Hydrogenated cycloolefin copolymer, hydrogenated cycloolefin resin composition and preparation method thereof

Abstract

The invention discloses a hydrogenated cycloolefin copolymer, a hydrogenated cycloolefin resin composition and a preparation method thereof. Under the condition that the monomer composition and molecular weight of the hydrogenated cycloolefin copolymer are certain, the hydrogenated cycloolefin copolymer with more excellent performance can be obtained by controlling the hydrogenation reaction conditions of the hydrogenated cycloolefin copolymer. The hydrogenated cycloolefin resin composition provided by the invention not only has the characteristics of high refractive index, low haze and aging and yellowing resistance, but also obviously improves the separation efficiency of a catalyst, has excellent processability, and has outstanding application prospects in the fields of medical packaging materials, high-end photoelectric materials and the like.

Description

Technical Field

[0001] This invention relates to a copolymer, specifically to a hydrogenated cyclic olefin copolymer, a resin composition comprising the copolymer, and a method for preparing the composition, belonging to the field of polymer materials technology. Background Technology

[0002] Ring-opening metathesis polymerization (ROMP) of cyclic olefins and its hydrogenated polymer (COP) are amorphous, highly transparent, high-end polyolefin resin materials. This process requires polymerization followed by hydrogenation to obtain the final product. Compared to metallocene catalytic addition polymerization (mCOC), ROMP has milder reaction conditions, higher product structural regularity, more uniform composition, and superior optical properties because hydrogenation saturates unsaturated bonds, making it more stable and resistant to yellowing and aging. It has been widely used in high-end fields such as optics, packaging, and medical applications. However, with increasingly stringent material performance requirements, the refractive index of existing cyclic olefin copolymers is gradually failing to meet the demands of emerging technologies. Especially in high-refractive-index applications such as high-end optical lenses, displays, and sensors, the required refractive index exceeds 1.6, even reaching 1.7. However, increasing the refractive index usually leads to a decrease in other properties such as transparency, heat resistance, or low hygroscopicity, resulting in poor overall performance and failing to meet the stringent requirements of high-end fields.

[0003] Currently, a great deal of work has been done on hydrogenated cyclic olefin polymers:

[0004] CN106687500A discloses that by adjusting the composition and polymerization conditions of cyclic olefin ring-opening polymer hydrides, the problem of poor moldability of tetracyclic dodecene ring-opening polymer hydrides has been solved, and resin molded bodies with excellent heat resistance to yellowing, high-temperature dimensional stability and moldability have been achieved, which are suitable for high-temperature optical components, but the refractive index of the product is not high enough.

[0005] CN119798616A describes the preparation of a novel cyclic olefin copolymer. By utilizing a specific monomer structure and catalyst combination, and employing steps such as ring-opening metathesis polymerization and hydrogenation, it solves the problem of insufficient refractive index of existing cyclic olefin copolymers, achieving high refractive index, excellent transparency, outstanding heat resistance, and low moisture absorption, thus meeting the multiple performance requirements of high-end optical fields. However, the monomer source is demanding, and the copolymer contains multiple benzene ring structures, making it susceptible to yellowing and requiring high product processing and formability.

[0006] In summary, based on existing technologies, there is a need to further develop cyclic olefin polymers that combine high refractive index, resistance to aging and yellowing, and excellent processing performance. Summary of the Invention

[0007] To improve the overall performance of cyclic olefin polymers, this invention provides a hydrogenated cyclic olefin copolymer, a hydrogenated cyclic olefin resin composition, and a method for preparing the same. The hydrogenated cyclic olefin resin composition exhibits high refractive index, low haze, and resistance to aging and yellowing, and also possesses excellent processing properties.

[0008] Based on the above research, in order to achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A hydrogenated cyclic olefin copolymer, the schematic structural formula of which is as follows:

[0010]

[0011] Among them, A1, A2, A3, and A4 are independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or substituents containing halogen atoms, silicon atoms, oxygen atoms, or nitrogen atoms, such as hydrogen atoms, halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, and -OC groups. x H y -OCOC x H y -C x H y -C6H5, -C6H4CH3, -C 10 H7, -CH2C6H5, -CH2CH2C6H5, -C x H y C6H5; where x is a positive integer less than or equal to 10, and y≤2x+1; A2 and A3 are optionally bonded to form a ring, A1 and A2 are optionally bonded to form an alkylidene group, A3 and A4 are optionally bonded to form an alkylidene group, and n represents an integer from 0 to 2;

[0012] In the structural units B' and C', the dashed lines indicate whether they are bonded or not; n1 is the number of carbon atoms, 0≤n1≤4; R is the substituent structure that it carries when it is bonded, and R comes from R1-R15; R1 is selected from hydrogen atoms, hydroxyl groups or mercapto groups;

[0013] The hydrogenated cyclic olefin copolymer satisfies the following conditions:

[0014] 0 ≤ IDC1 ≤ 0.2 wt%

[0015] In the formula, IDC1 represents the mass fraction of isomerized dicyclopentadiene (DCPD) in the hydrogenated cyclic olefin copolymer obtained by separating the hydrogenated cyclic olefin copolymer by gel permeation chromatography, where the weight average molecular weight is ≤50,000 based on repeating units composed of segments A', B', and C'.

[0016] As a preferred embodiment, the structural unit C' is derived from norbornene monomers containing alicyclic and aromatic rings and / or C4-C8 cyclic olefin monomers, specifically from one or more of the following compounds:

[0017]

[0018] As a preferred embodiment, in Formula II, the molar ratio of the three structures A', B', and C' is (10%-80%):(10%-80%):(10%-80%); preferably (20%-60%):(10%-40%):(20%-60%).

[0019] As a preferred embodiment, the weight-average molecular weight of the hydrogenated cyclic olefin copolymer is 1000-200000 g / mol, preferably 5000-100000 g / mol, and more preferably 10000-50000 g / mol.

[0020] Furthermore, as a preferred embodiment, the hydrogenated cyclic olefin copolymer satisfies the following conditions:

[0021] 0.2wt% < IDC2 ≤ 0.5wt%,

[0022] In the formula, IDC2 represents the mass fraction of isomerized DCPD in hydrogenated cyclic olefin copolymers with a weight average molecular weight of >50,000 and ≤100,000, based on repeating units composed of segments A', B', and C' obtained by gel permeation chromatography.

[0023] Furthermore, as a preferred embodiment, the hydrogenated cyclic olefin copolymer satisfies the following conditions:

[0024] 0.5wt% < IDC3 ≤ 1wt%

[0025] In the formula, IDC3 represents the mass fraction of isomerized DCPD in hydrogenated cyclic olefin copolymers obtained by gel permeation chromatography, where the weight average molecular weight is >100,000 and ≤200,000 based on repeating units composed of segments A', B', and C'.

[0026] A hydrogenated cyclic olefin resin composition comprising the hydrogenated cyclic olefin copolymer of the present invention, comprising the following components:

[0027] Hydrogenated cyclic olefin copolymers comprising 80-99.9% by weight;

[0028] Heterogeneous DCPD with a mass percentage of 0-1%;

[0029] Olefin monomers and / or oligomers comprising 0.1-20% by mass.

[0030] Furthermore, the structural schematic of the isomerized DCPD described in this invention is one or more of the following, wherein parentheses indicate the reaction sites:

[0031]

[0032] Preferably, the olefin monomer and / or oligomer is a hydride of a monomer of formula a, b1, b2, b3, or c, or an oligomer of any combination thereof, and / or one or more of hydrides of 1-octene and 1-hexene.

[0033]

[0034] Preferably, the resin composition of the hydrogenated cyclic olefin copolymer further includes 0-20 ppm of metal ions, more preferably 0-10 ppm, and even more preferably 0-1 ppm.

[0035] Preferably, the refractive index of the hydrogenated cyclic olefin copolymer resin composition is 1.55-1.65, Tg is 120-170℃, haze is 1-5, MFR is 30-100g / 10min, metal ion residue is <1ppm, and yellowness difference (ΔYI) is <20.

[0036] A method for preparing the hydrogenated cyclic olefin resin composition of the present invention comprises the following steps:

[0037] 1) Hydrogenation reaction: Aromatic cyclic olefin copolymer, solvent and catalyst are mixed and hydrogenated in multiple steps to obtain hydrogenated cyclic olefin copolymer;

[0038] 2) Post-processing: Separate the catalyst from the product of step 1), add the resulting solution to ethanol, precipitate white strip-shaped polymer, separate and dry.

[0039] As a preferred embodiment, the structural schematic of the aromatic cyclic olefin copolymer is shown in Formula I:

[0040]

[0041] Among them, A1, A2, A3, and A4 are independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or substituents containing halogen atoms, silicon atoms, oxygen atoms, or nitrogen atoms, such as hydrogen atoms, halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, -OCxHy, -OCOCxHy, -CxHy, -C6H5, -C6H4CH3, -C 10 H7, -CH2C6H5, -CH2CH2C6H5, -C x Hy C6H5; where x is a positive integer less than or equal to 10, and y≤2x+1; A2 and A3 are optionally bonded to form a ring, A1 and A2 are optionally bonded to form an alkylidene group, A3 and A4 are optionally bonded to form an alkylidene group, and n represents an integer from 0 to 2;

[0042] In the structural units B and C, the dashed lines indicate whether they are bonded or not; n1 is the number of carbon atoms, 0≤n1≤4; R is the substituent structure that it carries when it is bonded, and R comes from R1-R15; R1 is selected from hydrogen atoms, hydroxyl groups or mercapto groups.

[0043] Furthermore, as a preferred embodiment, the precursor of the unit structure represented by formula A is a tetracyclic dodecene compound represented by formula a; for example, tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-Tetracyclo[4.4.0.1 2,5 .1 7 ,10 ]-3-Dodecene, 8-Ethyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Cyclohexyl-Tetracyclo[4.4.0.1 2 ,5 .1 7,10 ]-3-Dodecene, 8-Cyclopentyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methoxycarbonyl-8-methyl-tetracyclo[4.4.0.1 2,5 .1 7,10 Unsubstituted or alkyl-containing tetracyclic dodecenes, such as 3-dodecene; 8-methylene-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Ethylene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Vinyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Propylene-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Cyclohexenyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Cyclopentenyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene and other tetracyclic dodecenes with exocyclic double bonds; 8-phenyl-tetracyclic [4.4.0.1] 2,5 .17,10 ]-3-Dodecene, 8-Phenoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-(4-phenylphenoxy)carbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 [3-Dodecene and other tetracyclic dodecenes with aromatic rings; 8-methoxycarbonyl-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-n-Propoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Isopropoxycarbonyl-tetracyclo[4.4.0.1 2, 5 .1 7,10 ]-3-Dodecene, 8-n-Butoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-n-propoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-isopropoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7 ,10 ]-3-Dodecene, 8-Methyl-8-n-Butoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-hydroxymethyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Carboxy-Tetracyclo[4.4.0.1 2,5 .1 7,10 Tetracyclic dodecenes, such as 3-dodecene, tetracyclic dodecene-8,9-dicarboxylic acid, and tetracyclic dodecene-8,9-dicarboxylic anhydride, are tetracyclic dodecenes with substituents containing oxygen atoms; 8-cyano-tetracyclic [4.4.0.1] 2,5 .1 7,10 Tetracyclic dodecenes such as 3-dodecene and tetracyclic dodecene-8,9-dicarboximide have substituents containing nitrogen atoms; 8-chloro-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene and other tetracyclic dodecenes having substituents containing halogen atoms; 8-trimethoxysilyl-tetracyclic [4.4.0.1] 2,5 .17 ,10 One or more of tetracyclic dodecenes, such as 3-dodecene, having substituents containing silicon atoms.

[0044] Furthermore, as a preferred embodiment, the precursor of the unit structure shown in Formula B is one of dicyclopentadiene, hydroxydicyclopentadiene, and mercaptodicyclopentadiene from Formulas b1, b2, and b3.

[0045]

[0046] Furthermore, as a preferred embodiment, the unit structure represented by Formula C is derived from norbornene monomers containing alicyclic and aromatic rings and / or C4-C8 cyclic olefin monomers, specifically from one or more of the following compounds:

[0047]

[0048] As a preferred embodiment, the multi-step hydrogenation includes the following steps: a first-stage reaction at a temperature of 50-120℃, preferably 70-100℃, with a pressure of 1-3 MPa; a second-stage reaction at a temperature of 120-200℃, preferably 140-180℃, with a pressure of 3-10 MPa.

[0049] As a preferred embodiment, the catalyst is one or more of the following: Raney nickel, supported Ni (Ni loading ≥ 30 wt%), supported Pd (Pd loading ≥ 0.3 wt%), supported Pt (Pt loading ≥ 0.3 wt%), supported rhodium (rhodium loading ≥ 0.3 wt%), etc.; preferably supported Pd (Pd loading ≥ 0.3 wt%) and / or supported Pt (Pt loading ≥ 0.3 wt%).

[0050] As a preferred embodiment, the amount of catalyst used is 0.1-50% of the mass of the aromatic cyclic olefin copolymer, preferably 0.5-30% of the mass of the aromatic cyclic olefin copolymer.

[0051] As a preferred embodiment, the catalyst of the present invention has a specific surface area of ​​80-200 m². 2 / g; average pore size 50-150nm, preferably 80-120nm.

[0052] The hydrogenation reaction time described in this invention is 1-20 hours, preferably 1-10 hours; more specifically, the first stage reaction time is preferably 1-4 hours, and the second stage reaction time is preferably 2-6 hours.

[0053] As a preferred embodiment, in step 1), the aromatic cyclic olefin copolymer is dissolved in a solvent to a mass percentage concentration of 5-50%, preferably 10-30%.

[0054] As a preferred embodiment, in step 1), the solvent used is one or more of alkanes and aromatics, preferably: aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; and alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decahydronaphthalene, and bicyclononane.

[0055] As a preferred embodiment, the post-processing includes the following steps: centrifuging the product from step 1), filtering the catalyst, adding the resulting solution to ethanol, precipitating out white strip-shaped polymer, separating by filtration, and drying under vacuum at 60-120°C for 6-24 hours to obtain the dried hydrogenated cyclic olefin copolymer.

[0056] As a preferred embodiment, in step 2) of the present invention, the catalyst separation process is employed; the filtration process employs a filter with a pore size <1µm.

[0057] Preferably, the resin composition further includes, by any means, additives, wherein the content of the additives is 0-5% of the total mass of the hydrogenated cyclic olefin copolymer and other cyclic olefin monomers or oligomers. The additives are selected from one or more of the following: mold release agents, flow aids, heat stabilizers, antioxidants, UV absorbers, IR absorbers, flame retardants, antistatic agents, and hydrophilic stabilizers.

[0058] The beneficial effects of the present invention are as follows: In the present invention, under the condition that the monomer composition and molecular weight of the hydrogenated cyclic olefin copolymer are certain, by controlling the hydrogenation reaction conditions of the hydrogenated cyclic olefin copolymer, a hydrogenated cyclic olefin copolymer with better performance can be obtained. In addition, the cyclic olefin resin composition containing the hydrogenated cyclic olefin copolymer described in the present invention has the characteristics of high refractive index, low haze and resistance to aging and yellowing, and also has excellent processing performance. Detailed Implementation

[0059] To better understand the technical solution of the present invention, the following embodiments will further illustrate the method provided by the present invention. However, the present invention is not limited to the listed embodiments, but should also include any other known modifications within the scope of the claims of the present invention.

[0060] Performance testing

[0061] 1. Glass transition temperature test:

[0062] The glass transition temperature of hydrogenated cycloolefin polymers was determined by DSC (Digital Subtraction Angiography). The instrument used for DSC testing was a Netzsch DSC 204F1. The conditions were nitrogen protection, 10℃ / min, and two cycles from room temperature to 230℃. The data from the second heating curve was taken.

[0063] 2. Melt Flow Index (MFI) Measurement:

[0064] According to ASTM D3159, the mass (g / 10min) of resin flowing out of a die with an inner diameter of 2mm and a length of 8mm at 280°C and a load of 5kg is taken as the MFI using a melt indexer.

[0065] 3. 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 using GPC. The instrument used was a Shimadzu HPLC system (LC-20AD feed system with RID-10A detector) paired with a Tosoh GPC column (TSKgel GMHHR). 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. An IR detector was prepared to measure the number of methyl groups per 1000 carbons in the products before and after hydrogenation; F represents the ratio of the number of methyl groups per 1000 carbons before and after hydrogenation.

[0067] Molecular weight fractionation: For hydrogenated cyclic olefin copolymers, each retention time is divided into 3 grades to obtain fractions. This process is repeated 100 times. The degree of hydrogenation of the fractions is measured by NMR.

[0068] 4. Refractive index:

[0069] The refractive index in the wavelength range of 400-1000nm was measured using a SE-VE-L type ellipsometer, and the refractive index corresponding to the wavelength of 589nm was selected.

[0070] 5. Visible light transmittance:

[0071] The average transmittance of the thin film in the wavelength range of 380–780 nm was measured using an ultraviolet spectrophotometer (manufactured by Hitachi, model U-3900).

[0072] 6. Degree of hydrogenation:

[0073] The hydrogenation rate of hydrogenated cycloolefin polymers was measured using nuclear magnetic resonance (NMR) spectroscopy. The instrument used for NMR testing was a Bruker AVANCE III HD 300, with deuterated chloroform and room temperature.

[0074] 7. Evaluation of heat resistance to yellowing:

[0075] Particles of a resin composition containing cyclic olefin ring-opening polymer hydrides were added to an injection molding machine (Fanuc Roboshot α-100B) under the following conditions: resin temperature 280°C, mold temperature (Tg-15)°C, and injection pressure 100 MPa. Resin plates measuring 70 mm long × 30 mm wide × 3 mm thick were produced. These resin plates were then used to make test pieces, which were placed in an oven at 125°C for 1000 hours. The yellowness index (YI) of the test pieces was measured using a colorimeter according to JIS K7103, with air as the blank control. The difference between the yellowness index of the test pieces and the yellowness index of air was taken as the yellowness difference (ΔYI). A smaller ΔYI indicates less yellowing at high temperatures and better heat resistance to yellowing.

[0076] ΔYI=YI 样品 -YI 空气

[0077] Preparation of hydrogenated polymers

[0078] The polymerization reactor was first purged four times with high-purity nitrogen to remove air. Then, under nitrogen protection, 120g of anhydrous toluene and monomers composed of A, B, and C as shown in Table 1 were added. Stirring was started, and 7.8mg of Grubbs 1st was dissolved in 10mL of toluene. After thorough stirring until completely dissolved, the solution was transferred to a transfer tank connected to the reactor via a feed pump. 7.8mg of Grubbs 1st was dissolved in 10mL of toluene, and the catalyst was transferred to the reactor via the feed pump. The reactor was then heated to 70℃ and reacted for 3 hours. Heating was stopped, and the reactor was cooled to 25℃. After polymerization, the reaction was terminated with ethanol, and a white powdery solid precipitated. This precipitate was washed with ethanol, filtered, and dried under vacuum at 70℃ for 8 hours to obtain the hydrogenated cyclic olefin polymer.

[0079] The catalysts used in the following examples and comparative examples can be obtained from Xi'an Kaili New Materials, and other main raw materials can be purchased commercially.

[0080] The structural unit composition of the aromatic polymer to be hydrogenated is shown in Table 1 below.

[0081] Table 1 Composition of the aromatic polymers to be hydrogenated

[0082]

[0083] Example 1

[0084] Take 30g of the polymer to be hydrogenated, a1 (10000g / mol), and add it to 570g of toluene solution (5wt%). The catalyst is 5wt% palladium / silica (80m). 26g (20%) of hydrogenated polymer A1 (120nm) was reacted at 90℃ and 3MPa hydrogen pressure for 2h, with hydrogen continuously added to maintain stable reaction pressure. The temperature was then raised to 150℃ and 5MPa hydrogen pressure, and the reaction continued for 4h. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol, precipitating out white strip-shaped polymers. The polymers were separated by filtration and dried at 70℃ for 21h under vacuum to obtain 29g of hydrogenated polymer A1.

[0085]

[0086] Example 2

[0087] Take 40g of the polymer to be hydrogenated, a2 (20000g / mol), and add it to 360g of xylene solution (10wt%). The catalyst is 5wt% platinum / alumina (100m). 2 12g (30%) of hydrogenated polymer A2 was reacted at 70℃ and 2MPa hydrogen pressure for 1h, with hydrogen continuously added to maintain stable reaction pressure. The reaction was then carried out at 140℃ and 5MPa hydrogen pressure for 3h. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers were precipitated, filtered, and dried at 60℃ for 24h under vacuum to obtain 38g of hydrogenated polymer A2.

[0088]

[0089] Example 3

[0090] Take 60g of the polymer to be hydrogenated, a3 (30000g / mol), and add it to 140g of n-hexane solution (30wt%). The catalyst is 3wt% palladium / calcium carbonate (200m). 2 1.2 g (2%) of hydrogenated polymer A3 was prepared at 100 °C and 2 MPa hydrogen pressure for 2 h, with hydrogen continuously added to maintain stable reaction pressure. The reaction was then carried out at 160 °C and 6 MPa hydrogen pressure for 5 h. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers were precipitated, separated by filtration, and dried at 80 °C for 18 h under vacuum to obtain 57 g of hydrogenated polymer A3.

[0091]

[0092] Example 4

[0093] Take 20g of the polymer to be hydrogenated, a4 (50000g / mol), and add it to 80g of n-heptane solution (20wt%). The catalyst is 10wt% platinum / barium sulfate (150m). 23g (15%) of hydrogenated polymer A4 was reacted at 80℃ and 1MPa hydrogen pressure for 2h, with hydrogen continuously added to maintain stable reaction pressure. The reaction was then carried out at 140℃ and 3MPa hydrogen pressure for 2h. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers were precipitated, filtered, and dried at 100℃ for 12h under vacuum to obtain 29g of hydrogenated polymer A4.

[0094]

[0095] Example 5

[0096] Take 30g of the polymer a5 (40000g / mol) to be hydrogenated and add it to 170g of cyclohexane solution (15wt%). The catalyst is 10wt% palladium / titanium dioxide (180m). 2 3g (10%) of hydrogenated polymer A5 was reacted at 90℃ and 3MPa hydrogen pressure for 2 hours, with hydrogen continuously added to maintain a stable reaction pressure. The reaction was then carried out at 170℃ and 7MPa hydrogen pressure for 5 hours. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers precipitated out, which were separated by filtration and dried at 120℃ for 6 hours under vacuum to obtain 28g of hydrogenated polymer A5.

[0097]

[0098] Example 6

[0099] Take 50g of the polymer to be hydrogenated, a6 (60000g / mol), and add it to 75g of methylcyclohexane solution (40wt%). The catalyst is 10wt% nickel / silica (150m). 2 0.25 g (0.5%) of hydrogenated polymer A6 was reacted at 100 °C and 3 MPa hydrogen pressure for 4 hours, with hydrogen continuously added to maintain a stable reaction pressure. The reaction was then carried out at 180 °C and 10 MPa hydrogen pressure for 6 hours. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers precipitated out, which were separated by filtration and dried at 90 °C for 15 hours under vacuum to obtain 47 g of hydrogenated polymer A6.

[0100]

[0101] Example 7

[0102] Take 30g of the polymer to be hydrogenated, a7 (30000g / mol), and add it to 30g of decahydronaphthalene solution (50wt%). The catalyst is 10wt% palladium / activated carbon (180m). 21.5 g (5%) of hydrogenated polymer A7 was prepared at 90 °C and 3 MPa hydrogen pressure for 3 hours, with hydrogen continuously added to maintain a stable reaction pressure. The reaction was then carried out at 160 °C and 8 MPa hydrogen pressure for 5 hours. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers were precipitated, filtered, and dried at 110 °C for 9 hours under vacuum to obtain 29 g of hydrogenated polymer A7.

[0103]

[0104] Comparative Example 1

[0105] Take 30g of the polymer to be hydrogenated, a1 (10000g / mol), and add it to 570g of toluene solution (5wt%). The catalyst is 5wt% palladium / silica (80m). 2 6g (20%) of hydrogenated polymer B1 (120nm) was reacted at 150℃ and 3MPa hydrogen pressure for 2h, during which hydrogen was continuously added to maintain the stability of the reaction pressure. Then the pressure was increased to 150℃ and 5MPa hydrogen pressure, and the reaction was continued for 4h. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol, precipitating out white strip-shaped polymers. The polymers were separated by filtration and dried at 70℃ for 21h under vacuum to obtain 29g of hydrogenated polymer B1.

[0106] Compared with Example 1, the conditions were the same except for the reaction temperature.

[0107] Comparative Example 2

[0108] Take 40g of the polymer to be hydrogenated, a2 (20000g / mol), and add it to 360g of xylene solution (10wt%). The catalyst is 5wt% platinum / alumina (100m). 2 12g (30%) of hydrogenated polymer B2 (100nm) was reacted at 140℃ and 5MPa hydrogen pressure for 4h. During the reaction, hydrogen was continuously added to maintain the stability of the reaction pressure. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol. White strip-shaped polymers were precipitated, filtered, and dried at 60℃ for 24h under vacuum to obtain 38g of hydrogenated polymer B2.

[0109] Compared with Example 2, the conditions were the same except for the reaction temperature and pressure in one stage.

[0110] Comparative Example 3

[0111] Take 30g of the polymer to be hydrogenated, b3 (10000g / mol), and add it to 570g of toluene solution (5wt%). The catalyst is 5wt% palladium / silica (80m). 26g (20%) of hydrogenated polymer B3 (120nm) was reacted at 90℃ and 3MPa hydrogen pressure for 2h, with hydrogen continuously added to maintain stable reaction pressure. The pressure was then increased to 150℃ and 5MPa hydrogen pressure, and the reaction continued for 4h. After the reaction was completed, the reaction solution was centrifuged, the catalyst was filtered, and the resulting solution was added to ethanol, precipitating white strip-shaped polymers. The polymers were separated by filtration and dried at 70℃ for 21h under vacuum to obtain 29g of hydrogenated polymer B3.

[0112] Compared with Example 1, all other conditions were the same except for the polymer monomer composition.

[0113]

[0114] The composition and performance test results of the hydrogenated cyclic olefin copolymers prepared in the examples and comparative examples are shown in Tables 2-4.

[0115] Table 2 Test data for hydrogenated cyclic olefin polymers

[0116]

[0117] Table 3 Composition data of hydrogenated cycloolefin compositions

[0118]

[0119]

[0120] Table 4 Performance data of hydrogenated cycloolefin polymers

[0121]

[0122] The data comparison above shows that, under the condition of fixed monomer composition and molecular weight, the hydrogenated cyclic olefin copolymer prepared by this invention can significantly reduce the content of isomerized DCPD in the prepared hydrogenated cyclic olefin copolymer by controlling the hydrogenation reaction conditions. This effectively prevents dispersion effects, significantly improves the refractive index, and enhances resistance to yellowing. Furthermore, the invention introduces aliphatic chains into the main chain structure, which increases the flexibility of the polymer chain, reduces the chain rigidity caused by the large steric hindrance of the polycyclic structure, and improves the processing flow properties of the polymer. In summary, the cyclic olefin resin composition containing the hydrogenated cyclic olefin copolymer prepared by this invention has the characteristics of high refractive index, low haze, and resistance to aging and yellowing, and also possesses excellent processing performance, making it suitable for applications in high-end flexible electronics and medical packaging fields.

[0123] Although the present invention has been described in detail through the preferred embodiments described 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, the schematic structural formula of which is as follows: in, A1, A2, A3, and A4 are independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or substituents containing halogen atoms, silicon atoms, oxygen atoms, or nitrogen atoms, such as hydrogen atoms, halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, and -OC groups. x H y -OCOC x H y -C x H y -C6H5, -C6H4CH3, -C 10 H7, -CH2C6H5, -CH2CH2C6H5, -C x H y C6H5; Where x is a positive integer less than or equal to 10, and y ≤ 2x + 1; A2 and A3 are optionally bonded to form a ring, A1 and A2 are optionally bonded to form an alkylidene group, A3 and A4 are optionally bonded to form an alkylidene group, and n represents an integer from 0 to 2; In the structural units B' and C', the dashed lines indicate whether they are bonded or not; n1 is the number of carbon atoms, 0≤n1≤4; R is the substituent structure that it carries when it is bonded, and R comes from R1-R15; R1 is selected from hydrogen atoms, hydroxyl groups or mercapto groups; The hydrogenated cyclic olefin copolymer satisfies the following conditions: 0 ≤ IDC1 ≤ 0.2 wt% In the formula, IDC1 represents the mass fraction of isomerized dicyclopentadiene (DCPD) in the hydrogenated cyclic olefin copolymer obtained by separating the hydrogenated cyclic olefin copolymer by gel permeation chromatography, where the weight average molecular weight is ≤50,000 based on repeating units composed of segments A', B', and C'.

2. The hydrogenated cyclic olefin copolymer according to claim 1, characterized in that, Structural unit C' is derived from norbornene monomers containing alicyclic and aromatic rings and / or C4-C8 cyclic olefin monomers, specifically from one or more of the following compounds:

3. The hydrogenated cyclic olefin copolymer according to claim 1, characterized in that, In Formula II, the molar ratio of the three structures A', B', and C' is (10%-80%):(10%-80%):(10%-80%); preferably (20%-60%):(10%-40%):(20%-60%).

4. The hydrogenated cyclic olefin copolymer according to claim 1, characterized in that, The weight-average molecular weight of the hydrogenated cyclic olefin copolymer is 1,000-200,000 g / mol, preferably 5,000-100,000 g / mol, and more preferably 10,000-50,000 g / mol.

5. The hydrogenated cyclic olefin copolymer according to claim 1, characterized in that, The hydrogenated cyclic olefin copolymer satisfies the following conditions: 0.2wt% < IDC2 ≤ 0.5wt%, In the formula, IDC2 represents the mass fraction of isomerized DCPD in hydrogenated cyclic olefin copolymers with a weight average molecular weight of >50,000 and ≤100,000, based on repeating units composed of segments A', B', and C' obtained by gel permeation chromatography.

6. The hydrogenated cyclic olefin copolymer according to claim 1, characterized in that, The hydrogenated cyclic olefin copolymer satisfies the following conditions: 0.5wt% < IDC3 ≤ 1wt% In the formula, IDC3 represents the mass fraction of isomerized DCPD in hydrogenated cyclic olefin copolymers obtained by gel permeation chromatography, where the weight average molecular weight is >100,000 and ≤200,000 based on repeating units composed of segments A', B', and C'.

7. A hydrogenated cyclic olefin resin composition comprising the following components: The hydrogenated cyclic olefin copolymer of any one of claims 1-6, comprising 80-99.9% by mass; Heterogeneous DCPD with a mass percentage of 0-1%; Olefin monomers and / or oligomers comprising 0.1-20% by mass; The structural schematic of the isomerized DCPD is one or more of the following formulas, where parentheses indicate the reaction sites: The olefin monomers and / or oligomers are hydrides of monomers of formula a, b1, b2, b3, or c, or oligomers of any combination thereof, and / or one or more hydrides of 1-octene and 1-hexene.

8. The hydrogenated cycloolefin resin composition according to claim 7, characterized in that, Refractive index 1.55-1.65, Tg 120-170℃, haze 1-5, MFR 30-100g / 10min, residual metal ions <1ppm, yellowness difference (ΔYI) <20 9. A method for preparing the hydrogenated cyclic olefin resin composition of claim 7 or 8, comprising the following steps: 1) Hydrogenation reaction: Aromatic cyclic olefin copolymer, solvent and catalyst are mixed and hydrogenated in multiple steps to obtain hydrogenated cyclic olefin copolymer; 2) Post-processing: Separate the catalyst from the product of step 1), add the resulting solution to ethanol, precipitate white strip-shaped polymer, separate and dry; The schematic structural formula of the aromatic cyclic olefin copolymer is Formula I: in, A1, A2, A3, and A4 are independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or substituents containing halogen atoms, silicon atoms, oxygen atoms, or nitrogen atoms, preferably hydrogen atoms, halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, -OCxHy, -OCOCxHy, -CxHy, -C6H5, -C6H4CH3, -C 10 H7, -CH2C6H5, -CH2CH2C6H5, -C x H y C6H5; Where x is a positive integer less than or equal to 10, and y ≤ 2x + 1; A2 and A3 are optionally bonded to form a ring, A1 and A2 are optionally bonded to form an alkylidene group, A3 and A4 are optionally bonded to form an alkylidene group, and n represents an integer from 0 to 2; In the structural units B and C, the dashed lines indicate whether they are bonded or not; n1 is the number of carbon atoms, 0≤n1≤4; R is the substituent structure that it carries when it is bonded, and R comes from R1-R15; R1 is selected from hydrogen atoms, hydroxyl groups or mercapto groups; The precursor of the unit structure shown in Formula A is a tetracyclic dodecene compound shown in Formula a; preferably, a tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Ethyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Cyclohexyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Cyclopentyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methoxycarbonyl-8-methyl-tetracyclo[4.4.0.1 2,5 .1 7,10 Unsubstituted or alkyl-containing tetracyclic dodecenes, such as 3-dodecene; 8-methylene-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Ethylene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Vinyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Propylene-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Cyclohexenyl-Tetracyclo[4.4.0.1 2, 5 .1 7,10 ]-3-Dodecene, 8-Cyclopentenyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene and other tetracyclic dodecenes with exocyclic double bonds; 8-phenyl-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Phenoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-(4-phenylphenoxy)carbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 [3-Dodecene and other tetracyclic dodecenes with aromatic rings; 8-methoxycarbonyl-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-n-Propoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Isopropoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-n-Butoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-n-propoxycarbonyl-tetracyclo[4.4.0.1 2, 5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-isopropoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-n-Butoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-hydroxymethyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Carboxy-Tetracyclo[4.4.0.1 2,5 .1 7,10 Tetracyclic dodecenes, such as 3-dodecene, tetracyclic dodecene-8,9-dicarboxylic acid, and tetracyclic dodecene-8,9-dicarboxylic anhydride, are tetracyclic dodecenes with substituents containing oxygen atoms; 8-cyano-tetracyclic [4.4.0.1] 2,5 .1 7,10 Tetracyclic dodecenes such as 3-dodecene and tetracyclic dodecene-8,9-dicarboximide have substituents containing nitrogen atoms; 8-chloro-tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene and other tetracyclic dodecenes having substituents containing halogen atoms; 8-trimethoxysilyl-tetracyclic [4.4.0.1] 2,5 .1 7,10 One or more of tetracyclic dodecenes, such as 3-dodecene, having substituents containing silicon atoms; Preferably, the precursor of the unit structure shown in Formula B is one of dicyclopentadiene, hydroxydicyclopentadiene, and mercaptodicyclopentadiene from Formulas b1, b2, and b3. Preferably, the unit structure represented by Formula C is derived from norbornene monomers containing alicyclic and aromatic rings and / or C4-C8 cyclic olefin monomers, more preferably from one or more of the following compounds:

10. The method according to claim 9, characterized in that, The multi-step hydrogenation process includes the following steps: a first-stage reaction at a temperature of 50-120℃, preferably 70-100℃, with a pressure of 1-3 MPa; a second-stage reaction at a temperature of 120-200℃, preferably 140-180℃, with a pressure of 3-10 MPa.

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