A hydrogenated cycloolefin copolymer, and a method for preparing and using the same

Abstract

The application discloses a hydrogenated cycloolefin copolymer and a preparation method and application thereof. The hydrogenated cycloolefin copolymer is obtained by hydrogenating a copolymer consisting of repeating units shown in formula I. By adjusting the microstructure and composition of the hydrogenated cycloolefin copolymer, the obtained hydrogenated cycloolefin resin composition is subjected to gel chromatography analysis, and formula (1) 0<SM1<5% is satisfied, and formula (2) 0<RPD1≤0.2% is satisfied. The hydrogenated cycloolefin copolymer provided by the application has high light transmittance, low birefringence, and significantly improved heat resistance, yellowing resistance and dimensional stability, and can be applied to medical packaging materials, optical lenses, optical film materials and electronic semiconductor materials.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and relates to a copolymer, specifically a hydrogenated cyclic olefin copolymer. Background Technology

[0002] COP is an amorphous, transparent, hydrogenated cyclic olefin copolymer material with a cyclic structure. COP is typically prepared by ring-opening metathesis copolymerization of dicyclopentadiene (DCPD) monomers, tetracyclic dodecene monomers, and aromatic ring-containing norbornene derivative monomers into ROMP, followed by deep hydrogenation saturation. The molecular chain structure contains flexible aliphatic hydrocarbon segments and a rigid cyclic structure. The aliphatic hydrocarbon segments enable the cyclic olefin polymer material to maintain good chemical resistance, water resistance, mechanical strength, and electrical insulation, while the rigid cyclic structure imparts a high glass transition temperature (Tg), improving heat resistance. Simultaneously, it disrupts the crystallinity of polyethylene, resulting in excellent optical properties. Furthermore, the double bonds in the hydrogenated saturated molecular chain improve the material's resistance to yellowing and aging. Therefore, COP has irreplaceable advantages in high-end pharmaceutical packaging, optical films, optical lenses, and semiconductor applications.

[0003] With demanding application scenarios such as all-weather outdoor environments, high temperatures and humidity in the south, and frigid conditions in the north, existing materials still have shortcomings in high-end optics, including high birefringence affecting image quality, insufficient long-term high-temperature resistance, and inability to resist heat yellowing. These limitations prevent the long-term guarantee of optical performance and appearance stability. In the pharmaceutical packaging industry, where storage and transportation often occur at -120°C or even -196°C, COP materials also face challenges in terms of internal stress and dimensional stability caused by freeze-thaw cycles.

[0004] During the material preparation process, it was found that the conversion rate during hydrogenation has a significant relationship with the material's performance. As the degree of hydrogenation increases, the material's optical properties (high transparency, low birefringence), mechanical properties (impact resistance, low internal stress), and thermal properties (high temperature resistance and yellowing resistance) are significantly improved.

[0005] WO2021107041A1 discloses a hydrogenated cyclic olefin copolymer containing naphthyl alicyclic compound structural units. In this copolymer, the carbon-carbon double bonds in the main chain are hydrogenated and saturated, while the double bonds of the naphthyl ring are retained and not hydrogenated. This cyclic olefin polymer has a high refractive index and Tg, but it also exhibits high birefringence, insufficient long-term high-temperature resistance, and inadequate resistance to heat yellowing.

[0006] CN116496446A discloses a norbornene-based hydrogenated ring-opening polymer. The hydrogenation rate of carbon-carbon unsaturated bonds in the aromatic ring of the polymer is less than 1.0%, and the hydrogenation rate of carbon-carbon unsaturated bonds other than the aromatic ring is more than 99%. This cyclic olefin polymer has a good stress optical coefficient and certain resistance to yellowing. However, it is not suitable for long-term high-temperature resistance in high-end optical fields such as HUD (Head-Up Display), AR / VR, phasor films, and automotive lenses. Its light stability and resistance to thermal yellowing are still insufficient, and its dimensional stability at high and low temperatures still needs to be improved.

[0007] To achieve high transparency, low birefringence, and high heat resistance, aromatic ring-containing cyclic olefin copolymers (COPs) must be fully hydrogenated (including double bond hydrogenation of >99.5% or even 99.9% for the benzene ring). However, deep hydrogenation is often accompanied by side reactions such as polymer degradation and cross-linking, producing a large amount of oligomers and gels, resulting in decreased product transparency, increased haze, and decreased modulus.

[0008] CN121086200A, by controlling the hydrogenation reaction conditions of hydrogenated cyclic olefin copolymers and employing a two-stage heating intermittent hydrogenation process, significantly reduces the content of isomerized DCPD in the prepared hydrogenated cyclic olefin copolymers, effectively preventing dispersion effects, significantly improving the refractive index, and enhancing resistance to yellowing. On the other hand, introducing aliphatic chains into the main chain structure can increase the flexibility of the polymer chain, reduce the chain rigidity caused by the large steric hindrance of the polycyclic structure, and improve the processing flow properties of the polymer.

[0009] CN121717996A addresses the issues of high internal stress and cracking, high birefringence, and insufficient heat resistance in high-end applications of hydrogenated cyclic olefin copolymers by controlling the microstructure and composition during polymerization and hydrogenation processes, adding suitable auxiliaries, and employing Grubbs ruthenium-based catalysts and alkali / alkaline earth metal-modified hydrogenation catalysts. This optimization of polymer molecular weight and distribution solves these problems. The resulting high transmittance, low birefringence, low haze, and high water and oxygen barrier properties are achieved. However, with continued research, the inventors discovered that over-hydrogenation is unavoidable in existing deep hydrogenation processes. Unexpectedly, they found that the five-membered rings containing double bonds in the side chains of the DCPD ring-opening polymerization structure in the copolymer chain undergo ring-opening during saturation, leading to a decrease in polymer modulus and a wider distribution. Furthermore, over-hydrogenation also generates a large amount of oligomers and gels, degrading product performance.

[0010] In summary, based on existing technologies, there is a need to further develop a hydrogenated cyclic olefin resin composition with low birefringence, high transparency, high heat resistance, and excellent dimensional stability. Summary of the Invention

[0011] This invention provides a hydrogenated cyclic olefin copolymer, its preparation method, and its applications. By controlling the microstructure and composition of this hydrogenated cyclic olefin copolymer, the hydrogenated cyclic olefin copolymer provided by this invention exhibits high light transmittance and low birefringence, while significantly improving heat resistance, yellowing resistance, and dimensional stability. It can be applied to medical packaging materials, optical lenses, optical film materials, and electronic semiconductor materials.

[0012] Based on the above research, in order to achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0013] A hydrogenated cyclic olefin copolymer is obtained by hydrogenating a copolymer composed of repeating units as shown in Formula I, wherein the hydrogenated cyclic olefin copolymer satisfies the following conditions:

[0014] (1) 0 < SM1 < 5%

[0015] In Equation (1), SM1 represents: the ratio of the value obtained by integrating dw / dln(M) when 6.21≤ln(M)≤8.52 in the differential molecular weight distribution curve obtained by gel permeation chromatography based on the hydrogenated repeating unit composed of segments (A), (B), and (C) in the hydrogenated cyclic olefin copolymer as the conversion standard, with the logarithm of molecular weight M ln(M) as the horizontal axis and dw / dln(M) obtained by differentiating the concentration percentage w with the logarithm of molecular weight ln(M) as the vertical axis, to the value obtained by integrating dw / dln(M) over the entire range of ln(M);

[0016] (2) 0 < RPD1 ≤ 0.2%

[0017] In formula (2), RPD1 represents the mass fraction of hydrogenated dicyclopentadiene (DCPD) with side ring opening in the hydrogenated cyclic olefin copolymer obtained by separating the hydrogenated cyclic olefin copolymer by gel permeation chromatography, based on the hydrogenated repeating unit composed of segments A, B, and C.

[0018] Formula I

[0019] ABC

[0020] In Formula I, A1, A2, A3, and A4 are each independently selected from hydrogen, halogen, unsubstituted or halogenated C1-C20 straight-chain or branched alkyl, unsubstituted or halogenated C3-C20 cycloalkyl, and C6-C20 aryl. A2 and A3 may be bonded to form a ring or not bonded. A1 and A2 may be bonded to form an alkylidene group or not bonded. A3 and A4 may be bonded to form an alkylidene group or not bonded. n represents an integer from 0 to 2. i and j represent integers from 0 to 2.

[0021] As a preferred embodiment, the polymeric structural unit A in Formula I is a tetracyclic dodecene structural unit; preferably, the structural segment represented by A is derived from at least one of the following structural monomers:

[0022]

[0023] A1A2A3A4A5

[0024] As a preferred embodiment, the polymeric structural unit C in Formula I is a norbornene structural unit containing an aromatic ring; preferably, the structural segment represented by C is derived from at least one of the monomers having the following structures:

[0025]

[0026] C1C2C3C4C5

[0027] As a preferred embodiment, the content of each polymeric structural unit A, B, and C in Formula I, based on the mass of the corresponding monomer, is in the ratio of (30-60):(20-50):(10-40).

[0028] The weight-average molecular weight of the hydrogenated copolymer is 5,000-100,000 g / mol, preferably 10,000-80,000 g / mol.

[0029] The PDI of the hydrogenated copolymer is 1.0-3.0, preferably 1.0-2.0.

[0030] As a preferred embodiment, the hydrogenated cyclic olefin copolymer further satisfies the following conditions:

[0031] 0 < RPD2 ≤ 0.5 wt%,

[0032] In the formula, RPD2 represents the mass fraction of hydrogenated DCPD with side ring opening in hydrogenated cyclic olefin copolymers with a weight average molecular weight of >10000 and ≤50000, based on hydrogenated repeating units composed of segments A, B, and C, obtained by gel permeation chromatography.

[0033] As a preferred embodiment, the hydrogenated cyclic olefin copolymer further satisfies the following conditions:

[0034] 0 < RPD3 ≤ 0.1 wt%,

[0035] In the formula, RPD3 represents the mass fraction of hydrogenated DCPD with side ring opening in hydrogenated cyclic olefin copolymers with a weight average molecular weight of >50,000 and ≤100,000, based on hydrogenated repeating units composed of segments A, B, and C, obtained by gel permeation chromatography.

[0036] Furthermore, the schematic diagram of the side-ring open-ring hydrogenated DCPD structure is as follows: Equation II:

[0037] Formula II.

[0038] A method for preparing a hydrogenated cyclic olefin copolymer includes the following steps:

[0039] S1 Continuous polymerization: A monomer composition including polymeric structural units A, B, and C undergoes a continuous ring-opening polymerization reaction in the presence of a ring-opening metastasis catalyst, a chain transfer agent, and an organic solvent to obtain a copolymer solution;

[0040] S2 First-stage continuous hydrogenation: The copolymer solution obtained in S1 undergoes a continuous hydrogenation reaction in the presence of hydrogenation catalyst CA1, diether internal electron donor, and hydrogen to obtain a selectively hydrogenated cyclic olefin copolymer solution.

[0041] S3 Secondary Continuous Hydrogenation: The copolymer solution obtained in S2 is subjected to a continuous hydrogenation reaction in the presence of hydrogenation catalyst CA2 and hydrogen to obtain a hydrogenated cyclic olefin copolymer solution.

[0042] S4 post-processing: The hydrogenated cyclic olefin copolymer solution obtained in S3 is subjected to adsorption and filtration to remove the catalyst, antioxidant is added, solvent is removed by flash evaporation, and then extrusion granulation is performed to obtain the hydrogenated cyclic olefin copolymer.

[0043] Furthermore, as a preferred embodiment, in S1, the polymerization catalyst is selected from at least one of tungsten-based catalysts, Grubbs series catalysts, and Schrock series catalysts; the amount of the polymerization catalyst added, based on the mass of the main metal element, is 0.1 to 100 ppm of the total mass of the monomer.

[0044] Furthermore, as a preferred embodiment, in S1, the organic solvent includes at least one of dichloromethane, cyclohexane, methylcyclohexane, n-hexane, toluene, or xylene.

[0045] Furthermore, as a preferred embodiment, in S1, the chain transfer agent is selected from at least one of 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, vinyl ether, etc.

[0046] Furthermore, as a preferred embodiment, in step S1, the amount of chain transfer agent added is 0.1% to 5% of the total mass of the monomer.

[0047] Furthermore, in S1, the polymerization reaction temperature is 30-150℃; the polymerization reaction pressure is 0.5-1.5MPa; and the polymerization reaction residence time is 1-30min.

[0048] Furthermore, as a preferred embodiment, in S2, the hydrogenation catalyst CA1 is a homogeneous catalyst, including one or more of Ziegler-Natta, metallocene, and homogeneous ruthenium catalysts, preferably one or more of nickel naphthenate, nickel acetylacetonate, cobalt octanoate, dichlorotitanene, tris(triphenylphosphine)chloride carbonyl ruthenium, and tris(triphenylphosphine)hydrochlorocarbonyl ruthenium.

[0049] Furthermore, as a preferred embodiment, in S2, the amount of hydrogenation catalyst added, based on the mass of the main metal element, is 10-3000 ppm of the total mass of the monomer.

[0050] Furthermore, as a preferred embodiment, in S2, the internal electron donor of the diether can be an alkyl diether or an aryl diether, preferably an alkyl diether, the structure of which is shown in Formula III.

[0051] Formula III

[0052] In Formula III, R1 and R2 can be independently straight-chain or branched alkyl groups from C1 to C6, and R3 and R4 can be independently H atoms, straight-chain or branched alkyl groups from C1 to C6.

[0053] Further preferably, the electron donor of the alkyl diether is selected from one or more of 2-methyl-1,3-propanediether, 2-ethyl-1,3-propanediether, 2-propyl-1,3-propanediether, and 2-butyl-1,3-propanediether. More specifically, it can be one or more of 2-methyl-1,3-propanedimethyl ether, 2-ethyl-1,3-propanedimethyl ether, 2-methyl-1,3-propanediethyl ether, and 2-methyl-1,3-propanedibutyl ether.

[0054] Furthermore, as a preferred embodiment, in step S2, the amount of the internal electron donor of the diether is 50-1000 ppm of the total mass of the monomer.

[0055] Furthermore, in S2, the first-stage continuous hydrogenation is a plug flow loop reaction; the reaction temperature is 60-120℃; the reaction hydrogen pressure is 2-4MPa; and the reaction residence time is 30-120min.

[0056] As a preferred embodiment, the hydrogenation catalyst CA2 is a heterogeneous catalyst, including one or more of metal-supported and Raney metal catalysts, preferably one or more of Raney nickel, Raney cobalt, supported nickel, and supported Pd.

[0057] As a preferred embodiment, the two-stage continuous hydrogenation is a fixed-bed reaction; the reaction temperature is 150-200℃; the reaction hydrogen pressure is 4-6 MPa; and the reaction mass hourly space velocity is 0.1-2 h⁻¹. -1 The gas-liquid ratio of hydrogen to polymer solution is 200-500 (V:V); the degree of hydrogenation of the hydrogenated cyclic olefin copolymer is ≥99.9%.

[0058] The hydrogenated cyclic olefin copolymer of the present invention has a light transmittance ≥92%, birefringence ≤10nm, dimensional change rate ≤0.4%, 5% thermogravimetric temperature T5% not lower than 420℃, ΔYI≤5, and Young's modulus ≥2200MPa.

[0059] Furthermore, the hydrogenated cycloolefin resin is used in medical packaging materials, optical lenses, optical film materials, and electronic semiconductor materials.

[0060] The beneficial effects of this invention are as follows: The aromatic ring-containing cyclic olefin copolymer (COP) backbone contains numerous bridged intraring double bonds, DCPD side ring double bonds, and benzene ring double bonds. Complete hydrogenation (hydrogenation degree > 99.5% or even 99.9%) under harsh high temperature and high pressure conditions is necessary to obtain COP with high transparency, low birefringence, and high heat resistance. However, deep hydrogenation often involves side reactions such as polymer molecule degradation, crosslinking, and DCPD side ring hydrogenation ring-opening, leading to deterioration of product performance. Through extensive research, the inventors of this invention discovered that a two-stage continuous hydrogenation process can be used to hydrogenate the double bonds in polymers in stages. By preferentially using a homogeneous hydrogenation catalyst and in the presence of an internal electron donor such as a diether, the hydrogenation of non-benzene ring double bonds can be efficiently completed under mild hydrogenation conditions. This process does not produce gelation. Then, the hydrogenation of the benzene ring is completed under relatively high temperature and pressure. On the one hand, complete hydrogenation of COP double bonds is achieved (hydrogenation degree > 99.9%), and on the other hand, the degradation of molecular chains and ring structure damage caused by excessive hydrogenation are greatly reduced. The resulting hydrogenated cyclic olefin resin composition has high light transmittance and low birefringence, while significantly improving heat resistance, yellowing resistance, and dimensional stability. Detailed Implementation

[0061] To facilitate understanding of the present invention, the following description, in conjunction with embodiments, will further illustrate the invention. It should be understood that the following embodiments are merely for a better understanding of the invention and do not imply that the invention is limited to these embodiments.

[0062] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0063] The main raw materials used in the following examples and comparative examples can all be purchased commercially.

[0064] Performance testing

[0065] 1. Weight-average molecular weight and molecular weight distribution test:

[0066] The weight-average molecular weight and molecular weight distribution of the hydrogenated cycloolefin polymers were determined by gas chromatography (GPC). The instrument used was a Shimadzu liquid chromatograph (LC-20AD feed system with RID-10A detector) paired with a Tosoh GPC column (model TSKgelGMHHR). The column temperature was 120°C, with o-dichlorobenzene as the eluent and a flow rate of 1.0 mL / min. The polymer solution concentration was 1 mg / mL.

[0067] Molecular weight fractionation was performed. For hydrogenated cyclic olefin copolymers, each retention time was divided into 3 grades to obtain fractions. This process was repeated 100 times. The structure of the fractions was determined by NMR.

[0068] 2. Visible light transmittance:

[0069] The average transmittance of the thin film in the wavelength range of 380~780nm was measured using an ultraviolet spectrophotometer (manufactured by Hitachi, model U-3900).

[0070] 3. Stress birefringence (CR):

[0071] The hydrogenated cyclic olefin polymer to be tested was prepared into a sample sheet with a thickness of 3 mm. Stress (F) was applied to the sample sheet, and then a high-precision optical stress birefringence polarimeter system WPA-200 was used to measure the two-dimensional distribution data image at a wavelength of 575 nm. The in-plane retardation (Re, in nm) and thickness (T, in mm) of the central part at a wavelength of 575 nm were obtained, and the optical path difference δn was calculated: δn=Re×(1 / T)×10 -6 ; Calculate stress birefringence C using δn and applied stress F. R :C R =δn / F; the closer the value of δn is to 0, the smaller the birefringence.

[0072] 4. Degree of hydrogenation:

[0073] The hydrogenation rate of hydrogenated cyclic olefin polymers was measured using nuclear magnetic resonance (NMR) spectroscopy. The instrument used for NMR testing was a Bruker AVANCE III HD300, with deuterated chloroform and room temperature.

[0074] 5. Yellowing resistance index ΔYI:

[0075] The hydrogenated cycloolefin polymer to be tested was oxidized in air at 250℃ for 60 min and then cut into samples with a thickness of 3 mm. The samples were tested according to the method of standard GB / T39822-2021 using a fully automatic colorimeter SC-80C (Beijing Kangguang Optical Instrument Co., Ltd.), with a CIE standard D65 light source and a 10-degree field of view. The tristimulus values ​​of the samples were measured, and the yellowing resistance index ΔYI was calculated using the formula specified in ISO17223-2014. The smaller the ΔYI index, the better the yellowing resistance.

[0076] 6. Dimensional stability:

[0077] According to the method of standard GB / T12027-2004, the hydrogenated cyclic olefin polymer to be tested is cut into samples according to the standard specified size, and after marking the specified distance on the surface, it is placed flat in the test chamber. After being stored at 100℃ for 30 minutes, the chamber is cooled to room temperature, and the distance of the marking is immediately measured. The dimensional stability of the sample is determined by measuring the dimensional change rate of the sample during the cooling process. The smaller the dimensional change rate, the better the dimensional stability.

[0078] 7. Young's modulus:

[0079] Hydrogenates of cyclic olefin polymers were added to an extruder for plasticization and injected into different molds to prepare tensile test specimens and stress-induced birefringent optical plates. Injection molding conditions: extruder plasticization temperature 280℃, screw speed 30 rpm, back pressure 3.5 MPa, screw feed speed 10 mm / s, holding time 15 s.

[0080] The polymer Young's modulus was tested using a standard dumbbell-shaped specimen (total length 170 mm, narrow section width 10 mm, thickness 4 mm) according to ISO 527 standard.

[0081] 8. 5% thermogravimetric temperature T5%

[0082] Thermogravimetric analysis (TGA) was performed according to the ISO 11358 standard. The temperature at which a 5% mass loss was achieved was determined from the TGA curve, which is T5.

[0083] Preparation of hydrogenated cyclic olefin copolymers:

[0084] Examples 1-5, Comparative Examples 1-3:

[0085] (1) Preparation of ring-opening copolymers

[0086] The polymerization reactor was heated and purged with nitrogen. A mixed monomer of formulas A, B, and C, chain transfer agent 1-hexene, and solvent cyclohexane were added to the monomer preparation tank according to the orientation shown in Table 1. The mixture was stirred until homogeneous, yielding a mixed monomer solution with a mass concentration of 30%. A polymerization catalyst solution (Grubbs third-generation catalyst, cyclohexane as solvent) was added to the catalyst feed tank. The monomer solution and catalyst solution were pumped into the polymerization reactor for continuous ring-opening polymerization to prepare the ring-opening copolymer. The reaction conditions are shown in Table 2.

[0087] Table 1 shows the percentage of chain transfer agent used in the system as a percentage of the total monomer mass in the examples.

[0088] Table 2 shows the amount of polymerization catalyst used in the examples, calculated by the mass of Ru metal in the catalyst system.

[0089] Table 1

[0090] Formula A monomer / wt% Formula B monomer (DCPD) / wt% Formula C monomer / wt% Chain transfer agent / wt% Example 1 A1（30%） （40%） C2（30%） 0.5 Example 2 A2（30%） （30%） C2（40%） 0.6 Example 3 A4（40%） （50%） C4（10%） 0.5 Example 4 A4（40%） （45%） C5（15%） 1.1 Example 5 A1（60%） （20%） C1（20%） 0.4 Comparison Column 1 A1（30%） （40%） C2（30%） 0.5 Comparative Example 2 A1（30%） （40%） C2（30%） 0.5 Comparative Example 3 A1（30%） （40%） C2（30%） 0.5

[0091] Table 2

[0092] Grubbs 3rd catalyst / ppm Polymerization temperature / °C Polymerization pressure / MPa Reaction residence time / min Example 1 5 90 1.0 10 Example 2 20 60 0.5 20 Example 3 20 150 1.2 15 Example 4 10 120 0.8 15 Example 5 1 100 1.5 20 Comparison Column 1 5 90 1.0 10 Comparative Example 2 5 90 1.0 10 Comparative Example 3 5 90 1.0 10

[0093] (2) Preparation of hydrogenated cyclic olefin copolymers

[0094] (2-1) The copolymer solution obtained in (1) and the prepared hydrogenation catalyst CA1 and internal electron donor 2-methyl-1,3-propanedimethyl ether were preheated and continuously pumped into the loop reactor to contact with hydrogen for a first-stage continuous hydrogenation reaction. The reaction conditions are shown in Table 3 to obtain a selectively hydrogenated cyclic olefin copolymer solution.

[0095] The homogeneous ruthenium catalysts in Table 3 do not require activation and can be directly added to the reactor.

[0096] The catalyst system of nickel acetylacetone + TIBA (triisobutylaluminum) was prepared in advance as follows: 500 ml of cyclohexane was added to a 1000 ml round-bottom flask in a glove box, and stirring was started. 5 mmol of nickel acetylacetone was weighed and dispersed in cyclohexane. 20 mmol of TIBA was added dropwise to the flask. After the addition was completed, the mixture was stirred at 60 °C for 20 min.

[0097] Table 3 shows the amounts of catalyst used in the system, calculated by the mass of Ni or Ru in the catalyst system.

[0098] Table 3

[0099] Hydrogenation catalyst CA1 Hydrogenation catalyst dosage / ppm Internal electron donor / ppm Hydrogenation temperature / °C Hydrogenation pressure / MPa Reaction residence time / min Example 1 RuCl(H)(CO)(PPh3)3 100 50 80 2 120 Example 2 RuCl(H)(CO)(PPh3)3 100 50 60 3 90 Example 3 RuCl(H)(CO)(PPh3)3 50 25 100 3 120 Example 4 Nickel acetylacetonate + TIBA 1000 500 120 3 120 Example 5 Nickel acetylacetonate + TIBA 2000 1000 100 4 120 Comparison Column 1 RuCl(H)(CO)(PPh3)3 100 0 80 2 120 Comparative Example 2 RuCl(H)(CO)(PPh3)3 100 50 80 2 120 Comparative Example 3 / / / / / /

[0100] (2-2) The primary hydrogenated copolymer solution obtained in (2-1) is preheated and then continuously pumped to a fixed bed reactor to contact the catalyst CA2 and hydrogen for a secondary continuous hydrogenation reaction. The reaction conditions are shown in Table 4, and the hydrogenated cyclic olefin copolymer solution is obtained.

[0101] Table 4

[0102] Hydrogenation catalyst CA2 Mass air velocity / h⁻¹ Hydrogenation temperature / °C Hydrogenation pressure / MPa Gas-liquid ratio / V:V Example 1 5%Pd / Al2O3 0.5 180 5 300 Example 2 Raney nickel 1.0 200 5 300 Example 3 5%Pd / Al2O3 1.0 200 6 400 Example 4 Raney nickel 0.6 200 5 300 Example 5 10%Pd / Al2O3 1.0 160 4 200 Comparative Example 1 5%Pd / Al2O3 0.5 180 8 300 Comparative Example 2 / / / / / Comparative Example 3 5%Pd / Al2O3 0.5 180 5 300

[0103] (2-3) The hydrogenated cyclic olefin copolymer solution obtained in (2-2) is subjected to adsorption and filtration to remove the catalyst, flash evaporation to remove the solvent, and extrusion granulation to obtain the hydrogenated cyclic olefin copolymer. The polymer particles are then mixed with antioxidant Irganox1010 (0.5wt%) and injection molded into a sample or cast into a film.

[0104] The composition and performance test results of the hydrides of cyclic olefin polymers prepared in each example and comparative example are shown in Tables 5-6:

[0105] Table 5

[0106] Weight-average molecular weight (104 g / mol) PDI Degree of hydrogenation (%) SM10-5 RPD1 (wt%) 0-0.2 RPD2 (wt%) 0-0.5 RPD3 (wt%) 0-0.1 Example 1 2.80 1.52 ＞99.9 2.10 0.10 0.10 0.03 Example 2 2.55 1.54 ＞99.9 2.61 0.12 0.21 0.05 Example 3 2.75 1.55 ＞99.9 2.48 0.11 0.25 0.06 Example 4 2.20 1.70 ＞99.9 3.18 0.15 0.39 0.04 Example 5 3.2 1.55 ＞99.9 1.92 0.08 0.28 0.09 Comparative Example 1 2.70 1.90 ＞99.9 6.75 0.35 0.62 0.45 Comparison Column 2 2.55 2.0 ＞99.9 8.66 0.50 0.77 0.12 Comparison Column 3 2.42 2.2 ＞99.9 10.20 1.21 1.02 0.28

[0107] Table 6

[0108] Light transmittance (%) Birefringence (nm) Young's modulus / MPa Thermogravimetric temperature T5% (°C) Dimensional change rate (%) Yellowing resistance index ΔYI Example 1 92 7 2400 435 0.20 2.1 Example 2 92 7 2350 430 0.31 3.2 Example 3 92 8 2400 430 0.22 3.3 Example 4 92 9 2280 425 0.36 4.0 Example 5 92 8 2320 436 0.28 2.6 Comparative Example 1 90 22 2000 415 0.62 10.2 Comparative Example 2 90 19 1850 408 0.80 12.5 Comparative Example 3 88 25 1700 390 1.10 15.8

[0109] This invention, through the control and coordination of structural units and characteristic indicators, enables the polymer molecule to simultaneously contain flexible aliphatic hydrocarbon segments, rigid bridged ring structures, and alicyclic structures obtained from the hydrogenation of aromatic rings. Furthermore, by controlling the microstructure and composition of this hydrogenated cyclic olefin copolymer, a two-stage continuous hydrogenation process is employed to stage the hydrogenation of double bonds in the polymer. Prioritizing the use of a homogeneous hydrogenation catalyst under mild hydrogenation conditions, the non-benzene ring double bonds are hydrogenated, followed by the hydrogenation of the benzene ring under relatively higher temperature and pressure. This achieves complete hydrogenation of COP double bonds (hydrogenation degree > 99.9%) while significantly reducing molecular chain degradation and ring structure damage caused by excessive hydrogenation. The resulting hydrogenated cyclic olefin resin exhibits high light transmittance, low haze, and significantly improved heat resistance, yellowing resistance, and dimensional stability. The resulting hydrogenated cyclic olefin resin has a light transmittance ≥ 92%, birefringence ≤ 10 nm, dimensional change rate ≤ 0.4%, 5% thermogravimetric temperature not lower than 420℃, ΔYI ≤ 5, and Young's modulus ≥ 2200 MPa. This hydrogenated cyclic olefin copolymer can be used in medical packaging materials, optical lenses, optical film materials, and electronic semiconductor materials.

[0110] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A hydrogenated cyclic olefin copolymer, obtained by hydrogenating a copolymer composed of repeating units as shown in Formula I, wherein the hydrogenated cyclic olefin copolymer satisfies the following conditions: (1) 0 < SM1 < 5% In Equation (1), SM1 represents: the ratio of the value obtained by integrating dw / dln(M) when 6.21≤ln(M)≤8.52 in the differential molecular weight distribution curve obtained by gel permeation chromatography based on the hydrogenated repeating unit composed of segments (A), (B), and (C) in the hydrogenated cyclic olefin copolymer as the conversion standard, with the logarithm of molecular weight M ln(M) as the horizontal axis and dw / dln(M) obtained by differentiating the concentration percentage w with the logarithm of molecular weight ln(M) as the vertical axis, to the value obtained by integrating dw / dln(M) over the entire range of ln(M); (2) 0 < RPD1 ≤ 0.2% In formula (2), RPD1 represents the mass fraction of hydrogenated dicyclopentadiene (DCPD) with side ring opening in the hydrogenated cyclic olefin copolymer obtained by separating the hydrogenated cyclic olefin copolymer by gel permeation chromatography, based on the hydrogenated repeating unit composed of segments A, B, and C. Equation I ABC In Formula I, A1, A2, A3, and A4 are each independently selected from hydrogen, halogen, unsubstituted or halogenated C1-C20 straight-chain or branched alkyl, unsubstituted or halogenated C3-C20 cycloalkyl, and C6-C20 aryl. A2 and A3 may be bonded to form a ring or not bonded. A1 and A2 may be bonded to form an alkylidene group or not bonded. A3 and A4 may be bonded to form an alkylidene group or not bonded. n represents an integer from 0 to 2. i and j represent integers from 0 to 2.

2. The hydrogenated cyclic olefin copolymer according to claim 1, characterized in that, In Formula I, the polymeric structural unit A is a tetracyclic dodecene-type structural unit; preferably, the structural segment represented by A is derived from at least one of the following structural monomers: A1A2A3A4A5; And / or, in Formula I, the polymeric structural unit C is a norbornene structural unit containing an aromatic ring; preferably, the structural segment represented by C is derived from at least one of the monomers having the following structures: C1C2C3C4C5.

3. The hydrogenated cyclic olefin copolymer according to claim 1 or 2, characterized in that, The content of each polymeric structural unit A, B, and C in Formula I, based on the mass of the corresponding monomer, is in the ratio of (30-60):(20-50):(10-40); and / or, the weight-average molecular weight of the hydrogenated copolymer is 5000-100000 g / mol, preferably 10000-80000 g / mol; and the PDI is 1.0-3.0, preferably 1.0-2.

0.

4. The hydrogenated cyclic olefin copolymer according to any one of claims 1-3, characterized in that, The hydrogenated cyclic olefin copolymer satisfies the following conditions: 0 < RPD2 ≤ 0.5 wt%, In the formula, RPD2 represents the mass fraction of hydrogenated DCPD with side ring opening in hydrogenated cyclic olefin copolymers with a weight average molecular weight of >10000 and ≤50000, based on hydrogenated repeating units composed of segments A, B, and C, obtained by gel permeation chromatography.

5. The hydrogenated cyclic olefin copolymer according to any one of claims 1-4, characterized in that, The hydrogenated cyclic olefin copolymer satisfies the following conditions: 0 < RPD3 ≤ 0.1 wt%, In the formula, RPD3 represents the mass fraction of hydrogenated DCPD with side ring opening in hydrogenated cyclic olefin copolymers with a weight average molecular weight of >50,000 and ≤100,000, based on hydrogenated repeating units composed of segments A, B, and C, obtained by gel permeation chromatography.

6. A method for preparing the hydrogenated cyclic olefin copolymer according to any one of claims 1-5, comprising the following steps: S1 Continuous polymerization: A monomer composition including polymeric structural units A, B, and C undergoes a continuous ring-opening polymerization reaction in the presence of a ring-opening metastasis catalyst, a chain transfer agent, and an organic solvent to obtain a copolymer solution; S2 First-stage continuous hydrogenation: The copolymer solution obtained in S1 undergoes a continuous hydrogenation reaction in the presence of hydrogenation catalyst CA1, diether internal electron donor, and hydrogen to obtain a selectively hydrogenated cyclic olefin copolymer solution. S3 Secondary Continuous Hydrogenation: The copolymer solution obtained in S2 is subjected to a continuous hydrogenation reaction in the presence of hydrogenation catalyst CA2 and hydrogen to obtain a hydrogenated cyclic olefin copolymer solution. S4 post-processing: The hydrogenated cyclic olefin copolymer solution obtained in S3 is subjected to adsorption and filtration to remove the catalyst, antioxidant is added, solvent is removed by flash evaporation, and then extrusion granulation is performed to obtain the hydrogenated cyclic olefin copolymer.

7. The method according to claim 6, characterized in that, In S2, the hydrogenation catalyst CA1 is a homogeneous catalyst, including one or more of Ziegler-Natta, metallocene, and homogeneous ruthenium catalysts, preferably one or more of nickel naphthenate, nickel acetylacetonate, cobalt octanoate, titanium dichlorodichloro, ruthenium tri(triphenylphosphine)chloride carbonyl, and ruthenium tri(triphenylphosphine)hydrochlorocarbonyl; and / or, the hydrogenation catalyst CA2 is a heterogeneous catalyst, including one or more of metal-supported and Raney metal catalysts, preferably one or more of Raney nickel, Raney cobalt, supported nickel, and supported Pd.

8. The method according to claim 6, characterized in that, In S2, the internal electron donor of the diether is selected from alkyl diethers and aryl diethers, preferably alkyl diethers, with the structure shown in Formula III. Formula III In Formula III, R1 and R2 can be independently C1 to C6 straight-chain and / or branched alkyl groups, and R3 and R4 can be independently H atoms, C1-C6 straight-chain or branched alkyl groups; more preferably, one or more of 2-methyl-1,3-propanediether, 2-ethyl-1,3-propanediether, 2-propyl-1,3-propanediether, and 2-butyl-1,3-propanediether; and / or, the amount of electron donor added to the diether is 50-1000 ppm of the total mass of the monomer.

9. The hydrogenated cyclic olefin copolymer according to any one of claims 1-5 or the hydrogenated cyclic olefin copolymer prepared by the method according to any one of claims 6-8, characterized in that, The hydrogenated cyclic olefin copolymer has a light transmittance of ≥92%, birefringence of ≤10nm, dimensional change rate of ≤0.4%, a 5% thermal weight loss temperature (T5%) of not less than 420℃, ΔYI ≤5, and Young's modulus of ≥2200MPa.

10. The application of the hydrogenated cyclic olefin copolymer of claim 9 in medical packaging materials, optical lenses, optical film materials, and electronic semiconductor materials.

Images