A high-barrier cycloolefin polymer and a method for preparing the same

Abstract

The application discloses a high-barrier cycloolefin polymer and a preparation method thereof. The high-barrier cycloolefin polymer has a structural unit shown in formula I. Compared with a commercially available cycloolefin polymer, the high-barrier cycloolefin polymer has obviously improved water and oxygen barrier rate, and meanwhile, the high-barrier cycloolefin polymer still has the advantages of high optical transmittance and high heat resistance of the cycloolefin polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyolefins, in particular to a high-barrier cyclic olefin polymer and a preparation method thereof. BACKGROUND

[0002] High-barrier polymer material is a kind of material with special function. This kind of material has the property of "high barrier" and low permeability to low molecular weight chemicals such as water vapor and oxygen. When it is made into a film and used in food packaging (especially meat processing products, raw meat, cheese, salad dressing, sauce, agricultural products and seafood processing products), it can prevent oxidation and microbial reproduction caused by the penetration of oxygen and other gases, and prevent the outflow of flavors, soups and other contents, thereby improving the storage of the contents. In addition, the high-barrier polymer film should also have strong water vapor barrier property to prevent mold growth of the contents due to the penetration of water vapor.

[0003] Existing high-barrier polymers are mainly PE, PP, PVC and other polyolefin materials, PET polyester, PA nylon, EVOH and other materials. Among them, PE, PP and other polyolefin materials have excellent water barrier performance, but the interaction between the molecular chains is weak, and the oxygen barrier performance is general. PA nylon material and EVOH material have a large number of hydrogen bonds between the molecular chains, which makes them have excellent oxygen barrier performance, but the presence of polar groups makes their water barrier performance general.

[0004] In order to achieve high barrier to water and oxygen at the same time, the existing technical solutions are: (1) multi-layer composite of polyolefin materials with excellent water barrier performance and nylon, EVOH and other materials with excellent oxygen barrier performance; (2) plating aluminum on the polyolefin substrate to improve the barrier property. In these two types of solutions, in addition to the need to introduce complex multi-layer co-extrusion film forming process or high temperature aluminum plating process, another component is introduced in the product in addition to polyolefin, which needs to be peeled off in material recycling, making it difficult to achieve fast recycling and causing serious environmental burden.

[0005] Cyclic olefin polymer (COP) is a kind of amorphous transparent polymer with high steric hindrance cyclic alkane structure in the main chain of the molecule. It is prepared by ring-opening metathesis polymerization of cyclic olefins and hydrogenation. The commercialized COP materials are ZEONEX and ZEONOR of ZEON Corporation in Japan, and ARTON of JSR Corporation in Japan. Due to the excellent properties of COP materials such as good light transmission, good molding processability and low moisture absorption, COP is widely used in polarizing plates, medical materials, packaging materials and other fields. The ZEONEX and ZEONOR series of COP products of ZEON Corporation are composed of pure C and H elements, and their water barrier performance is better than that of PE, PP and other polyolefin packaging materials. When used with PE and PP, the water barrier performance of PE and PP can be improved, but the oxygen barrier performance cannot be significantly improved. Therefore, improving the oxygen barrier performance of COP is still the direction of material improvement. SUMMARY

[0006] In view of the above problems in the prior art, the present application aims to provide a high-barrier cycloolefin polymer with oxygen and water resistance and a preparation method thereof. The high-barrier cycloolefin polymer has high transparency and high heat resistance in addition to the barrier property.

[0007] To achieve the above technical effects, the present application adopts the following solutions:

[0008] In a first aspect, the present application provides a high-barrier cycloolefin polymer comprising a structural unit represented by the following Formula I:

[0009]

[0010] In Formula I, L is -CH2-CH2- or -CH=CH-; n is an integer of 0-2; R is one or more of fluoroalkyl, fluoroaryl, preferably trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and the like; trifluorophenyl, pentafluorophenyl, and the like; and x is 10-500.

[0011] In some preferred embodiments, the high-barrier cycloolefin polymer of the present application further comprises a structural unit represented by the following Formula II:

[0012]

[0013] In Formula II, RC is any one of an alkyl group, a cycloalkyl group, preferably any one of a C4-C8 alkyl group, a C5-C 15 cycloalkyl group, more preferably any one of a C4-C8 alkylene group, a C5-C 15 cycloalkane structure-containing group; and y is 50-500.

[0014] In some preferred embodiments, the high-barrier cycloolefin polymer of the present application has a combination of blocks of the structural unit represented by Formula I and blocks of the structural unit represented by Formula II, and the total number of blocks of the structural unit represented by Formula I and the structural unit represented by Formula II is 2-5.

[0015] In some preferred embodiments, the structural unit represented by Formula I is prepared by ring-opening polymerization of a compound represented by Formula I-A in the presence of a chain transfer agent:

[0016]

[0017] In Formula I-A, R and n have the same definitions as those of R and n in Formula I above.

[0018] Preferably, the compound of formula I-A is selected from at least one of the following compounds of M-1, M-2, M-3, M-4, M-5 having the following structures:

[0019]

[0020] In some preferred embodiments, the structural unit of formula II is prepared from a cycloalkene compound of formula II-A:

[0021]

[0022] wherein RC is defined the same as RC in formula II above;

[0023] Preferably, the cycloalkene compound of formula II-A is selected from at least one of cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, norbornene, dicyclopentadiene, tetracyclododecene.

[0024] In the present application, the high-barrier cycloalkene polymer has a number average molecular weight of 5000-100000, such as 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000.

[0025] In the present application, the high-barrier cycloalkene polymer has a double bond mole content of ≤50%, such as 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1%, preferably ≤1%.

[0026] In the present application, the high-barrier cycloalkene polymer has a water vapor transmission rate <1 g / (m 2 .24h) under GB / T1037 standard;

[0027] In the present application, the high-barrier cycloalkene polymer has an oxygen transmission rate of 50-100 cm 3 / (m 2 .24h.0.1MPa) under GB / T1038 standard;

[0028] In the present application, the high-barrier cycloalkene polymer has a visible light band transmittance of 89%-93% under GB / T2410 standard;

[0029] In a second aspect, the present application also provides a preparation method of the above high-barrier cycloalkene polymer. The preparation method of olefin polymer is well known to those skilled in the art, and the following only provides an exemplary description, but does not constitute any limitation.

[0030] An exemplary method for preparing the high-barrier cyclic olefin polymer is obtained by two steps of step (1) polymerization and step (2) hydrogenation. The reaction route is shown as follows:

[0031]

[0032] Specifically, the method for preparing the high-barrier cyclic olefin polymer comprises the following steps:

[0033] (1) Polymerization:

[0034] S1: ring-opening metathesis polymerization of the compound shown in formula I-A under the action of a catalyst to obtain a polymer block I;

[0035] S2: adding a cyclic olefin compound shown in formula II-A to the polymer block I obtained in S1 for further polymerization to obtain a two-block copolymer;

[0036] Optionally, S3: adding a cyclic olefin compound shown in formula I-A and / or formula II-A to the two-block copolymer obtained in S2 for polymerization to obtain a block copolymer.

[0037] (2) Hydrogenation: hydrogenation reaction of the block copolymer obtained in step (1) with hydrogen to obtain the high-barrier cyclic olefin polymer.

[0038] In the present application, the polymerization process in step (1) is specifically:

[0039] S1: adding the compound shown in formula I-A to a solvent, and adding a ring-opening metathesis polymerization catalyst for solution polymerization reaction to obtain a polymer block shown in formula I. The molar ratio of the compound shown in formula I-A to the catalyst is 10-500:1, preferably 10-200:1.

[0040] S2: adding the compound shown in formula II-A to the reaction solution obtained in S1 for solution polymerization reaction to obtain a two-block polymer of formula I-II. The molar ratio of the cyclic olefin compound shown in formula II-A to the catalyst added in S1 is 50-500:1, preferably 50-200:1.

[0041] Optionally, S3: when a three-segment or more multi-block copolymer is needed, adding formula I-A or formula II-A to the two-block copolymer obtained in S2 for polymerization reaction, and the step S3 can be repeated multiple times as needed; when a three-segment or more multi-block copolymer is not needed, then step (1) only performs steps S1 and S2.

[0042] Preferably, the molar ratio of the compound of formula I-A to the amount of catalyst in S1 is 10-500:1, and the molar ratio of the cycloolefin compound of formula II-A to the amount of catalyst in S1 is 50-500:1.

[0043] The open ring metathesis polymerization catalyst can be selected according to the conventional method in the art, and the present application does not have a special requirement therefor, for example, can be any one or at least two combinations of a multi-component tungsten-based catalyst, a Grubbs series catalyst, and a Schrock series catalyst, and is preferably a Grubbs series catalyst.

[0044] The solvent in S1 is at least one selected from aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, and ether solvents.

[0045] Preferably, the aliphatic hydrocarbon solvent is at least one selected from n-hexane and heptane.

[0046] Preferably, the alicyclic hydrocarbon solvent is at least one selected from cyclopentane, cyclohexane, methylcyclohexane, and dimethylcyclohexane.

[0047] Preferably, the aromatic hydrocarbon solvent is at least one selected from benzene, toluene, and xylene.

[0048] Preferably, the halogenated aromatic hydrocarbon solvent is at least one selected from chlorobenzene and dichlorobenzene.

[0049] Preferably, the ether solvent is at least one selected from diethyl ether and tetrahydrofuran.

[0050] Preferably, the mass of the compound of formula I-A and the optional cycloolefin compound of formula II-A is 5-70% of the mass of the solvent, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70%, and preferably 20-50%.

[0051] The solution polymerization reaction is carried out at a temperature of 0-200°C, for example, 0, 10, 30, 50, 80, 100, 130, 150, 180, 200°C, and preferably 50-150°C, and for a time of 1-60 min, for example, 1, 10, 20, 30, 40, 50, 60 min, and preferably 1-30 min.

[0052] In the present application, the hydrogenation process in step (2) is specifically as follows: the block copolymer prepared in step (1) is subjected to hydrogenation reaction with hydrogen in the presence of a hydrogenation catalyst to obtain the high-barrier cycloolefin polymer.

[0053] The hydrogenation catalyst includes a homogeneous or heterogeneous catalyst, which can be selected by using conventional methods in the field, and the present application does not have special requirements therefor.

[0054] Preferably, the heterogeneous catalyst is selected from at least one of metal-loaded silicon dioxide, metal-loaded aluminum oxide, metal-loaded titanium oxide, skeletal nickel, palladium-carbon catalyst, and the like; wherein the metal is selected from at least one of nickel, palladium, platinum, rhodium, and ruthenium.

[0055] Preferably, the amount of the heterogeneous catalyst added is 0.5-10% of the mass of the reaction solution in step (2), for example, 0.5, 1, 3, 5, 7, 9, 10%.

[0056] Preferably, the homogeneous catalyst is selected from at least one of soluble complexes of nickel, titanium, palladium, platinum, rhodium, ruthenium, and the like, for example, a Ziegler hydrogenation catalyst composed of a nickel salt and an alkyl aluminum, a titanium metallocene-alkyllithium hydrogenation catalyst, a Ru(X)Cl(CO)L2 complex catalyst, and the like.

[0057] Preferably, the amount of the homogeneous catalyst added is 0.001-10% of the mass of the reaction solution in step (2), for example, 0.001, 0.01, 0.1, 0.5, 1, 3, 5, 7, 9, 10%, preferably 2-10% of the mass of the reaction solution.

[0058] In step (2), the reaction solution is the reaction solution obtained in step (1) or the diluted reaction solution.

[0059] The hydrogenation reaction is carried out at high temperature and high pressure; the hydrogenation temperature is 80-200°C, for example, 80, 100, 130, 150, 180, 200°C; the hydrogen feeding amount is determined by the charging pressure, and the charging hydrogen pressure is controlled to be 1-7 MPa of the reaction pressure, for example, 1, 2, 3, 4, 5, 6, 7 MPa.

[0060] Preferably, when the double bond molar content in the prepared high-barrier cyclic olefin polymer is ≤50%, for example, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1%, preferably ≤1%, the hydrogenation reaction is terminated.

[0061] In the present application, step (1) further includes terminating the reaction, and step (2) further includes the post-processing processes of acidification, flocculation, washing, drying, and the like, which are all conventional operations in the field, and the present application does not make specific limitations.

[0062] Compared with the prior art, the technical scheme of the present application has the following beneficial effects:

[0063] The high-barrier cycloolefin polymer has strong intermolecular forces and forms a dense structure to improve water and oxygen barrier properties of the material by introducing strong electronegative fluorine atoms. DETAILED DESCRIPTION

[0064] In order to better understand the technical solutions of the present application, the content of the present application will be further described below in combination with the following specific examples, but the content of the present application is not limited to the following examples.

[0065] The experimental methods used in the following examples are conventional methods unless otherwise specified.

[0066] The source information of the raw materials used in the following examples is as follows, and other conventional raw materials in the art are used unless otherwise specified, and the purity specifications used are analytical pure or chemical pure:

[0067] High-purity hydrogen: 99.999%, Dalian Guangming Special Gases Co., Ltd.;

[0068] Dicyclopentadiene: 98% (GC), Sigma-Aldrich;

[0069] Norbornene: 98%, TCI;

[0070] Tetracyclododecene: 98%, TCI;

[0071] Trifluoropropene: 99%, Balingwei Technology;

[0072] Pentafluorostyrene: 97%, Balingwei Technology;

[0073] Trifluorostyrene: 95%, Balingwei Technology;

[0074] Grubbs 3rd generation catalyst: 99.95%, Shanghai Aladdin;

[0075] Methyl norbornene: 98%, Shanghai Aladdin;

[0076] Phenyl norbornene: 98%, Pharmalink;

[0077] Palladium on carbon catalyst: Pd@C, Alfa;

[0078] Nickel acetylacetone: 95%, Shanghai Aladdin;

[0079] Triisobutylaluminum: 1.0M n-hexane solution, Shanghai Aladdin.

[0080] The compound and polymer structure synthesized in the application are measured by a Bruker ARX-400 nuclear magnetic resonance instrument, deuterated chloroform (CDCl3), deuterated benzene (C6D6), deuterated 1,1,2,2-tetrachloroethane (C2D2Cl4) as the solvent, and at room temperature or 90°C.

[0081] The polymer molecular weight and molecular weight distribution synthesized in the application are obtained by testing at 150°C by using a PL-GPC220, three PLgel 10μm MIXED-B separation columns connected in series, and 1,2,4-trichlorobenzene as the solvent.

[0082] The water vapor transmission rate of the polymer is determined according to the GB / T1037 standard.

[0083] The oxygen transmission rate of the polymer is determined according to the GB / T1038 standard.

[0084] The visible light transmittance of the polymer is determined according to the GB / T2410 standard. Specific embodiments

[0086] (I) Monomer preparation

[0087] Monomer synthesis example-1

[0088]

[0089] In a 2L stainless steel autoclave, 3.8mol of dicyclopentadiene, 9.6mol of trifluoropropene, and 0.06mol of 2,6-di-tert-butyl-4-methylphenol were added, the atmosphere in the autoclave was replaced with nitrogen, and then heated to 180°C. After stirring was started, the reaction was carried out for 6h. After the reaction was completed, the autoclave was cooled to room temperature, and the reaction product was purified by column chromatography (ethyl acetate / petroleum ether = 1 / 13) to obtain the corresponding monomer. 1H NMR (400MHz, CDCl3): δ = 6.16 (1H), δ = 5.96 (1H), δ = 2.95-2.89 (2H), δ = 2.66 (1H); δ = 2.06 (1H); δ = 1.49-1.59 (2H); δ = 1.13 (1H).

[0090] Monomer synthesis example-2

[0091]

[0092] The preparation of monomer M-2 is the same as that of monomer M-1, except that trifluorostyrene is used instead of trifluoropropene. 1H NMR (400MHz, CDCl3): δ = 7.08 (2H), δ = 6.24 (1H), δ = 5.88 (1H), δ = 2.93-3.05 (3H); δ = 2.00 (1H); δ = 1.47-1.58 (2H); δ = 1.09 (1H).

[0093] Monomer synthesis example-3

[0094]

[0095] The preparation of monomer M-3 was identical to monomer M-1 except that pentafluorostyrene was used instead of trifluoropropene.1H NMR (400 MHz, CDC13): δ = 6.24 (1H), δ = 5.87 (m, 1H), δ = 3.56 (1H), δ = 3.13 (1H); δ = 2.94 (1H); δ = 2.10 (1H); δ = 1.47-1.58 (2H); δ = 1.19 (1H).

[0096] Monomer synthesis example-4

[0097]

[0098] The preparation of monomer M-4 was identical to monomer M-1 except that M-2 was used instead of trifluoropropene.1H NMR (400 MHz, CDC13): δ = 7.09 (2H), δ = 5.85 (2H), δ = 2.93-3.05 (3H); δ = 3.42 (1H); δ = 2.85-2.87 (2H); δ = 2.12 (1H); δ = 1.93-1.99 (2H); δ = 1.72 (1H); δ = 1.56 (1H); δ = 1.45 (1H); δ = 1.34 (2H); δ = 1.21 (1H); δ = 1.04 (1H).

[0099] Monomer synthesis example-5

[0100]

[0101] In a 2L stainless steel autoclave, dicyclopentadiene 1.9 mol, monomer M-1 4.1 mol, 2,6-di-tert-butyl-4-methylphenol 0.03 mol were added, the atmosphere in the reactor was replaced by nitrogen, and then heated to 180°C with stirring. After 6h of reaction, the reactor was cooled to room temperature, and then dicyclopentadiene 1.8 mol was added to the reactor. The atmosphere in the reactor was replaced by nitrogen again, and then heated to 160°C with stirring. After 8h of reaction, the reaction product was purified by column chromatography (ethyl acetate / petroleum ether = 1 / 16) to obtain the corresponding monomer.1H NMR (400 MHz, CDC13): δ = 5.85 (2H), δ = 2.88-2.82 (3H); δ = 2.10-1.95 (6H); δ = 1.84-1.56 (6H); δ = 1.35-1.31 (3H); δ = 1.04 (1H).

[0102] (B) Polymer preparation

[0103] Example 1

[0104] Preparation of HPM-1

[0105]

[0106] (1-1) Preparation of ring-opening polymer (PM-1)

[0107] In a glove box, monomer M-1 1.6 g (10 mmol) was dissolved in 20 g of xylene and added to a 250 ml flask equipped with a magnetic bar, stirring was started and heating was applied; when the temperature reached 40°C, 0.8 g (1 mmol) of Grubbs third generation catalyst was added to the flask and polymerization was started. After 30 min of polymerization, dicyclopentadiene 13.2 g (100 mmol) was dissolved in 20 g of xylene and added to the reaction mixture and the reaction was continued; after 30 min of polymerization, M-1 1.6 g (10 mmol) was dissolved in 20 g of xylene and added to the reaction mixture and the reaction was continued for 30 min; 1 g of ethanol was added to stop the active centers. The total amount of the reaction mixture was 60 g. The ring-opening polymer had a weight average molecular weight Mw of 2.5 x 10 4 , and the conversion of monomer to polymer was > 99%.

[0108] (1-2) Preparation of hydrogenated ring-opening polymer (HPM-1)

[0109] In a glove box, nickel acetylacetonate 51.6 mg (200 μmol) was weighed and dispersed in 5 g of xylene, triisobutylaluminum 0.8 g (1.0 mmol) was extracted and injected into the nickel acetylacetonate, and the reaction was carried out for 2 min to prepare a hydrogenation catalyst.

[0110] The ring-opening polymer reaction mixture 60 g in (1-1) was diluted with 30 g of xylene and transferred to a stainless steel reactor which had been dried in advance, and the atmosphere in the reactor was replaced with nitrogen and then with hydrogen for 3 times each. The hydrogenation catalyst prepared above 5 g was injected into the reactor, and the pressure was increased to 4 MPa with hydrogen, stirring was started and heating was applied to 80°C. After 4 hours of reaction, the double bond content in the product was reduced to 1% and the hydrogenation reaction was terminated, and the corresponding hydrogenated polymer solution was obtained. After cooling, the reaction mixture was poured into acidified ethanol, and the polymer was precipitated and washed three times with deionized water, and dried in a vacuum oven. The hydrogenated polymer, polymer HPM-1, had a weight average molecular weight Mw of 2.7 x 10 4 , and the residual double bond content was < 1%.

[0111] (1-3) Preparation of hydrogenated polymer film

[0112] Take 5 g of the polymer obtained in step (1-2) and dissolve it in 20 ml of xylene. Pour the obtained polymer solution into a clean mold and evaporate the solvent to obtain a corresponding polymer film.

[0113] The permeability, water vapor transmission, oxygen transmission, etc. of the polymer HPM-1 obtained by the foregoing method were tested, and the results are shown in Table 1.

[0114] Example 2

[0115] Preparation of HPM-2

[0116]

[0117] (2-1) Preparation of ring-opening polymer (PM-2)

[0118] In a glove box, take 4.5 g (20 mmol) of monomer M-2 and dissolve it in 30 g of xylene and add it to a 250 ml flask equipped with a magnetic stirrer and heat; when the temperature is raised to 40°C, add 0.8 g (1 mmol) of Grubbs third-generation catalyst to the flask to start polymerization. After 30 minutes of polymerization, take 4.6 g (35 mmol) of dicyclopentadiene and 1.4 g (15 mmol) of norbornene, dissolve them in 20 g of xylene and add them to the reaction solution to continue the reaction; after 30 minutes of polymerization, take 4.5 g (20 mmol) of M-2, dissolve it in 20 g of xylene and add it to the reaction solution to continue the reaction for 30 minutes; add 1 g of ethanol to terminate the active center. The total amount of the reaction solution is 70 g. The weight average molecular weight Mw of the ring-opening polymer is 2.8 x 10 4 , and the conversion rate of monomer to polymer is >99%.

[0119] (2-2) Hydrogenation of ring-opening polymer (HPM-2)

[0120] Take 60 g of the ring-opening polymer reaction solution in (2-1), add 10 g of cyclohexane for dilution, and transfer it to a previously dried stainless steel reaction kettle. Add 2.8 g of palladium-carbon catalyst to the kettle, seal the kettle, and replace the atmosphere in the kettle with nitrogen and hydrogen 3 times in sequence. Pressurize with hydrogen to 4 MPa, start stirring and heat to 130°C. After 4 hours of reaction, the double bond content in the product is reduced to 1%, which is the end point of the hydrogenation reaction, to obtain the corresponding hydrogenated polymer solution. After cooling, centrifugal separation, pouring the supernatant into acidified ethanol, and flocculation and washing three times, the precipitated polymer is washed three times with deionized water and dried in a vacuum oven. The obtained hydrogenated polymer, i.e. polymer HPM-2, has a weight average molecular weight Mw of 2.9 x 10 4 , and the residual double bond content is <1%.

[0121] (2-3) Preparation of hydrogenated polymer film

[0122] Take 5 g of the hydrogenated polymer obtained in step (2-2) and dissolve it in 10 ml of xylene. Pour the polymer solution obtained by dissolving into a clean mold, and volatilize the solvent to obtain a corresponding hydrogenated polymer film.

[0123] The permeability, water vapor transmission amount, oxygen gas transmission amount, etc. of the polymer HPM-2 obtained by the aforementioned method were tested, and the results are shown in Table 1.

[0124] Example 3

[0125] Preparation of HPM-3

[0126]

[0127] (3-1) Preparation of ring-opening polymer (PM-3)

[0128] In a glove box, take 5.8 g (20 mmol) of monomer M-4, dissolve it in 30 g of xylene, and add it to a 250 ml flask equipped with a magnetic bar, and start stirring and heating; when the temperature is raised to 40°C, add 0.8 g (1 mmol) of Grubbs third-generation catalyst to the flask, and start polymerization. After 30 min of polymerization, take 3.33 g (25 mmol) of dicyclopentadiene and 4.0 g (25 mmol) of tetracyclododecene, dissolve them in 20 g of xylene, and add them to the reaction solution to continue the reaction; after 30 min of polymerization, take 6.8 g (20 mmol) of M-4, dissolve it in 20 g of xylene, and add it to the reaction solution to continue the reaction for 30 min; add 1 g of ethanol to terminate the active center. The total amount of the reaction solution is 70 g. The weight average molecular weight Mw of the ring-opening polymer is 3.1 x 10 4 , and the conversion rate of monomer to polymer is >99%.

[0129] (3-2) Hydrogenation of ring-opening polymer (HPM-3)

[0130] In a glove box, weigh 25.8 mg (100 μmol) of nickel acetylacetonate, and disperse it in 5 g of xylene. Extract 0.4 g (0.5 mmol) of triisobutylaluminum, and inject it into the nickel acetylacetonate to prepare a hydrogenation catalyst for 2 min.

[0131] Take 30 g of the ring-opening polymer reaction solution in (3-1), add 10 g of xylene for dilution, and transfer it to a previously dried stainless steel reaction kettle. Replace the atmosphere in the kettle with nitrogen and hydrogen 3 times in sequence. Inject 1 g of the hydrogenation catalyst prepared above into the reaction kettle, pressurize to 4 MPa with hydrogen, start stirring, and heat to 80°C. After 4 hours of reaction, the double bond content in the product is reduced to 1%, which is the hydrogenation reaction endpoint. After cooling, pour the reaction solution into acidified ethanol, flocculate and wash three times, wash the precipitated polymer with deionized water three times, and dry it in a vacuum oven. The obtained hydrogenated polymer, i.e., polymer HPM-3, has a weight average molecular weight Mw of 3.3 x 10 4 , and a residual double bond content of <1%.

[0132] (3-3) Preparation of hydrogenated polymer film

[0133] Take 5 g of the hydrogenated polymer obtained in step (3-2) and dissolve it in 10 ml of xylene. Pour the obtained polymer solution into a clean mold, and evaporate the solvent to obtain the corresponding hydrogenated polymer film.

[0134] The permeability, water vapor transmission amount, and oxygen transmission amount of the polymer HPM-3 obtained by the foregoing method were tested, and the results are shown in Table 1.

[0135] Example 4

[0136] Preparation of HPM-4

[0137]

[0138] (4-1) Preparation of ring-opening polymer (PM-4)

[0139] In a glove box, take 3.9 g (15 mmol) of monomer M-3, dissolve it in 30 g of xylene, and add it to a 250 ml flask equipped with a magnetic stirrer and heat it. When the temperature rises to 40°C, add 0.8 g (1 mmol) of Grubbs third-generation catalyst to the flask, and start the polymerization. After 30 min of polymerization, take 13.2 g (100 mmol) of dicyclopentadiene, dissolve it in 20 g of xylene, and add it to the reaction solution for continued reaction. After 30 min of polymerization, take 3.9 g (15 mmol) of M-3, dissolve it in 20 g of xylene, and add it to the reaction solution for continued reaction for 30 min. Add 1 g of ethanol to terminate the active centers. The total amount of the reaction solution is 70 g. The ring-opening polymer has a weight average molecular weight Mw of 4.1 x 10 4 , and a monomer conversion to polymer of >99%.

[0140] (4-2) Hydrogenation of ring-opening polymer (HPM-4)

[0141] In a glove box, weigh nickel acetylacetonate 25.8 μmol (100 μmol) and disperse it in 5 g of xylene, draw 0.4 g of triisobutylaluminum (0.5 mmol) and inject it into the nickel acetylacetonate, and react for 2 min to prepare a hydrogenation catalyst.

[0142] Weigh 20 g of the ring-opening polymer reaction solution in (4-1), add 20 g of xylene to dilute it, and transfer it to a stainless steel reaction kettle that has been dried in advance, and replace the atmosphere in the kettle with nitrogen, hydrogen, and nitrogen in this order for 3 times. Inject 2 g of the hydrogenation catalyst prepared above into the reaction kettle, pressurize it to 4 MPa with hydrogen, start stirring, and heat it to 80°C. After 4 hours of reaction, the content of double bonds in the product is reduced to 1% as the end point of the hydrogenation reaction, and a corresponding hydrogenated polymer solution is obtained. After cooling, pour the reaction solution into acidified ethanol, and perform flocculation and washing three times. The precipitated polymer is washed with deionized water three more times, and dried in a vacuum oven. The obtained hydrogenated polymer, i.e., polymer HPM-4, has a weight average molecular weight Mw of 4.5 x 104, and a residual double bond content of <1%. 4

[0143] (4-3) Preparation of a hydrogenated polymer film

[0144] Take 5 g of the hydrogenated polymer obtained in step (4-2), dissolve it in 10 ml of xylene, and pour the obtained polymer solution into a clean mold. Evaporate the solvent to obtain a corresponding hydrogenated polymer film.

[0145] Test the permeability, water vapor permeation amount, and oxygen permeation amount of the polymer HPM-4 obtained by the foregoing method, and the results are shown in Table 1.

[0146] Example 5

[0147] Preparation of HPM-1-2

[0148] (5-1) Preparation of a ring-opening polymer (PM-1-2)

[0149] In a glove box, take 8.1 g (50 mmol) of monomer M-1, dissolve it in 30 g of xylene, and add it to a 250 ml flask equipped with a magnetic stirrer, and start stirring and heating. When the temperature is raised to 40°C, add 0.08 g (0.1 mmol) of Grubbs third-generation catalyst to the flask, and start polymerization. After 30 min of polymerization, take 5.9 g (50 mmol) of dicyclopentadiene, dissolve it in 20 g of xylene, and add it to the reaction solution to continue the reaction. After 30 min of polymerization, take 8.1 g (50 mmol) of M-1, dissolve it in 30 g of xylene, and add it to the reaction solution to continue the reaction for 30 min. Add 1 g of ethanol to terminate the active centers. The total amount of the reaction solution is 80 g. The ring-opening polymer has a weight average molecular weight Mw of 24.5 x 104. 4 ​, the conversion of monomer to polymer is >99%.

[0150] (5-2) Hydrogenation of the ring-opening polymer (HPM-1-2)

[0151] In a glove box, weigh nickel acetylacetonate 25.8 μmol (100 μmol) and disperse it in 5 g of decalin, extract triisobutylaluminum 0.4 g (0.5 mmol) and inject it into the nickel acetylacetonate, react for 2 min to prepare the hydrogenation catalyst.

[0152] Weigh 20 g of the ring-opening polymer reaction solution in (5-1), add 20 g of xylene to dilute it, and transfer it to a stainless steel reactor that has been dried in advance, and replace the atmosphere in the reactor with nitrogen, hydrogen, and nitrogen respectively for 3 times. Inject 2 g of the hydrogenation catalyst prepared above into the reactor, pressurize with hydrogen to 4 MPa, start stirring and heat to 80°C. After 4 hours of reaction, the double bond content in the product is reduced to 1% as the hydrogenation reaction endpoint, and the corresponding hydrogenated polymer solution is obtained. After cooling, pour the reaction solution into acidified ethanol, flocculate and wash three times, and wash the precipitated polymer with deionized water three times, and dry it in a vacuum oven. The obtained hydrogenated polymer, polymer HPM-1-2, has a weight average molecular weight Mw of 25.5 x 10 4 , and the residual double bond content is <1%.

[0153] (5-3) Preparation of hydrogenated polymer film

[0154] Take 5 g of the hydrogenated polymer obtained in step (5-2) and dissolve it in 10 ml of xylene, pour the obtained polymer solution into a clean mold, and evaporate the solvent to obtain the corresponding hydrogenated polymer film.

[0155] The permeability, water vapor transmission amount, and oxygen transmission amount of the polymer HPM-1-2 obtained by the foregoing method were tested, and the results are shown in Table 1.

[0156] Example 6

[0157] Preparation of HPM-5

[0158]

[0159] (6-1) Preparation of ring-opening polymer (PM-5)

[0160] In a glove box, monomer M-2 16.8 g (75 mmol) was dissolved in 40 g of xylene and added to a 250 ml flask equipped with a magnetic bar, stirring was started and heating was applied; when the temperature reached 40°C, 0.8 g (1 mmol) of Grubbs third generation catalyst was added to the flask and polymerization was started. After 30 min of polymerization, dicyclopentadiene 6.6 g (50 mmol), tetracyclododecene 8.0 g (50 mmol) were dissolved in 40 g of xylene and added to the reaction mixture and the polymerization was continued; after 30 min of polymerization, M-2 16.8 g (75 mmol) was dissolved in 40 g of xylene and added to the reaction mixture and the polymerization was continued for 30 min; 1 g of ethanol was added to stop the active centers. The total amount of the reaction mixture was 120 g. The weight average molecular weight Mw of the ring-opening polymer was 4.9 x 10 4 The conversion of monomer to polymer was > 99%.

[0161] (6-2) Hydrogenation of the ring-opening polymer (HPM-5)

[0162] In a glove box, acetylacetonatonickel 25.8 μmol (100 μmol) was weighed and dispersed in 5 g of decalin, 0.4 g (0.5 mmol) of triisobutylaluminum was extracted and injected into the acetylacetonatonickel, and the reaction was carried out for 2 min to prepare a hydrogenation catalyst.

[0163] The ring-opening polymer reaction mixture 20 g in (6-1) was weighed, 20 g of xylene was added for dilution, and it was transferred to a stainless steel reaction kettle which was dried in advance, and the atmosphere in the kettle was replaced with nitrogen, hydrogen, respectively, 3 times in sequence. The 2 g of hydrogenation catalyst prepared above was injected into the reaction kettle, and the pressure was increased to 4 MPa with hydrogen, the stirring was started and the temperature was increased to 80°C. After 4 hours of reaction, the double bond content in the product was reduced to 1% as the end point of the hydrogenation reaction, the corresponding hydrogenated polymer solution was obtained, after cooling, the reaction mixture was poured into acidified ethanol, flocculation and washing were carried out three times, the precipitated polymer was washed with deionized water three times, and dried in a vacuum oven. The obtained hydrogenated polymer, i.e. polymer HPM-5, had a weight average molecular weight Mw of 5.2 x 10 4 The residual amount of double bond was < 1%.

[0164] (6-3) Preparation of hydrogenated polymer film

[0165] 5 g of the hydrogenated polymer obtained in step (6-2) was taken, dissolved in 10 ml of xylene, and the obtained polymer solution was poured into a clean mold, and the solvent was evaporated to obtain the corresponding hydrogenated polymer film.

[0166] The permeability, water vapor transmission amount, oxygen transmission amount, etc. of the polymer HPM-5 obtained by the foregoing method were tested, and the results are shown in Table 1.

[0167] Example 7

[0168] HPM-6 preparation

[0169]

[0170] (7-1) Preparation of ring-opening polymer (PM-6)

[0171] In a glove box, monomer M-11.6 g (10 mmol) was dissolved in 20 g of xylene and added to a 250 ml flask equipped with a magnetic bar, stirring was started and heating was applied; when the temperature reached 40°C, 0.8 g (1 mmol) of Grubbs third generation catalyst was added to the flask and polymerization was started. After 30 min of polymerization, dicyclopentadiene 13.2 g (100 mmol) was dissolved in 20 g of xylene and added to the reaction mixture and the reaction was continued; after 30 min of polymerization, M-5 2.9 g (10 mmol) was dissolved in 20 g of xylene and added to the reaction mixture and the reaction was continued for 30 min; 1 g of ethanol was added to stop the active centers. The total amount of the reaction mixture was 78 g. The weight average molecular weight Mw of the ring-opening polymer was 3.6 x 105and the conversion of monomer to polymer was > 99%. 4

[0172] (7-2) Preparation of hydrogenated ring-opening polymer (HPM-6)

[0173] In a glove box, nickel acetylacetonate 51.6 mg (200 μmol) was weighed and dispersed in 5 g of xylene, triisobutylaluminum 0.8 g (1.0 mmol) was extracted and injected into the nickel acetylacetonate, and the reaction was carried out for 2 min to prepare the hydrogenation catalyst.

[0174] The ring-opening polymer reaction mixture 60 g in (1-1) was diluted with 30 g of xylene and transferred to a stainless steel reactor previously dried, and the atmosphere in the reactor was replaced with nitrogen, hydrogen, and nitrogen three times in this order. The hydrogenation catalyst prepared above 5 g was injected into the reactor, and the pressure was increased to 4 MPa with hydrogen, stirring was started and heating was applied to 80°C. After 4 hours of reaction, the double bond content in the product was reduced to 1% and the hydrogenation reaction was terminated, and the corresponding hydrogenated polymer solution was obtained. After cooling, the reaction mixture was poured into acidified ethanol, flocculated and washed three times, the precipitated polymer was washed with deionized water three times, and dried in a vacuum oven. The hydrogenated polymer, i.e. polymer HPM-6, had a weight average molecular weight Mw of 2.7 x 105and a double bond residual amount of < 1%. 4

[0175] (7-3) Preparation of hydrogenated polymer film

[0176] ​​5 g of the polymer obtained in step (7-2) was dissolved in 20 ml of xylene, and the obtained polymer solution was poured into a clean mold, and the solvent was evaporated to obtain a corresponding polymer film.

[0177] The permeability, water vapor transmission amount, oxygen transmission amount, etc. of the polymer HPM-6 obtained by the foregoing method were tested, and the results are shown in Table 1.

[0178] Comparative Example 1

[0179] The polymer was prepared according to the preparation method of Reference Example 1, except that monomer M-1 was replaced by an equal amount of methyl norbornene, and other operations and parameters were unchanged, and the performance test results are shown in Table 1.

[0180] Comparative Example 2

[0181] The polymer was prepared according to the preparation method of Reference Example 2, except that monomer M-2 was replaced by an equal amount of phenyl norbornene, and other operations and parameters were unchanged, and the performance test results are shown in Table 1.

[0182] In addition, the performance of three brands of cyclic olefin polymers on the market, ZEONEX K26R and ZEONEX 690R of ZEON Company and ARTON F4520 of JSR Company, were also determined under the same conditions, and the results are shown in Table 1.

[0183] Table 1 Properties of polymers prepared in the examples and comparative examples of the present application and performance of commercially available cyclic olefin polymers

[0184]

[0185] Compared with the mainstream brands of commercial cyclic olefin polymers and the comparative examples, the water vapor transmission amount and the oxygen transmission amount were significantly reduced, while the high transparency of the material was also taken into account. According to the present application, a barrier material advantageously used for packaging can be provided.

Claims

1. A high-barrier cyclic olefin polymer, characterized by, comprising a structural unit represented by the following formula I: In formula I, L is -CH2-CH2- or -CH=CH-; n is an integer of 0-2; R is one of trifluoromethyl, pentafluoroethyl, heptafluoropropyl, trifluorophenyl, pentafluorophenyl; x is 10-500; comprising a structural unit represented by the following formula II: In Formula II, RC is a C4-C8 alkyl group, C5-C6 alkyl group, C6-C7 alkyl group, C6-C8 alkyl group, C6-C6 ... 15 Any of the cycloalkyl groups, where y is 50-500; The total number of the structural units represented by formula I and formula II is 2-5.

2. The high-barrier cyclic olefin polymer according to claim 1, characterized in that, In Formula II, RC is a C4-C8 alkylene group, C5-C6 alkylene group, C6-C6 alkylene group, C7-C8 alkylene group, C8-C6 alkylene group, C7 ... 15 Any one of the groups containing a cyclopentane structure.

3. The high-barrier cyclic olefin polymer according to claim 1, characterized by The structural unit represented by formula I is prepared from a compound represented by formula I-A: In formula I-A, R and n have the same definitions as R and n in formula I.

4. The high-barrier cyclic olefin polymer according to claim 3, characterized by The compound represented by formula I-A is selected from at least one of the following compounds M-1, M-2, M-3, M-4, M-5 having the following structures:

5. The high-barrier cyclic olefin polymer according to claim 3, characterized by The structural unit represented by formula II is prepared from a cyclic olefin compound represented by formula II-A: In formula II-A, RC has the same definition as RC in formula II.

6. The high-barrier cyclic olefin polymer according to claim 5, characterized by The cyclic olefin compound represented by formula II-A is selected from at least one of the following compounds: cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, norbornene, dicyclopentadiene, and tetracyclododecene.

7. The high-barrier cyclic olefin polymer according to claim 1, characterized by The high-barrier cyclic olefin polymer has a number average molecular weight of 5000-100000.

8. The high-barrier cyclic olefin polymer according to claim 1, characterized by The high-barrier cyclic olefin polymer has a double bond molar content of ≤50%.

9. The high-barrier cyclic olefin polymer according to claim 8, characterized by The high-barrier cyclic olefin polymer has a double bond molar content of ≤1%.

10. A method of producing the high barrier cyclic olefin polymer of claim 5, characterized by the steps of The method comprises: (1) polymerization: S1: ring-opening metathesis polymerization of the compound represented by formula I-A under the action of a catalyst to obtain a polymer block I; S2: adding the cyclic olefin compound represented by formula II-A to the polymer block I obtained in S1 to continue polymerization to obtain a two-block copolymer; Optionally, S3: adding the cyclic olefin compound represented by formula I-A and / or formula II-A to the two-block copolymer obtained in S2 to perform polymerization to obtain a multi-block copolymer; (2) hydrogenation: hydrogenation of the block copolymer obtained in step (1) to obtain the high-barrier cyclic olefin polymer.

11. The method of claim 10, wherein, A certain proportion of the compound represented by formula I-A and the cyclic olefin compound represented by formula II-A is added to a solvent, and a ring-opening metathesis polymerization catalyst is added to perform polymerization.

12. The method of claim 11, wherein, The ring-opening metathesis polymerization catalyst is any one or a combination of at least two of the following: a multi-component tungsten-based catalyst, a Grubbs series catalyst, and a Schrock series catalyst.

13. The method of claim 11, wherein, The solvent is selected from at least one of the following: an aliphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, and an ether solvent.

14. The method of claim 13, wherein, The aliphatic hydrocarbon solvent is selected from at least one of the following: n-hexane and heptane; the cycloaliphatic hydrocarbon solvent is selected from at least one of the following: cyclopentane, cyclohexane, methylcyclohexane, and dimethylcyclohexane; the aromatic hydrocarbon solvent is selected from at least one of the following: benzene, toluene, and xylene; the halogenated aromatic hydrocarbon solvent is selected from at least one of the following: chlorobenzene and dichlorobenzene; and the ether solvent is selected from at least one of the following: diethyl ether and tetrahydrofuran.

15. The preparation method according to claim 11, characterized in that, The mass of the compound represented by formula I-A and the cyclic olefin compound represented by formula II-A accounts for 5-70% of the mass of the solvent.

16. The method of claim 15, wherein, The compound of formula I-A and the cycloolefin compound of formula II-A have a mass of 20-50% of the mass of the solvent.

17. The method of claim 10, wherein, The mass ratio of the compound of formula I-A to the ring-opening metathesis polymerization catalyst in each addition in the optional step S3 is 10-500:

1.

18. The method of claim 10, wherein, The mass ratio of the compound of formula II-A to the ring-opening metathesis polymerization catalyst in each addition in the optional step S3 is 50-500:

1.

19. The method of claim 10, wherein, The polymerization reaction is carried out at a temperature of 0-200°C for 1-60 min.

20. The method of claim 19, wherein, The polymerization reaction is carried out at a temperature of 50-150°C for 5-30 min.

21. The method of claim 10, wherein, The hydrogenation in step (2) is specifically carried out by hydrogenating the block copolymer prepared in step (1) with hydrogen in the presence of a hydrogenation catalyst to obtain a high-barrier cycloolefin polymer.

22. The method of claim 21, wherein, The hydrogenation catalyst includes a homogeneous or heterogeneous catalyst; the heterogeneous catalyst is at least one selected from metal-loaded silica, metal-loaded alumina, metal-loaded titania, skeletal nickel, and palladium-carbon catalyst, wherein the metal is at least one selected from nickel, palladium, platinum, rhodium, and ruthenium; the homogeneous catalyst is at least one selected from soluble complexes of nickel, titanium, palladium, platinum, rhodium, and ruthenium.

23. The method of claim 22, wherein, The amount of the heterogeneous catalyst added is 0.5-10% of the mass of the reaction solution in step (2).

24. The method of claim 22, wherein, The amount of the homogeneous catalyst added is 0.001-10% of the mass of the reaction solution in step (2).

25. The method of claim 21, wherein, The hydrogenation reaction in step (2) is carried out at a temperature of 80-200°C; the amount of hydrogen is determined by the charging pressure, and the charging hydrogen pressure is controlled to be 1-7 MPa.

26. The method of claim 21, wherein, When the molar content of double bonds in the obtained high-barrier cycloolefin polymer is ≤50%, the hydrogenation reaction is terminated.

27. The method of claim 26, wherein, When the molar content of double bonds in the obtained high-barrier cycloolefin polymer is ≤1%, the hydrogenation reaction is terminated.

Images