A method for chain shuttling production of narrow distribution cyclic olefin block copolymers using a non-metallocene catalyst

Abstract

The present application relates to the field of synthesizing narrow distribution cyclic olefin multi-block copolymer by chain shuttling method, and particularly relates to a method for preparing narrow distribution cyclic olefin block copolymer by non-metallocene catalyst chain shuttling. The method for preparing narrow distribution cyclic olefin block copolymer by non-metallocene catalyst chain shuttling comprises the following steps: carrying out chain shuttling polymerization reaction of cyclic olefin monomer and ethylene in the presence of a chain shuttling agent under the action of a non-metallocene mixed catalyst; the non-metallocene mixed catalyst comprises a beta-diketone monoimine catalyst and a salicylaldimine catalyst. The present application synthesizes cyclic olefin multi-block copolymer by selecting two non-metallocene catalysts with similar structures and large differences in selectivity for ethylene and cyclic olefin comonomer for the first time. The present application synthesizes soft / hard alternating narrow distribution cyclic olefin multi-block copolymer with low cyclic olefin insertion rate segments as soft segments and high cyclic olefin insertion rate segments as hard segments.

Description

Technical Field

[0001] This invention relates to the field of synthesizing narrowly distributed cyclic olefin multiblock copolymers by chain shuttle method, and particularly to a method for preparing narrowly distributed cyclic olefin block copolymers by chain shuttle method using a non-metallocene catalyst. Background Technology

[0002] Cycloolefin copolymers (COCs) are an important class of high-performance thermoplastic materials, typically copolymerized from olefins such as ethylene and cycloolefin monomers such as norbornene. Due to their unique molecular structure, COC materials possess a range of superior properties, such as high transparency (close to PMMA), low birefringence, excellent water vapor barrier properties, low density, and good heat and chemical resistance. Therefore, COCs are widely used in high-end optical components (such as lenses and displays), medical devices (such as syringes and pre-filled packaging), capacitor films, and food packaging.

[0003] Currently, commercially available COC materials are typically prepared via coordination polymerization using a single-center metallocene catalyst, resulting in polymer chains that are mostly random copolymers. However, these traditional COC materials suffer from a significant performance defect: high brittleness. To achieve a high glass transition temperature (Tg) to meet the requirements of heat-resistant applications, the insertion rate of cyclic olefin monomers (such as norbornene) needs to be increased during polymerization. High insertion rates result in rigid cyclic olefin segments, leading to a sharp decrease in molecular chain flexibility. Macroscopically, this manifests as extremely low elongation at break (typically around 2-3%), exhibiting obvious brittle fracture characteristics, which severely limits their application in scenarios requiring a certain degree of flexibility or impact resistance.

[0004] Block copolymers, by linking segments with different properties through chemical bonds, achieve synergistic and balanced material properties, such as the classic thermoplastic elastomer SBS. Inspired by this, researchers began exploring the synthesis of cycloolefin block copolymers (COBCs), hoping to toughen high-Tg "hard segments" by introducing low-Tg "soft segments." However, traditional methods for synthesizing cycloolefin block copolymers, such as those using olefin-active polymerization catalysts and employing segmented feeding, suffer from harsh reaction conditions and low production efficiency, making them unsuitable for large-scale industrial production.

[0005] Chain-shutling polymerization (CSP) offers a novel and efficient method for the preparation of olefin block copolymers. By combining two or more catalysts with different monomer selectivities and a chain shuttle (such as diethylzinc), polymer chains can reversibly transfer between different active sites, enabling the efficient one-pot preparation of multi-block copolymers with alternating hard and soft segments in a single polymerization process. However, successfully applying CSP to the preparation of cyclic olefin multi-block copolymers still faces numerous challenges. For example, poor chain shuttle efficiency can lead to heterogeneous product composition and a high content of homopolymers; or the catalyst may undergo uncontrollable transfer reactions beyond those to the chain transfer agent. The key lies in developing catalyst combinations with matched polymerization activities and significantly different copolymerization capabilities for cyclic olefin monomers to obtain uniformly distributed, structurally and structurally stable COC block copolymers. Currently, although there are research reports on ethylene-norbornene block copolymers, the range of control over their mechanical properties, especially how to achieve a significant improvement in toughness while maintaining high transparency and strength, still requires further investigation.

[0006] In summary, developing a highly efficient chain-shuttle catalytic system that can effectively control the chain structure of cyclic olefin multi-block copolymers through a simple process, combining copolymer segment structures with high and low insertion rates, and achieving uniform molecular chain composition and distribution with a component distribution of <1.83, thereby significantly improving the toughness of the material while maintaining its high transparency and high heat resistance, and realizing a highly efficient and tunable preparation method from plastics to elastomers, has significant research value and broad application prospects. Summary of the Invention

[0007] Based on the above, the present invention provides a method for preparing narrowly distributed cyclic olefin block copolymers by non-metallocene catalyst chain shuttle.

[0008] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention is a method for preparing narrowly distributed cyclic olefin block copolymers by non-metallocene catalyst chain shuttle, comprising the following steps: In the presence of a chain shuttle agent, cyclic olefin monomers and ethylene undergo chain shuttle polymerization under the action of a non-metallocene mixed catalyst. The non-metallocene mixed catalyst includes a β-diketone monoimide catalyst and a salicylaldehyde imide catalyst.

[0009] In a preferred embodiment of the present invention, the general structural formula of the β-diketone monoimine catalyst is shown in Formula (I); the general structural formula of the salicylaldehyde imine catalyst is shown in Formula (II). Equation (I); Formula (II); In formula (Ⅰ), when R1 = Ph, R2 = CF3 or CH3; when R1 = thiophene, R2 = CF3; when R1 = furanyl, R2 = CF3; when R1 = CF3, R2 = CH3; when R1 = CH3, R2 = CF3; R3 is an alkyl or aromatic group; X is Me, Cl, Bn or NMe2; M is Ti, Zr or Hf; In equation (II), when R1= t When Bu, R2 = t Bu or H; when R1=Ph, R2=Ph or H; when R1=CPhMe2, R2=CPhMe2 or H; when R1=CPh2Me, R2=CPh2Me or H; when R1=CPh3, R2=CPh3 or H; R3 is an alkyl or aromatic group; X is Me, Cl, Bn or NMe2; M is Ti, Zr or Hf.

[0010] In a preferred embodiment of the present invention, the molar ratio of the β-diketone monoimide catalyst and the salicylaldehyde imide catalyst in the non-metallocene mixed catalyst is 5:1 to 1:5. More preferably, the molar ratio of the β-diketone monoimide catalyst and the salicylaldehyde imide catalyst in the non-metallocene mixed catalyst is 1:1, 1:2, 1:3, 1:4, 1:5, or any value between the two aforementioned ratios.

[0011] In a preferred embodiment of the present invention, the chain shuttle is diethylzinc; the amount of the chain shuttle added is 5 to 80 times (preferably 10 to 50 times) the amount of the non-metallocene mixed catalyst.

[0012] In a preferred embodiment of the present invention, the cyclic olefin monomer is one or more of norbornene, norbornediene, dicyclopentadiene, and dimethyl-bridged octahydronaphthalene, and its concentration in the reaction system is 0.15–1.0 mol / L.

[0013] In a preferred embodiment of the present invention, the chain shuttle polymerization reaction is carried out under an ethylene atmosphere, with an ethylene pressure of 1~5 atm, a polymerization temperature of 25~80 ℃, and a polymerization time of 1~10 min.

[0014] In a preferred embodiment of the present invention, a co-catalyst is also added to the reaction system.

[0015] In a preferred embodiment of the present invention, the co-catalyst is one or more of methylaluminoxane, a mixture of triisobutylaluminum and tris(pentafluorophenyl)borane, a mixture of triisobutylaluminum and triphenylcarbazone(pentafluorophenyl)borate, and modified methylaluminoxane; the molar ratio of the co-catalyst to the non-metallocene mixed catalyst is 2000:1 to 100:1. After the chain shuttle polymerization reaction is completed, the process further includes quenching, precipitation, and drying steps. The drying temperature is 60-80 ℃, and the drying time is 6-8 hours.

[0016] The quenching agent used is an acidified ethanol solution, and the acid used is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and formic acid. The volume fraction of the acid in the acidified ethanol solution is 10%.

[0017] The reaction system uses an inert organic solvent; the inert organic solvent is one or more of straight-chain hydrocarbons, cyclic hydrocarbons, and aromatic hydrocarbons. Preferably, the solvent is toluene.

[0018] This invention is the first to synthesize cyclic olefin multiblock copolymers by selecting two non-metallocene catalysts with significant differences in selectivity for ethylene and cyclic olefin comonomers and similar structures. In a polymerization system, the two catalysts, combined with a cocatalyst and a chain transfer agent, undergo chain shuttle polymerization to synthesize narrowly distributed cyclic olefin multiblock copolymers with alternating soft / hard segments, characterized by soft segments with low cyclic olefin insertion rates and hard segments with high cyclic olefin insertion rates.

[0019] The second technical solution of the present invention is a cyclic olefin block copolymer prepared by the above method.

[0020] The third technical solution of the present invention is the application of the above-mentioned cyclic olefin block copolymer in the preparation of optical components, medical devices, capacitor films or food packaging materials.

[0021] Compared with the prior art, the present invention has the following beneficial effects: This invention utilizes catalysts with different selectivity for cyclic olefin monomers during the polymerization process to prepare unimodal cyclic olefin multiblock copolymers via chain shuttle polymerization. By adjusting the content of soft and hard segments, high-performance COC materials can be obtained. The continuous polymerization process enables one-pot preparation of cyclic olefin multiblock copolymers, showing broad prospects for industrial applications.

[0022] The cyclic olefin block copolymers prepared by the method of this invention have excellent temperature resistance, excellent visible light transmittance, adjustable elongation at break within a certain range, and significantly enhanced toughness. The preparation method is simple and convenient, and it has very important application prospects for COC polymer modification and expansion of application fields. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 The GPC curve of the cyclic olefin block copolymer obtained in Example 1 of this invention; Figure 2 The GPC curve of the cyclic olefin block copolymer obtained in Example 2 of this invention; Figure 3 The GPC curve of the cyclic olefin block copolymer obtained in Example 3 of this invention; Figure 4 The GPC curve of the cyclic olefin block copolymer obtained in Example 4 of this invention; Figure 5 The GPC curve of the cyclic olefin block copolymer obtained in Example 5 of this invention; Figure 6 The GPC curve of the cyclic olefin block copolymer obtained in Example 6 of this invention; Figure 7 The GPC curve of the cyclic olefin block copolymer obtained in Example 7 of this invention; Figure 8 The GPC curve of the cyclic olefin block copolymer obtained in Example 8 of this invention; Figure 9 The differential scanning calorimetry (DSC) second-rise curves of the cyclic olefin block copolymers obtained in Examples 1-3 of this invention are shown below. Figure 10 The stress-strain curves of the cyclic olefin block copolymers obtained in Examples 1-3 of this invention are shown. Figure 11 The stress-strain curves of the cyclic olefin block copolymers obtained in Examples 4-8 of this invention are shown. Figure 12 Stress-strain curves for commercial material Topas 6013; Figure 13 The stress-strain curves are of the cyclic olefin block copolymers obtained in Examples 1-2 and the cyclic olefin copolymers obtained in Comparative Examples 1-2 of this invention. Figure 14 The transmittance curves are for the cyclic olefin block copolymers obtained in Examples 1, 3, 7, and 8 of this invention. Figure 15 The 1H NMR spectrum of the cyclic olefin block copolymer prepared in Example 1 of this invention; Figure 16The carbon NMR spectrum of the cyclic olefin block copolymer prepared in Example 1 of this invention; Figure 17 This is the carbon NMR spectrum of the cyclic olefin block copolymer obtained in Example 2 of the present invention. Detailed Implementation

[0025] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0026] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0027] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0028] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0029] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0030] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0031] In the embodiments of the present invention, the β-diketone monoimide catalyst and salicylaldehyde imide catalyst are prepared by condensation reaction. The obtained ligand is mixed with a metal source at a ratio of 1:1 to obtain the corresponding catalyst.

[0032] The synthesis steps of β-diketone monoimine catalyst are as follows: (1) 20 mmol of β-diketone and the corresponding aniline were mixed 1:1 and added to a 100 mL round-bottom flask. 50 mL of methanol was added to dissolve the mixture, and 1 mL of formic acid was added as a catalyst. The mixture was purged with nitrogen for 5 min and refluxed for 48 h. The reaction was monitored by TLC plate. The substrate disappeared, indicating that the reaction was complete. Heating was then stopped. Methanol was removed to obtain a dark red oily crude product. The product was separated by column chromatography (petroleum ether / ethyl acetate = 100 / 1, v / v) to obtain the target product.

[0033] (2) Under a nitrogen atmosphere, 2 mmol of the ligand was added to a 100 mL Schlenk flask, dissolved in 20 mL of anhydrous diethyl ether, cooled to -78 °C, and 0.8 mL of a hexane solution of n-butyllithium (2.5 mol / L, 2 mmol) was slowly added dropwise. The solution gradually turned red. After returning to room temperature, the reaction was carried out for 2 h. At -78 °C, the solution was transferred to another 100 mL Schlenk flask containing 1 mmol of TiCl4 diethyl ether solution within 30 min. The solution gradually turned blackish-red. After returning to room temperature, the reaction was carried out for 12 h. The solvent was dried under vacuum, 20 mL of dichloromethane was added, and the mixture was filtered under vacuum. The filtrate was dried under vacuum, and the residue was washed with 20 mL of n-hexane to obtain the target catalyst.

[0034] The synthesis steps of the salicylaldehyde-imine catalyst are as follows: (1) 20 mmol of salicylaldehyde and the corresponding aniline were mixed 1:1 and added to a 100 mL round-bottom flask. 50 mL of methanol was added to dissolve the mixture, and 1 mL of formic acid was added as a catalyst. The mixture was purged with nitrogen for 5 min and refluxed for 48 h. The reaction was monitored by TLC plate. The substrate disappeared, indicating that the reaction was complete. Heating was then stopped. Methanol was removed to obtain a yellow crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 20 / 1, v / v) to obtain the target product.

[0035] (2) Under a nitrogen atmosphere, 2 mmol of the ligand was added to a 100 mL Schlenk flask, dissolved in 20 mL of anhydrous diethyl ether, cooled to -78 °C, and 0.8 mL of a hexane solution of n-butyllithium (2.5 mol / L, 2 mmol) was slowly added dropwise. The solution gradually turned red. After returning to room temperature, the reaction was carried out for 2 h. At -78 °C, the solution was transferred to another 100 mL Schlenk flask containing 1 mmol of TiCl4 diethyl ether solution within 30 min. The solution gradually turned blackish-red. After returning to room temperature, the reaction was carried out for 12 h. The solvent was dried under vacuum, 20 mL of dichloromethane was added, and the mixture was filtered under vacuum. The filtrate was dried under vacuum, and the residue was washed with 20 mL of n-hexane to obtain the target catalyst.

[0036] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0037] In the following examples, the glass transition temperature of the polymer was determined using a TA Q2000 differential scanning calorimeter. The heating rate was 20 °C / min, the cooling rate was 20 °C / min, and the scanning range was -50 to 200 °C. A two-stage heating curve was used. The tensile mechanical properties of the obtained polymer were tested using an Instron 3369 universal testing machine. The molecular weight and distribution of the polymer were determined using an Agilent PL-GPC220 high-temperature gel permeation chromatography system at 150 °C. The mobile phase was 1,2,4-trichlorobenzene with 0.05 wt% 2,6-di-tert-butyl-4-methylphenol added as an antioxidant. The flow rate was set to 1.0 mL / min, and PL EasiCal PS-1 was used as a standard. The polymer's... 1 H and 13 C10 NMR was measured by a Bruker-400 NMR spectrometer at 120 °C, with TMS as an internal standard and deuterated o-dichlorobenzene or deuterated 1,1,2,2-tetrachloroethane as the solvent. The transmittance of the polymer was measured at room temperature using a Shimadzu UV2700 visible-ultraviolet spectrophotometer.

[0038] Example 1 This embodiment describes a polymerization process at a polymerization temperature of 25°C, an ethylene pressure of 1 atm, a diethylzinc molar content 50 times that of the mixed catalyst, and a mixed catalyst consisting of a β-diketone monoimide catalyst (R1 = CF3, R2 = CH3, R3 = Ph, M = Ti, X = Cl) and a salicylaldehyde imide catalyst (R1 = ...). t Bu, R2 = t Chain shuttle polymerization was carried out with a molar ratio of Bu, R3=C6F5, M=Ti, X=Cl of 1:1 and a polymerization time of 10 min.

[0039] In this embodiment, the chain shuttle polymerization steps are as follows: (1) Weighing the chain shuttle catalyst: Weigh 5 kiloton monoimide catalysts using an analytical balance in the glove box. μ mol and salicylaldehyde imine catalyst 5 μ mol, with a molar ratio of 1:1, is fully dissolved in toluene and reserved for later use.

[0040] (2) Adding cyclic olefin monomers and adjusting polymerization temperature: Add norbornene monomer dissolved in toluene (the molar amount of norbornene relative to the volume of toluene in the polymerization reactor is 0.3 mol / L) to the polymerization reactor; introduce ethylene at a pressure of 1 atm; add toluene to flush the residual comonomer at the feed port so that all of it enters the polymerization reactor; adjust the temperature of the polymerization reactor to 25 ℃.

[0041] (3) Addition of co-catalyst and chain shuttle: Methylaluminoxane dissolved in toluene is added to the polymerization reactor as a co-catalyst (the molar ratio of co-catalyst to mixed catalyst is 1000:1); then diethylzinc dissolved in toluene is added to the polymerization reactor as a chain shuttle, and stirred for 3 min; the temperature of the polymerization reactor is kept at 25 °C.

[0042] (4) Add catalyst for chain shuttle polymerization: Keep the temperature of the polymerization reactor at 25 °C, use a syringe to quantitatively extract the mixed catalyst prepared in step (1) and add it to the polymerization container. Add toluene and rinse the mixed catalyst remaining at the feed port so that it is all in the polymerization reactor. The polymerization reaction time is 10 min.

[0043] (5) Termination of polymerization reaction: After the polymerization reaction reaches the polymerization time of 10 min, open the polymerization reactor and add a mixed solution of ethanol and hydrochloric acid. The volume fraction of hydrochloric acid in the mixed solution is 10%, which will quench the polymerization reaction.

[0044] (6) Polymer solution precipitation and drying: The polymer solution was poured into a mixed solution of ethanol and hydrochloric acid (the volume fraction of hydrochloric acid in the mixed solution was 10%), stirred to precipitate, filtered through a Buchner funnel, and dried in a vacuum drying oven at 60 °C for 8 hours to obtain 3.3 g of constant weight cyclic olefin multiblock copolymer.

[0045] High-temperature GPC analysis of the obtained polymer showed that, Figure 1 As shown, the horizontal axis is logM w The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 160 kDa, M n = 114 kDa, = 1.39), Figure 9 Studies of DSC and related physical properties show that chain shuttle polymerization can be achieved under these conditions to obtain cyclic olefin multiblock copolymers. Figure 10 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 74.4%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC.

[0046] Figure 14 It can be seen that the cyclic olefin multiblock copolymer has good light transmittance, with a transmittance of up to 83.6%.

[0047] The 1H NMR spectrum of the cyclic olefin block copolymer prepared in Example 1 is as follows: Figure 15As shown, the carbon NMR spectrum is as follows: Figure 16 As shown.

[0048] Example 2 The only difference from Example 1 is that the mixed catalyst β-diketone monoimide catalyst (R1=CF3, R2=CH3, R3=Ph, M=Ti, X=Cl) 5 μ mol and salicylaldehyde imine catalyst (R1= t Bu, R2 = t Bu, R3=C6F5, M=Ti, X=Cl) 15 μ The molar ratio was 1:3; the remaining steps and parameters were the same as in Example 1, and 3.9 g of constant-weight cyclic olefin multiblock copolymer was obtained.

[0049] High-temperature GPC analysis of the obtained polymer showed that, Figure 2 As shown, the horizontal axis is logM w The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 97 kDa, M n = 64 kDa, = 1.51), Figure 9 Studies of DSC and related physical properties show that chain shuttle polymerization can be achieved under these conditions to obtain cyclic olefin multiblock copolymers. Figure 10 The figure shows the stress-strain curve, and it can be seen from the graph that the elongation at break of the cyclic olefin multiblock copolymer is 109.1%. Figure 12 The stress-strain curve of the commercially available Topas 6013 shows an elongation at break of only 4.1%, indicating a significant improvement in the toughness of the COC. The carbon NMR spectrum of the cyclic olefin block copolymer prepared in Example 2 is shown below. Figure 17 As shown.

[0050] Example 3 The only difference from Example 1 is that the mixed catalyst β-diketone monoimide catalyst (R1=CF3, R2=CH3, R3=Ph, M=Ti, X=Cl) 5 μ mol and salicylaldehyde imine catalyst (R1= t Bu, R2 = t Bu, R3=C6F5, M=Ti, X=Cl) 25 μ The molar ratio was 1:5; the remaining steps and parameters were the same as in Example 1, and 4.0 g of constant-weight cyclic olefin multiblock copolymer was obtained.

[0051] High-temperature GPC analysis of the obtained polymer showed that, Figure 3 As shown, the horizontal axis is logMw The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 64 kDa, M n = 40 kDa, = 1.60). Figure 9 Studies of DSC and related physical properties demonstrate that chain shuttle polymerization can be achieved under these conditions, yielding cyclic olefin multiblock copolymers. Figure 10 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 135.8%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC.

[0052] Figure 14 It can be seen that the cyclic olefin multiblock copolymer has good light transmittance, with a transmittance of up to 87.6%.

[0053] Example 4 The only difference from Example 3 is that the molar content of diethylzinc is 20 times that of the mixed catalyst; the remaining steps and parameters are the same as in Example 3, and 4.5 g of constant-weight cyclic olefin multiblock copolymer is obtained.

[0054] High-temperature GPC analysis of the obtained polymer showed that, Figure 4 As shown, the horizontal axis is logM w The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 116 kDa, M n = 74 kDa, = 1.56). Figure 11 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 194.4%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC.

[0055] Example 5 The only difference from Example 3 is that the molar content of diethylzinc is 10 times that of the mixed catalyst; the rest of the steps and parameters are the same as in Example 3, and 3.9 g of constant-weight cyclic olefin multiblock copolymer is obtained.

[0056] High-temperature GPC analysis of the obtained polymer showed that, Figure 5 As shown, the horizontal axis is logM wThe molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 149 kDa, M n = 106 kDa, = 1.40). Figure 11 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 252.6%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC.

[0057] Example 6 The only difference from Example 4 is that the molar amount of norbornene relative to the volume of toluene in the polymerization reactor is 0.15 mol / L; the other steps and parameters are the same as in Example 4, and 3.7 g of constant-weight cyclic olefin multiblock copolymer is obtained.

[0058] High-temperature GPC analysis of the obtained polymer showed that, Figure 6 As shown, the horizontal axis is logM w The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 97 kDa, M n = 53 kDa, = 1.83). Figure 11 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 491.3%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC.

[0059] Example 7 The only difference from Example 4 is that the molar amount of norbornene is 0.6 mol / L relative to the volume of toluene in the polymerization reactor; the other steps and parameters are the same as in Example 4, and 4.3 g of constant-weight cyclic olefin multiblock copolymer is obtained.

[0060] High-temperature GPC analysis of the obtained polymer showed that, Figure 7 As shown, the horizontal axis is logM w The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 121 kDa, M n = 85 kDa, = 1.42). Figure 11 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 41.1%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC. Figure 14 It can be seen that the cyclic olefin multiblock copolymer has good light transmittance, with a transmittance of up to 90.9%.

[0061] Example 8 The only difference from Example 4 is that the molar amount of norbornene is 1.0 mol / L relative to the volume of toluene in the polymerization reactor; the other steps and parameters are the same as in Example 4, and 4.0 g of constant-weight cyclic olefin multiblock copolymer is obtained.

[0062] High-temperature GPC analysis of the obtained polymer showed that, Figure 8 As shown, the horizontal axis is logM w The molecular weight distribution exhibits a symmetrical unimodal distribution, and the molecular weight distribution varies within a relatively narrow range. M w = 91 kDa, M n = 68 kDa, = 1.34). Figure 11 The figure shows the stress-strain curve, indicating that the elongation at break of the cyclic olefin multiblock copolymer is 7.3%. Figure 12 The stress-strain curve of commercial Topas 6013 shows that the elongation at break is only 4.1%, indicating a significant improvement in the toughness of COC. Figure 14 It can be seen that the cyclic olefin multiblock copolymer has good light transmittance, with a transmittance of up to 92.3%.

[0063] Example 9 The only difference from Example 1 is that the mixed catalyst is a β-diketone monoimide catalyst (R1= Ph, R2= CF3, R3= Ph, M= Ti, X= Cl). μ mol and salicylaldehyde imine catalyst (R1= t Bu, R2 = t Bu, R3=C6F5, M=Ti, X=Cl) 25 μ mol; the remaining steps and parameters were the same as in Example 1, and 3.8 g of constant-weight cyclic olefin multiblock copolymer was obtained.

[0064] Example 10 The only difference from Example 1 is that the mixed catalyst is a β-diketone monoimine catalyst (R1 = thiophene, R2 = CF3, R3 = Ph, M = Ti, X = Cl). μmol and salicylaldehyde imine catalyst (R1= t Bu, R2 = t Bu, R3=C6F5, M=Ti, X=Cl) 25 μ mol; the remaining steps and parameters were the same as in Example 1, and 3.4 g of constant-weight cyclic olefin multiblock copolymer was obtained.

[0065] Example 11 The only difference from Example 1 is that the mixed catalyst is a β-diketone monoimide catalyst (R1 = furanyl, R2 = CF3, R3 = Ph, M = Ti, X = Cl). μ mol and salicylaldehyde imine catalyst (R1= t Bu, R2 = t Bu, R3=C6F5, M=Ti, X=Cl) 25 μ mol; the remaining steps and parameters were the same as in Example 1, and 3.6 g of constant-weight cyclic olefin multiblock copolymer was obtained.

[0066] Example 12 The only difference from Example 1 is that the mixed catalyst is a β-diketone monoimine catalyst (R1 = CF3, R2 = CH3, R3 = Ph, M = Ti, X = Cl). μ mol and salicylaldehyde imine catalyst (R1=CPhMe2, R2=H, R3=C6F5, M=Ti, X=Cl) 25 μ The molar ratio was 1:5; the remaining steps and parameters were the same as in Example 1, and 4.0 g of constant weight cyclic olefin multiblock copolymer was obtained.

[0067] Comparative Example 1 The only difference from Example 1 is that the chain shuttle diethylzinc is not added; the other steps and parameters are the same as in Example 1, and 3.7 g of constant weight cyclic olefin random copolymer is obtained.

[0068] result: Figure 13 The stress-strain curves show that, compared to Example 1 with diethylzinc as a chain shuttle, the elongation at break of the cyclic olefin random copolymer in Comparative Example 1 without diethylzinc is only 25.3%. The toughening effect of the cyclic olefin block copolymer is more significant than that of the random copolymer.

[0069] Comparative Example 2 The only difference from Example 2 is that the chain shuttle diethylzinc was not added; all other steps and parameters were the same as in Example 2. 4.0 g of a constant-weight cyclic olefin random copolymer was obtained.

[0070] result: Figure 13The stress-strain curves show that, compared to Example 2 with diethylzinc added as a chain shuttle, Comparative Example 2 without diethylzinc is a cyclic olefin random copolymer with an elongation at break of only 45.3%. The toughening effect of the cyclic olefin block copolymer is more significant than that of the random copolymer.

[0071] Comparative Example 3 The only difference from Example 1 is that the addition of the salicylaldehyde imine catalyst was omitted, and the mixed catalyst was replaced with a single β-diketone monoimine catalyst (R1=CF3, R2=CH3, R3=Ph, M=Ti, X=Cl). The remaining steps and parameters were the same as in Example 1, and 2.0 g of constant-weight cyclic olefin copolymer was obtained.

[0072] Results: Compared with Example 1 using a dual catalyst system, the cyclic olefin random copolymer obtained by Comparative Example 3 using a single catalyst system had an elongation at break of only 3.8%. The toughening effect of the cyclic olefin block copolymer obtained by the dual catalyst system was more obvious than that of the random copolymer obtained by the single catalyst system.

[0073] Comparative Example 4 The only difference from Example 1 is that the addition of the β-diketone monoimide catalyst is omitted, and the mixed catalyst is replaced with a single salicylaldehyde imide catalyst (R1= t Bu, R2 = t Bu, R3=C6F5, M=Ti, X=Cl), the remaining steps and parameters are the same as in Example 1, and 0.9 g of constant weight cyclic olefin copolymer is obtained.

[0074] Results: Compared with Example 1 using a dual catalyst system, the cyclic olefin random copolymer obtained by Comparative Example 4 using a single catalyst system had an elongation at break of 310.5%, but a tensile strength of only 20.1 MPa and a glass transition temperature of only 5 °C. The tensile strength and temperature resistance of the cyclic olefin block copolymer obtained by the dual catalyst system were superior to those of the random copolymer obtained by the single catalyst system.

[0075] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for preparing narrowly distributed cyclic olefin block copolymers by chain shuttle using a non-metallocene catalyst, characterized in that, Includes the following steps: In the presence of a chain shuttle agent, cyclic olefin monomers and ethylene undergo chain shuttle polymerization under the action of a non-metallocene mixed catalyst. The non-metallocene mixed catalyst includes a β-diketone monoimide catalyst and a salicylaldehyde imide catalyst.

2. The method according to claim 1, characterized in that, The general structural formula of the β-diketone monoimine catalyst is shown in Formula (I); the general structural formula of the salicylaldehyde imine catalyst is shown in Formula (II). Equation (I); Formula (II); In formula (Ⅰ), when R1 = Ph, R2 = CF3 or CH3; when R1 = thiophene, R2 = CF3; when R1 = furanyl, R2 = CF3; when R1 = CF3, R2 = CH3; when R1 = CH3, R2 = CF3; R3 is an alkyl or aromatic group; X is Me, Cl, Bn or NMe2; M is Ti, Zr or Hf; In equation (II), when R1= t When Bu, R2 = t Bu or H; when R1=Ph, R2=Ph or H; when R1=CPhMe2, R2=CPhMe2 or H; when R1=CPh2Me, R2=CPh2Me or H; when R1=CPh3, R2=CPh3 or H; R3 is an alkyl or aromatic group; X is Me, Cl, Bn or NMe2; M is Ti, Zr or Hf.

3. The method according to claim 2, characterized in that, The molar ratio of β-diketone monoimide catalyst and salicylaldehyde imide catalyst in the non-metallocene mixed catalyst is 5:1 to 1:

5.

4. The method according to claim 1, characterized in that, The chain shuttle is diethylzinc; the amount of the chain shuttle added is 5 to 80 times the amount of the non-metallocene mixed catalyst.

5. The method according to claim 1, characterized in that, The cyclic olefin monomer is one or more of norbornene, norbornediene, dicyclopentadiene, and dimethyl-bridged octahydronaphthalene, and its concentration in the reaction system is 0.15–1.0 mol / L.

6. The method according to claim 1, characterized in that, The chain shuttle polymerization reaction is carried out in an ethylene atmosphere, with an ethylene pressure of 1~5 atm, a polymerization temperature of 25~80 ℃, and a polymerization time of 1~10 min.

7. The method according to claim 1, characterized in that, A co-catalyst was also added to the reaction system.

8. The method according to claim 7, characterized in that, The co-catalyst is one or more of the following: methylaluminoxane, triisobutylaluminum and tris(pentafluorophenyl)borane, triisobutylaluminum and triphenylcarbazone(pentafluorophenyl)borate, and modified methylaluminoxane; the molar ratio of the co-catalyst to the non-metallocene mixed catalyst is 2000:1 to 100:

1. After the chain shuttle polymerization reaction is completed, the process also includes quenching, precipitation, and drying steps.

9. A cyclic olefin block copolymer prepared by the method according to any one of claims 1 to 8.

10. The use of the cyclic olefin block copolymer as described in claim 9 in the preparation of optical components, medical devices, capacitor films or food packaging materials.

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