-phenyl-4-azatricyclo[5.2.1.0]dec-8-en-2,4-dione, 4-n-hexyl-4-azatricyclo[5.2.1.0]dec-8-en-2,4-dione

[0102] The structural formulas for B5-1~18 are as follows:

[0103]

[0104] In some embodiments, the substituted or unsubstituted norbornene is at least one of the structures shown in C1, C2, C3, C4, and C5. C5 is dicyclopentadiene, abbreviated as DCPD.

[0105] Specifically, the structure shown in C1 includes 13 compounds from C1-1 to C1-13, namely norbornene, 5-methyl-substituted norbornene, 5-aldehyde-substituted norbornene, 5-cyano-substituted norbornene, 5-acetyl-substituted norbornene, 5-acetoxy-substituted norbornene, 5-carboxyl-substituted norbornene, 5-Boc-substituted norbornene, 5-ethyl ester-substituted norbornene, 5-aminomethyl-substituted norbornene, 5-bromomethyl-substituted norbornene, 5-vinyl-substituted norbornene, and 5-ethylidene norbornene.

[0106] The structural formulas for C1-1~13 are as follows:

[0107]

[0108] The structure shown in C2 specifically includes C2-1 to C2-15, a total of 15 compounds, namely 2-fluorophenyl-substituted norbornene, 2-chlorophenyl-substituted norbornene, 2-bromophenyl-substituted norbornene, 2-trifluoromethylphenyl norbornene, 2-methoxyphenyl norbornene, 2-methylphenyl norbornene, 3-methylphenyl norbornene, 3-ethylphenyl norbornene, 3-isopropylphenyl norbornene, 3-tert-butylphenyl norbornene, 3-nitrophenyl norbornene, 3-cyanophenyl norbornene, 2,5-dimethylphenyl norbornene, 3,4-dimethoxyphenyl norbornene, and 2,3,4,5-tetramethylphenyl norbornene.

[0109] The structural formulas for C2-1~15 are as follows:

[0110]

[0111] The structure shown in C3 specifically includes 25 compounds from C3-1 to C3-25, namely 5,6-dimethyl-substituted norbornadiene, norbornadiene, 5,6-diacetyl-substituted norbornadiene, 5,6-dicarboxyl-substituted norbornadiene, 5,6-diethyl ester-substituted norbornadiene, 5,6-diaminomethyl-substituted norbornadiene, 5,6-dibromomethyl-substituted norbornadiene, 5,6-dibenzyl-substituted norbornadiene, 5,6-dimethoxy-substituted norbornadiene, exo-5,6-dimethyl-substituted norbornene, exo-5,6-diacetyl-substituted norbornene, exo-5,6-dicarboxyl-substituted norbornene, and exo-5,6-diethyl ester-substituted norbornene. exo-5,6-diaminomethyl-substituted norbornene, exo-5,6-dibromomethyl-substituted norbornene, exo-5,6-dibenzyl-substituted norbornene, exo-5,6-dimethoxy-substituted norbornene, endo-5,6-dimethyl-substituted norbornene, endo-5,6-diacetyl-substituted norbornene, endo-5,6-dicarboxyl-substituted norbornene, endo-5,6-diethyl-substituted norbornene, endo-5,6-diaminomethyl-substituted norbornene, endo-5,6-dibromomethyl-substituted norbornene, endo-5,6-dibenzyl-substituted norbornene, endo-5,6-dimethoxy-substituted norbornene.

[0112] The structural formulas for C3-1~25 are as follows:

[0113]

[0114] The structure shown in C4 specifically includes C4-1 to C4-14, a total of 14 compounds, namely exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, exo-7-thiabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, exo-7-aminomethylhexabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, exo-7-methylenehexabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, exo-7-isopropylhexabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, exo-7-bromomethylhexabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and exo-7-cyclopropylhexabicyclo[2.2.1]hept-5 -en-2,3-dicarboxylic anhydride, endo-7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, endo-7-thiobicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, endo-7-aminomethylbicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, endo-7-methylenebicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, endo-7-isopropylbicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, endo-7-bromomethylbicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, endo-7-cyclopropylbicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride.

[0115] The structural formulas for C4-1~14 are as follows:

[0116]

[0117] Copolymerization between cyclopropylenes with different substituents, for example:

[0118]

[0119] Copolymerization between cyclobutenes with different substituents, for example:

[0120]

[0121] Copolymerization between norbornene with different substituents, for example:

[0122]

[0123] Copolymerization between cyclopropylene and cyclobutene, for example:

[0124]

[0125] Copolymerization between cyclopropylene and norbornene, for example:

[0126]

[0127] Copolymerization between cyclobutene and norbornene, for example:

[0128]

[0129] Preferred copolymerization conditions:

[0130] - Atmosphere: Protected by inert gases such as argon and nitrogen;

[0131] -Temperature: -10~50℃, no high temperature required, mild reaction conditions;

[0132] - Catalyst dosage: The molar ratio of catalyst to monomer is 1:(200~1000), resulting in high catalytic efficiency;

[0133] - Monomer ratio: The molar ratio of cyclic olefin monomers is 1:1;

[0134] -Reaction solvents: dichloromethane, toluene, n-hexane, haloalkanes / aromatic hydrocarbons / aliphatic hydrocarbons, with good solubility and excellent compatibility with catalytic systems;

[0135] -Reaction time: Based on monomer conversion rate monitoring, it is generally 10~60 min, and the simultaneous monomer conversion rate can reach over 99%, resulting in high reaction efficiency.

[0136] The copolymer of this application is formed by alternating copolymerization of cyclic olefin monomers in a 1:1 ratio through ring-opening metathesis, and has a highly ordered alternating sequence structure. Characterized by gel permeation chromatography (GPC), one-dimensional / two-dimensional nuclear magnetic resonance, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile testing, the copolymer exhibits the following excellent properties:

[0137] 1. Molecular weight and distribution: Number-average molecular weight (M n The molecular weight distribution index (PDI) ranges from 200 to 990 kDa, and the PDI is 1.2 to 1.9. The PDI of copolymers obtained by some monomer combinations is as low as 1.2, indicating excellent polymerization controllability.

[0138] 2. Thermal properties: The glass transition temperature (T) of most copolymers g The temperature range is 40~70℃, and the temperature of norbornene copolymer containing benzo[a]substituents is T. g The temperature can be increased to 100~170℃; the main chain thermal decomposition temperature is 330~360℃, and the thermal stability is good.

[0139] 3. Mechanical properties: Tensile strength ≥ 12 MPa, elastic modulus ≥ 350 MPa, elongation at break up to 184%, toughness ≥ 17 MJ·m -3 It far surpasses homopolymers and random copolymers, possessing both high strength, high modulus, and excellent ductility.

[0140] The alternating cyclic olefin copolymers of this application, with their regular structure, balanced mechanical properties, heat and solvent resistance, optical transparency, and excellent biocompatibility, can be widely used in the fields of high-performance elastomers, film materials, biomedical materials, and functional coating materials. Furthermore, the copolymers can be functionalized and customized by modifying the functional groups of monomers to expand their application scenarios according to actual needs. As elastomers, they can be used in high-end sealing, shock absorption, and fatigue-resistant components; as film materials, they are suitable for high-barrier, high-transparency, and dimensionally stable optical films and packaging films; in the biomedical field, they can be used to manufacture medical devices, in vitro diagnostic consumables, drug carriers, and implantable auxiliary materials, meeting sterilization and biosafety requirements; in functional coatings, they can be used to prepare wear-resistant, weather-resistant, corrosion-resistant, insulating, and surface-protective coatings, improving the service life and functionality of the substrate. In summary, the alternating cyclic olefin copolymers of this application provide a high-performance solution for the field of high-end polymer materials and have broad industrialization prospects.

[0141] The present application will be further described in detail below through specific embodiments. These embodiments are merely illustrative and should not be construed as limiting the present application. In the following embodiments, many details are described to facilitate a better understanding of the present application. However, those skilled in the art will readily recognize that some features may be omitted in different situations, or may be replaced by other devices, materials, or methods. In some cases, certain operations related to the present application are not shown or described in the specification to avoid obscuring the core parts of the present application with excessive description. For those skilled in the art, detailed description of these related operations is not necessary; a complete understanding of the related operations can be obtained from the description in the specification and general technical knowledge in the art.

[0142] Example

[0143] The synthesis of some raw materials in this example is as follows:

[0144] A1-1 Synthesis Technology Route:

[0145]

[0146] Under argon protection, compound S0 (Guangzhou Xiaofan Technology Co., Ltd. 6262-42-6) (1.0 equivalent) was added to anhydrous toluene (concentration 0.1 mol / L), stirred, and cooled to 0 °C. Subsequently, tributyltin hydride (Bu3SnH, 2.0 equivalent) was added dropwise to the reaction system. After the addition was complete, the reaction mixture was slowly raised to room temperature and stirred for 12 hours. The reaction progress was monitored by thin-layer chromatography (TLC, developing solvent: n-hexane / ethyl acetate = 20:1). After the starting material was completely consumed, the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography to finally obtain a colorless oily liquid compound, namely Al-1. The NMR results are as follows: 1 H NMR (400 MHz, CDCl3, δ ppm): 5.21 (s, 2H); 13 C NMR (100MHz, CDCl3, δ ppm): 128.3, 89.2.

[0147] A5-1 Synthesis Technology Route:

[0148]

[0149] Starting from 1,1-diphenylethylene (S1), the target product 1,1-diphenyl-substituted cyclopropene (A5-1) was constructed via a three-step reaction: First, using S1 (1.0 equivalent) as the substrate, a phase-transfer catalyzed [2+1] cycloaddition reaction occurred with tribromomethane (2.0~3.0 equivalent) and 10.0 equivalent of sodium hydroxide aqueous solution in dichloromethane under the action of the phase-transfer catalyst tetradecyltrimethylammonium bromide (TTAB, 0.1 equivalent). The in-situ generated dibromocarbene added to the double bond to give 1,1-diphenyl-2,2-dibromocyclopropane (S2). Second, using S2 (1.0 equivalent) as the substrate, selective debromination and hydrolysis were carried out in a tetrahydrofuran / diethyl ether mixed solvent in a low-valent titanium reduction system generated in situ from tetraisopropoxytitanium (1.2 equivalent) and ethyl magnesium bromide (2.5 equivalent), resulting in the cleavage of only one C-Br group. The first step involved the formation of a cyclopropene double bond, yielding 1,1-diphenyl-2-bromocyclopropane (S3). In the third step, using S3 (1.0 equivalent) as a substrate, and activated by 1.2 equivalents of 18-crown-6, it underwent a β-elimination reaction with potassium tert-butoxide (2.0–3.0 equivalents) in tetrahydrofuran, resulting in the removal of one molecule of HBr and successfully constructing a cyclopropene double bond, ultimately yielding the target product, 1,1-diphenyl-substituted cyclopropene (A5-1). The NMR results are as follows: 1H NMR (400 MHz, CDCl3) δ 7.55-7.47 (m, 2H), 7.36 (t, J = 7.5 Hz, 2H), 7.26 (s, 3H), 7.22-7.16(m, 1H), 7.14-7.00 (m, 3H), 6.92 (dd, J = 7.1, 1.9 Hz, 2H). 13 C NMR (100 MHz, CDCl3, δ ppm): 141.8, 129.2, 128.2, 126.2, 125.2, 46.8.

[0150] B3-1 Synthesis Technology Route:

[0151]

[0152] Starting with cyclohexene (S4, 1.0 equivalent), a [2+1] cycloaddition reaction was carried out with trichloroacetyl chloride (1.0~1.2 equivalent) in the presence of zinc powder (Zn, 2.5 equivalent) to give dichlorobicyclo[4.2.0]octanone S5. S5 (1.0 equivalent) underwent carbonyl reduction with sodium borohydride (1.5~2.0 equivalent), followed by methanesulfonyl anhydride (1.2~1.5 equivalent) in the presence of triethylamine (2.0~2.5 equivalent) to give the target product S6, i.e., B3-1. The NMR results are as follows: 1 HNMR (400 MHz, CDCl3) δ 5.96 (s, 2H), 2.76 (dd, 2H), 1.27-1.71 (m, 12H). 13 CNMR (100 MHz, CDCl3) δ 139.50, 48.20, 30.68, 28.81, 27.50, 26.36.

[0153] Experiment 1: Alternating copolymerization of cyclopropylene A1 and cyclopropylene A5 catalyzed by chiral ruthenium catalyst

[0154] The general formula for alternating copolymerization is as follows:

[0155]

[0156] 1. Copolymerization reaction: Under argon protection, 0.01 mmol of chiral ruthenium catalyst Cat.1 was added to a dry Shrek flask, dissolved in 10 mL of toluene, and stirred until dissolved. Then, 5 mmol of dichloro-substituted CPE monomer A1-1 and 5 mmol of diphenyl-substituted CPE monomer A5-1 were added, and the mixture was stirred at 0 °C for 5 min. The chiral ruthenium catalyst Cat.1 has the structure shown in formula (1), and the catalyst CCDC number is 2281666. The structural schematic diagram is shown below. Figure 1 As shown, the synthesis method of the catalyst is based on publicly available literature: Development of Highly Enantio- and Z-Selective Grubbs Catalysts via Controllable C–H Bond Activation (doi.org / 10.1021 / jacs.3c08420). The same catalyst was used in all the following experiments.

[0157] 2. Post-treatment: The reaction was terminated by adding 1 mL of vinyl ether. The reaction solution was poured into 100 mL of methanol to precipitate the solid, which was then filtered to obtain a solid. The solid was washed three times with methanol and dried under vacuum at 60 °C for 12 h to obtain the cyclic olefin alternating copolymer poly(A1-alt-A5-1) with a yield of 95%. The structural formula of the cyclic olefin alternating copolymer poly(A1-alt-A5-1) is as follows:

[0158]

[0159] Experiment 2: Alternating copolymerization of cyclopropylene A1 and cyclobutene B3 catalyzed by chiral ruthenium catalyst

[0160] The general formula for alternating copolymerization is as follows:

[0161]

[0162] 1. Copolymerization reaction: Under argon protection, 0.01 mmol of chiral ruthenium catalyst Cat.1 was added to a dry Shrek bottle, dissolved in 10 mL of toluene, stirred and dissolved, and then 5 mmol of dichloroCPE monomer A1-1 and 5 mmol of bicyclo[4.2.0]oct-1(8)-ene B3-1 were added and stirred at 0 °C for 5 min;

[0163] 2. Post-treatment: The reaction was terminated by adding 1 mL of vinyl ether. The reaction solution was poured into 100 mL of methanol to precipitate the solid, which was then filtered to obtain a solid. The solid was washed three times with methanol and dried under vacuum at 60 °C for 12 h to obtain the cyclic olefin alternating copolymer poly(A1-alt-B3-1) with a yield of 93%. The structural formula of the cyclic olefin alternating copolymer poly(A1-alt-B3-1) is as follows:

[0164]

[0165] Experiment 3: Alternating copolymerization of cyclopropylene A1 and norbornene C1 catalyzed by chiral ruthenium catalyst

[0166] The general formula for alternating copolymerization is as follows:

[0167]

[0168] 1. Copolymerization reaction: Under argon protection, 0.01 mmol of chiral ruthenium catalyst Cat.1 was added to a dry Shrek flask, dissolved in 10 mL of toluene, and stirred until dissolved. Then, 5 mmol of dichloro CPE monomer A1-1 and 5 mmol of NBE monomer C1-1 (Guangzhou Kemeng Biotechnology Co., Ltd. D060048) were added and stirred at 0 °C for 5 min.

[0169] 2. Post-treatment: The reaction was terminated by adding 1 mL of vinyl ether. The reaction solution was poured into 100 mL of methanol to precipitate the solid, which was then filtered to obtain a solid. The solid was washed three times with methanol and dried under vacuum at 60 °C for 12 h to obtain the cyclic olefin alternating copolymer poly(A1-alt-C1-1) with a yield of 93%. The structural formula of the cyclic olefin alternating copolymer poly(A1-alt-C1-1) is as follows:

[0170]

[0171] Experiment 4: Alternating copolymerization of cyclobutene B4 and cyclobutene B3 catalyzed by chiral ruthenium catalyst

[0172] The general formula for alternating copolymerization is as follows:

[0173]

[0174] 1. Copolymerization reaction: Under argon protection, 0.01 mmol of chiral ruthenium catalyst Cat.1 was added to a dry Shrek flask, dissolved in 10 mL of toluene, and stirred until dissolved. Then, 5 mmol of dichloroCBE monomer B4-2 (SIGMA-ALDRICH2957-95-1) and 5 mmol of bicyclo[4.2.0]oct-1(8)-ene B3-1 were added and stirred at room temperature for 5 min.

[0175] 2. Post-treatment: The reaction was terminated by adding 1 mL of vinyl ether. The reaction solution was poured into 100 mL of methanol to precipitate the solid, which was then filtered to obtain a solid. The solid was washed three times with methanol and dried under vacuum at 60 °C for 12 h to obtain the cyclic olefin alternating copolymer poly(B4-2-alt-B3-1) with a yield of 97%. The structural formula of the cyclic olefin alternating copolymer poly(B4-2-alt-B3-1) is as follows:

[0176]

[0177] Experiment 5: Alternating copolymerization of cyclobutene B4 and norbornene C1 catalyzed by chiral ruthenium catalyst

[0178] The general formula for alternating copolymerization is as follows:

[0179]

[0180] 1. Copolymerization reaction: Under argon protection, 0.01 mmol of chiral ruthenium catalyst Cat.1 was added to a dry Shrek flask, dissolved in 10 mL of toluene, and stirred until dissolved. Then, 5 mmol of dichloro CBE monomer B4-2 (SIGMA-ALDRICH2957-95-1) and 5 mmol of NBE monomer C1-1 (Guangzhou Kemeng Biotechnology Co., Ltd. D060048) were added and stirred at room temperature for 30 min.

[0181] 2. Post-treatment: The reaction was terminated by adding 1 mL of vinyl ether. The reaction solution was poured into 100 mL of methanol to precipitate the solid, which was then filtered to obtain a solid. The solid was washed three times with methanol and dried under vacuum at 60 °C for 12 h to obtain the cyclic olefin alternating copolymer poly(B4-2-alt-C1-1) with a yield of 91%. The structural formula of the cyclic olefin alternating copolymer poly(B4-2-alt-C1-1) is as follows:

[0182]

[0183] Experiment 6: Alternating copolymerization of norbornene C1 and norbornene C2 catalyzed by chiral ruthenium catalyst

[0184] The general formula for alternating copolymerization is as follows:

[0185]

[0186] 1. Copolymerization reaction: Under argon protection, 0.01 mmol of chiral ruthenium catalyst Cat.1 was added to a dry Shrek flask, dissolved in 10 mL of toluene, and stirred until dissolved. Then, 5 mmol of NBE monomer C1-1 (Guangzhou Kemeng Biotechnology Co., Ltd. D060048) and 5 mmol of phenyl-substituted NBE monomer C2-1 (Shanghai Bid Pharmaceutical Technology Co., Ltd. BD54659) were added, and stirred at room temperature for 60 min.

[0187] 2. Post-treatment: The reaction was terminated by adding 1 mL of vinyl ether. The reaction solution was poured into 100 mL of methanol to precipitate the solid, which was then filtered to obtain a solid. The solid was washed three times with methanol and dried under vacuum at 60 °C for 12 h to obtain the cyclic olefin alternating copolymer poly (C1-1-alt-C2-1) with a yield of 92%. The structural formula of the cyclic olefin alternating copolymer poly (C1-1-alt-C2-1) is as follows:

[0188]

[0189] The alternating copolymers prepared in Experiments 1 to 6 were characterized by gel permeation chromatography (GPC), one-dimensional / two-dimensional nuclear magnetic resonance, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile testing. The specific test methods are as follows:

[0190] GPC test: Number average molecular weight of the sample (M n The molecular weight and distribution index (Đ = Mw / Mn) were determined using a Waters 1515 gel permeation chromatography (GPC) system equipped with a differential refractive index (RI), with polystyrene as the standard. The chromatographic column used tetrahydrofuran (THF) as the mobile phase, with a flow rate of 1.0 mL / min and a column temperature of 40 °C. Before testing, a 5.0 mg / mL solution of the sample and standard THF was prepared, filtered through a 0.22 μm filter membrane, and injected. The final molecular weight data were calculated using the standard curve method.

[0191] TGA Test Method: The decomposition temperature (Td, defined as the temperature at which a 5% mass loss occurs) of the polymer was determined using a TA Instrument Q50 thermogravimetric analyzer (TGA). The TGA analyzer was turned on and a nitrogen (N2) gas flow was introduced. After the instrument baseline stabilized, an appropriate amount of polymer sample was placed in a TGA-specific crucible, weighed accurately, and the value was recorded. The nitrogen gas flow conditions were set, and the sample was heated from room temperature to 700 °C at a heating rate of 10 °C / min. The crucible containing the sample was placed in the test chamber, and the test was started. The mass change curve of the sample with temperature was recorded in real time. The curve was analyzed using the instrument's software to determine the temperature corresponding to a 5% mass loss, which is Td. After the test, the heating program was turned off, and the crucible was removed after the instrument cooled to room temperature. The apparatus was cleaned up, and the nitrogen gas and instrument power were turned off.

[0192] DSC Testing: The thermal properties of the polymer were characterized using a TA DSC 2500 differential scanning calorimeter (DSC). The DSC analyzer was turned on and inert gas was introduced for protection. The baseline was calibrated until the instrument was operating normally. An appropriate amount of polymer sample was accurately weighed and sealed in a dedicated aluminum crucible for DSC. An empty aluminum crucible was used as a reference. A "heat-cool-heat" program was used, with heating and cooling at a constant rate of 10 °C / min within the range of -80 to 160 °C. The sample crucible and the reference crucible were placed in their corresponding positions to start the test, and the heat flow versus temperature curve was recorded. The curve was analyzed using the instrument's software, and the glass transition temperature (Tg) was read from the second heating scan. g After the test is completed, close the test program, wait for the instrument to cool to room temperature, remove the crucible, clean the test chamber, and turn off the instrument power and inert gas.

[0193] Mechanical property testing method: Tensile properties of the samples were tested at room temperature using a CMT1500 electronic universal testing machine. The relative humidity was approximately 30%, and the tensile rate was set to 5 mm / min. The samples used were dumbbell-shaped specimens with a gauge length of 2 mm, a length of 20 mm, and a thickness of approximately 0.5 mm. Each group of samples was tested in parallel five times, and the average value was taken as the final test result.

[0194] GPC spectrum as shown Figures 2 to 7 As shown, Figures 2 to 7 The GPC spectra of the alternating copolymers from Experiment 1 to Experiment 6 are shown in sequence; the DSC spectra are as follows. Figure 8 As shown; TGA spectrum as follows Figure 9 As shown; the mechanical property curves of the partially alternating copolymers are as follows. Figure 10 The results are shown in Table 2; the remaining results are shown in Table 1.

[0195] Table 1. NMR data and M values ​​of the alternating copolymers obtained from each experiment. n and T g

[0196] serial number Alternating copolymers NMR spectroscopy H spectrum NMR C-spectrum Experiment 1 <![CDATA[M n = 195 kDaPDI = 1.4T g =69 ℃T d = 352 ℃]]> <![CDATA[ 1 H (400 MHz, CDCl3): δ 7.29-7.51 (m, 10H), 6.24-6.311(m, 2H), 5.53-5.68 (m, 2H) ppm]]> <![CDATA[ 13 C (101 MHz, CDCl3): δ 137.4, 129.2,129.1,127.5,127.3,126.4,126.3,125.8, 125.7, 72.7 ppm]]> Experiment 2 <![CDATA[M n = 193 kDaPDI = 1.4T g =51 ℃T d = 331 ℃]]> <![CDATA[ 1 H (400 MHz, CDCl3): δ 5.31-5.87 (m, 4H), 2.10-2.55(m, 4H), 1.23-1.73 (m, 8H) ppm]]> <![CDATA[ 13 C (101 MHz, CDCl3): δ 137.5, 135.5,127.8,126.8,75.3, 41.3, 37.2, 36.2, 31.6, 31.5 ppm]]> Experiment 3 <![CDATA[M n = 261 kDaPDI = 1.6T g =49 ℃T d = 353 ℃]]> <![CDATA[ 1 H (400 MHz, CDCl3): δ 5.43-5.65 (m, 4H), 2.14-2.20(m, 2H), 1.03-1.75 (m, 6H), ppm]]> <![CDATA[ 13 C (101 MHz, CDCl3): δ 137.5, 137.4, 127.8, 127.6,72.6, 44.4, 35.1, 35.0, 34.6, 36.5 ppm]]> Experiment 4 <![CDATA[M n = 169 kDaPDI = 1.7T g =64 ℃T d = 354 ℃]]> <![CDATA[ 1 H (400 MHz, CDCl3): δ 5.49-5.93 (m, 4H), 4.22-4.74(m, 2H), 2.03-2.55 (m, 2H), 1.04-1.83 (m, 8H) ppm]]> <![CDATA[ 13 C (101 MHz, CDCl3): δ 137.7,137.6, 125.9, 125.8,56.1, 56.0, 36.7, 36.6, 31.6, 31.5, 26.3, 26.2 ppm]]> Experiment 5 <![CDATA[M n = 456 kDaPDI = 1.6T g =68 ℃T d = 330 ℃]]> <![CDATA[ 1 H (400 MHz, CDCl3): δ 5.22-6.03 (m, 6H), 2.11-2.23(m, 2H), 1.08-1.82 (m, 6H), ppm]]> <![CDATA[ 13 C (101 MHz, CDCl3): δ 137.5, 137.3, 127.8, 127.7,56.7, 56.8, 44.6, 35.1, 35.0, 34.6, 36.4 ppm]]> Experiment 6 <![CDATA[M n = 201 kDaPDI = 1.7T g =109 ℃T d = 349 ℃]]> <![CDATA[ 1 H (400 MHz, CDCl3): δ 7.13-7.24 (m, 4H), 5.33-6.21(m, 4H), 3.47-3.74 (m, 2H), 1.05-2.35 (m, 10H) ppm]]> <![CDATA[ 13 C (101 MHz, CDCl3): δ 151.9, 151.8, 131.8, 131.7,129.1, 129.0, 126.1, 125.9, 121.4, 121.3, 49.6,44.7, 39.2, 39.1, 36.5, 36.3, 34.6, 34.5 ppm]]>

[0197] Table 2. Test results of mechanical properties of poly(B4-2-alt-C1-1)

[0198] Tensile strength Elongation at break elastic modulus toughness poly(B4-2-alt-C1-1) 12.45 MPa 184.3% 357.2 MPa <![CDATA[17.29 MJ·m -3 ]]>

[0199] Whether 1:1 insertion is possible is determined by the monomer conversion rate of copolymerization and self-polymerization systems. Specifically, the real-time monomer conversion rate is monitored using coarse NMR spectroscopy. Some results are shown below. Figure 11 As shown. The linear fitting curve of poly(B4-2-alt-C1-1) for polyvinyl chloride is as follows. Figure 12As shown. Real-time conversion results indicate that the two monomers are converted in a 1:1 ratio, and the curve of the self-polymerization system rules out self-polymerization blending. Figure 11 As shown; meanwhile, for example, from the copolymerization rate of poly(B4-2-alt-C1-1), r1=0.0385, r2=0.0022, r1≈r2≈0, it can be seen that the copolymerization rate is significantly faster than that of homopolymerization, which further supports the formation of alternating copolymerization.

[0200] In summary, the NMR results show that the cyclic olefin ring-opening alternating copolymer prepared in this example has a precise 1:1 alternating insertion copolymer structure with high alternation degree; furthermore, the number-average molecular weight (M0) of the cyclic olefin ring-opening alternating copolymer prepared in this example is high. n The molecular weight distribution index (PDI) is between 1.2 and 1.9, with some monomer combinations yielding copolymers with a PDI as low as 1.2, demonstrating excellent polymerization controllability. The glass transition temperature (Tg) of most copolymers is also high. g (T) Norbornene copolymers containing benzo[a]substituents, at temperatures between 40 and 70°C g The temperature can be increased to 100~170℃; the main chain thermal decomposition temperature is between 330~360℃, and the thermal stability is good; in terms of mechanical properties, the copolymer in this example has a tensile strength ≥12 MPa, an elastic modulus ≥350 MPa, an elongation at break of 184%, and a toughness ≥17 MJ·m. -3 It far surpasses homopolymers and random copolymers, possessing high strength, high modulus, and excellent ductility; Table 2 only provides test data for poly(B4-2-alt-C1-1), while the performance of other alternating copolymers is comparable.

[0201] The above description, in conjunction with specific embodiments, provides a further detailed explanation of this application and should not be construed as limiting the specific implementation of this application to these descriptions. Those skilled in the art to which this application pertains can make several simple deductions or substitutions without departing from the concept of this application.

Claims

1. A cyclic olefin ring-opening metathesis alternating copolymer, characterized in that: It is formed by alternating 1:1 ring-opening metathesis of any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene.

2. The cyclic olefin ring-opening metastasis alternating copolymer according to claim 1, characterized in that: The substituted cyclopropene has the structure shown in Formula A, the substituted cyclobutene has the structure shown in Formula B, and the substituted norbornene has the structure shown in Formula C. 、 、 ， Ring-opening metathesis 1:1 alternating copolymerization reactions occur between cyclopropenes with different substituents, between cyclobutenes with different substituents, between norbornene with different substituents, between cyclopropene and cyclobutene, between cyclopropene and norbornene, or between cyclobutene and norbornene.

3. The cyclic olefin ring-opening alternating copolymer according to claim 2, characterized in that: The substituted cyclopropene is at least one of the structures shown in A1, A2, A3, A4, and A5. ； Wherein, x is at least one of Cl, Br, and F; The groups attached to the 2nd, 3rd, and 4th carbons of the Ar group are at least one of H, F, Cl, Br, CF3, OMe, Me, iPr, tBu, NO2, CN, NH2, OH, and COOMe, and / or the groups attached to the 2nd, 4th, and 6th carbons of the Ar group are at least one of F, Br, CF3, OMe, Me, and Et, and / or the groups attached to the 3rd and 5th carbons of the Ar group are at least one of F, Br, CF3, OMe, Me, and Et; R1 is selected from Me, Et, iPr, tBu, OH, OMe, NH2, NMe2 or COOMe, and R2 is selected from H, Me, Et, iPr or tBu.

4. The cyclic olefin ring-opening alternating copolymer according to claim 2, characterized in that: The substituted cyclobutene is at least one of the structures shown in B1, B2, B3, B4, and B5. ； Where x is O or SO2, and n is 1, 2 or 3; R3 and R5 can be repeatedly selected from COCH3, COCl3, COCF3, Ts, Boc, Cbz, Me, Et, iPr, tBu, Ph or Hex; R4 is selected from F, Cl, Br, OH, OMe, OTBS, COOMe, Bn, CH2OH, CH2OBn, CH2OBz, CH2NH, CH2NMe2, CH2tBu, or CH2OBoc.

5. The cyclic olefin ring-opening alternating copolymer according to claim 2, characterized in that: The substituted or unsubstituted norbornene is at least one of the structures shown in C1, C2, C3, C4, and C5. ； Where x is O, S, NMe, CH2, CMe2, CHBr, or CPE; The groups attached to the 2nd and 3rd carbons of the Ar group are at least one of F, Cl, Br, CF3, OMe, Me, Et, iPr, tBu, NO2, CN, NH2, OH, OEt, and COOMe. R6 is selected from H, Me, CHO, CN, COCH3, OCOCH3, COOH, Boc, COOEt, CH2NH2, CH2Br, Vinyl, or Ethylidene; R7 is selected from Me, H, Ph, COCH3, OCOCH3, COOH, COOEt, CH2NH2, CH2Br, Bn, or OMe.

6. The method for preparing the cyclic olefin ring-opening alternating copolymer according to any one of claims 1-5, characterized in that: The method includes using any two cyclic olefin monomers selected from substituted or unsubstituted cyclopropylene, substituted or unsubstituted cyclobutene, and substituted or unsubstituted norbornene as raw materials, and employing a chiral ruthenium catalyst to perform a 1:1 alternating ring-opening and metastasis copolymerization reaction of the two cyclic olefin monomers to generate the cyclic olefin alternating ring-opening and metastasis copolymer. The chiral ruthenium catalyst has the structure shown in formula (1). Equation (1) , In formula (1), R1 is phenyl, R2 is isopropyl, R3 isopropyl, R4 is hydrogen, R5 is tert-butyl, and R6 isopropyl.

7. The preparation method according to claim 6, characterized in that: The reaction temperature for the alternating copolymerization reaction is -10℃ to 50℃.

8. The preparation method according to claim 6, characterized in that: The alternating copolymerization reaction is carried out under inert gas protection; Optionally, the inert gas includes at least one of argon and nitrogen.

9. The preparation method according to any one of claims 6-8, characterized in that: The molar ratio of the two cyclic olefin monomers is 1:1; And / or, the molar ratio of the chiral ruthenium catalyst to the monomer is 1:(200~1000); And / or, the alternating copolymerization reaction is carried out in a solvent; And / or, the solvent is at least one of dichloromethane, toluene, n-hexane, haloalkanes, aromatic hydrocarbons, and aliphatic hydrocarbons; And / or, the alternating copolymerization reaction takes 10 to 60 minutes.

10. The use of the cyclic olefin ring-opening alternating copolymer according to any one of claims 1-5 in the preparation of elastomer materials, film materials, biomedical materials or functional coating materials.

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