A polynorbornene, a modified polynorbornene, and a method for producing the same

Abstract

The application provides a polynorbornene, a modified polynorbornene and a preparation method thereof, and belongs to the technical field of polymer materials. The polynorbornene is a random copolymer of norbornene, ethylidenenorbornene and phenylnorbornene. The polynorbornene provided by the application has a high molecular weight and a narrow molecular weight distribution, different functional groups can be introduced at different side chain positions of the same molecular chain, and the copolymer can be endowed with more new functions.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polynorbornene, modified polynorbornene, and a method for preparing the same. Background Technology

[0002] Polynorbornene (VA-PNB), obtained by addition polymerization of norbornene, has a fully saturated backbone and its structural unit is norbornene with two rings. It exhibits excellent aging resistance, thermal stability, and chemical stability. Furthermore, its unique cyclic structure endows VA-PNB with a high glass transition temperature and excellent transparency, making it widely applicable in optical materials and film materials. However, the non-polar nature of the norbornene structural unit in VA-PNB limits its applications. To expand the application range of VA-PNB, modifying it by introducing functional groups into the norbornene structural unit has become the main approach. However, existing VA-PNBs are mainly copolymers of norbornene and vinyl norbornene, which can only introduce functional groups through the carbon-carbon double bonds in the vinyl norbornene structural unit. Moreover, due to the limited reactivity of carbon-carbon double bonds, it is not possible to simultaneously introduce multiple functional groups into the copolymer, thus hindering the effective expansion of its application range.

[0003] Therefore, there is an urgent need to provide a polynorbornene that can simultaneously introduce multiple functional groups. Summary of the Invention

[0004] To address one or more technical problems existing in the prior art, the present invention provides a polynorbornene, modified polynorbornene, and a method for preparing the same. The polynorbornene provided by the present invention has a high molecular weight and a narrow molecular weight distribution, and can introduce different functional groups at different side chain positions on the same molecular chain, thereby endowing the copolymer with more new functions.

[0005] In a first aspect, the present invention provides a polynorbornene, wherein the polynorbornene is a random copolymer of norbornene, ethylidene norbornene and phenylnorbornene.

[0006] Preferably, the polynorbornene has a weight-average molecular weight of 40,000–400,000 g / mol, more preferably 45,000–380,000 g / mol, and a molecular weight distribution index of not more than 1.8, more preferably not more than 1.5; and / or

[0007] The polynorbornene comprises 15-60 wt% norbornene structural units, 20-70 wt% ethylene norbornene structural units, and 15-45 wt% phenyl norbornene structural units.

[0008] In a second aspect, the present invention provides a method for preparing the polynorbornene described in the first aspect, the method comprising:

[0009] A mixed solution containing norbornene, ethylene norbornene, and phenyl norbornene was mixed with a catalytic system and copolymerized to obtain the polynorbornene.

[0010] Preferably, the concentrations of norbornene, phenyl norbornene, and ethylidene norbornene in the mixed solution are independently 0.1–3.0 mol / L, more preferably 0.2–2.5 mol / L, and even more preferably 0.5–2.0 mol / L;

[0011] The solvent in the mixed solution is a solvent that does not contain active hydrogen, preferably at least one of C3-C10 saturated alkanes, C3-C10 cycloalkanes, C1-C5 haloalkanes, and C6-C15 aromatic hydrocarbons, more preferably at least one of propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane, toluene, xylene, dichloromethane, and 1,1,2,2-tetrachloroethane;

[0012] The copolymerization reaction is carried out at a temperature of -10°C to 80°C, preferably 0°C to 70°C, and more preferably 5°C to 60°C; and / or

[0013] The copolymerization reaction time is 0.5 to 48 hours, preferably 1.0 to 36 hours, and more preferably 1.5 to 24 hours.

[0014] Preferably, the catalytic system is one of a nickel catalytic system and a palladium catalytic system;

[0015] The main catalyst of the nickel catalytic system is a nickel complex, preferably an α-diimine nickel complex; more preferably, the structural formula of the α-diimine nickel complex is shown below:

[0016]

[0017] In the formula, R 1 Each is independently hydrogen or methyl; R 2 R 3 R 4 R 5 R 6 Each is independently selected from at least one of hydrogen, C1-C15 alkyl, C3-C15 cycloalkyl, and halogen; X is independently chlorine or bromine; preferably, R 2 R 3 R 4 R 5 R 6 Each is independently at least one of hydrogen, methyl, ethyl, and isopropyl;

[0018] The main catalyst of the palladium catalytic system is a palladium complex, preferably an allyl palladium chloride or an α-diimine palladium complex, more preferably an allyl palladium chloride; and / or

[0019] The cocatalysts of the nickel catalytic system and the palladium catalytic system are independently at least one selected from alkylaluminum halides, alkylaluminoxanes, and boron compounds; preferably, the alkylaluminum halides have the general formula R. m AlX 3-m Wherein, R is at least one of C1-C10 alkyl, C3-C10 cycloalkyl, C7-C10 aralkyl, and C6-C10 aryl; m is 1, 1.5, 2, or 3; X is a halogen, preferably Cl or Br; the alkylaluminoxane is at least one of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; and / or, the boron compound is at least one of AgBF4, B(C6F5)3, and sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; more preferably, the molar ratio of nickel to aluminum in the main catalyst of the nickel catalytic system is 1:50-3. The molar ratio of palladium in the main catalyst to aluminum in the co-catalyst of the palladium catalytic system is 1:50 to 3000, preferably 1:80 to 2500, more preferably 1:100 to 2300; and / or, the molar ratio of palladium in the main catalyst to boron in the co-catalyst of the palladium catalytic system is 1:1 to 5 (for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5), preferably 1:1 to 3, more preferably 1:1 to 2.

[0020] In a third aspect, the present invention provides a modified polynorbornene, wherein polar groups are introduced into the side chains of the polynorbornene described in the first aspect;

[0021] The polar group is at least one of sulfonic acid group, quaternary ammonium salt group, and -SX; wherein -X is at least one of aliphatic group containing hydroxyl group, aliphatic group containing carboxyl group, and aliphatic group containing ester group.

[0022] The present invention provides a method for preparing the modified polynorbornene described in the third aspect in a fourth aspect, characterized in that the preparation method comprises:

[0023] An initiator and a mercapto reagent are added to a solution containing the polynorbornene described in the first aspect to carry out a first reaction. The resulting solution is then precipitated and dried to obtain the modified polynorbornene.

[0024] Preferably, the initiator is at least one of azo initiators and organic peroxide initiators, and more preferably at least one of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, benzoyl peroxide, and methyl ethyl ketone peroxide.

[0025] The thiol reagent is a thiol containing different functional groups, preferably at least one of thiols containing hydroxyl groups, thiols containing carboxyl groups, and thiols containing ester groups, more preferably at least one of 3-mercapto-1-propanol, 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 2-mercaptoacetic acid, ethyl 2-mercaptoacetate, 3-mercaptopropionic acid, and ethyl 3-mercaptopropionate; and / or

[0026] The temperature of the first reaction is 20–100°C, and the time is 1–10 h.

[0027] Preferably, after precipitation and drying, the process further includes: dissolving the dried first product in an organic solvent, adding acesulfonic acid to carry out a second reaction, and then precipitating and drying the resulting solution; preferably, the temperature of the second reaction is -10 to 50°C, and the time is 1 to 48 hours.

[0028] Preferably, after precipitation and drying, the process further includes:

[0029] The dried first product, trioxymethylene, and trimethylchlorosilane were dissolved in an organic solvent, and anhydrous tin chloride was added to carry out the third reaction. The solution after the reaction was precipitated and dried to obtain the third product.

[0030] The third product was dissolved in an organic solvent, and an amine was added to carry out the fourth reaction. The resulting solution was then precipitated and dried.

[0031] Preferably, the amine is a tertiary amine;

[0032] The third reaction is carried out at a temperature of -10 to 50°C for a time of 1 to 48 hours; and / or

[0033] The temperature of the fourth reaction is 25–60°C, preferably 40–60°C; the time of the fourth reaction is 1–24 h, preferably 3–10 h.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects:

[0035] This invention provides a random polynorbornene with a high molecular weight and narrow molecular weight distribution, obtained by copolymerizing norbornene (NB), ethylene-nenorbornene (ENB), and phenylnorbornene (PNB). The side chains of this polynorbornene simultaneously contain functionalizable double bonds and benzene rings, allowing for the introduction of different functional groups at different positions on the same molecular chain, thus endowing the copolymer with more novel functions. Compared to carbon-carbon double bonds, benzene ring structures can undergo a wider range of functionalization reactions. Therefore, copolymerizing phenylnorbornene with norbornene and ethylene-nenorbornene allows for the introduction of more diverse functional groups into the side chains of the same molecular chain of the copolymer, broadening its application range.

[0036] The modified polynorbornene provided by this invention introduces polar groups onto the side chains of polynorbornene. Specifically, -SX groups are attached to the side chains of ethylene norbornene units, while sulfonic acid groups and quaternary ammonium salt groups are attached to the side chains of phenyl norbornene units. Simultaneously, the norbornene units are nonpolar units, giving the modified polynorbornene both polar and nonpolar properties, as well as hydrophilic and oleophilic properties. Furthermore, different polar groups can be attached to the side chains of different units within the same molecular chain of the modified polynorbornene, allowing the polymer to possess more functions and effectively broadening its application range. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0038] In one aspect, the present invention provides a polynorbornene, wherein the polynorbornene is a random copolymer of norbornene, ethylidene norbornene and phenylnorbornene.

[0039] This invention provides a random polynorbornene with a high molecular weight and narrow molecular weight distribution, obtained by copolymerizing norbornene, ethylene-nebornene, and phenylnorbornene. The side chains of this polynorbornene simultaneously contain functionalizable double bonds and benzene rings, allowing for the introduction of different functional groups at different positions on the same molecular chain, thus endowing the copolymer with more novel functions. Compared to carbon-carbon double bonds, benzene ring structures can undergo a wider range of functionalization reactions. Therefore, copolymerizing phenylnorbornene with norbornene and ethylene-nebornene allows for the introduction of more diverse functional groups into the side chains of the same molecular chain of the copolymer, effectively broadening its application range.

[0040] According to some preferred embodiments, the polynorbornene has a weight-average molecular weight of 40,000–400,000 g / mol, preferably 45,000–380,000 g / mol, and a molecular weight distribution index of not more than 1.8, preferably not more than 1.5; and / or

[0041] The polynorbornene comprises 15-60 wt% norbornene structural units, 20-70 wt% ethylene norbornene structural units, and 15-45 wt% phenyl norbornene structural units.

[0042] The present invention provides a method for preparing the polynorbornene described in the first aspect in a second aspect, characterized in that the preparation method comprises:

[0043] A mixed solution containing norbornene, ethylene norbornene, and phenyl norbornene was mixed with a catalytic system and copolymerized to obtain the polynorbornene.

[0044] This invention, for the first time, utilizes a suitable catalyst to catalyze the addition copolymerization of norbornene (NB), ethylene norbornene (ENB), and phenyl norbornene (PNB) to prepare polynorbornene with side chains containing both carbon-carbon double bonds and benzene rings. This polynorbornene is a random copolymer with a high molecular weight and a narrow molecular weight distribution. The reaction formula for preparing this polynorbornene is shown below:

[0045]

[0046] It should be noted that, in this invention, the reaction can be terminated with an acidic alcohol solution after a certain period of time in the third copolymerization reaction. In some preferred embodiments of this invention, the acidic alcohol solution is a hydrochloric acid-ethanol solution.

[0047] In some preferred embodiments of the present invention, the mixed solution comprising norbornene, ethylidene norbornene, and phenyl norbornene is mixed with the catalyst system in one of the following ways:

[0048] (1) Add the main catalyst first and then the co-catalyst to a mixed solution containing norbornene, ethylene norbornene and phenyl norbornene;

[0049] (2) Add the co-catalyst first and then the main catalyst to the mixed solution containing norbornene, ethylene norbornene and phenyl norbornene;

[0050] (3) Add the main catalyst and the co-catalyst simultaneously to a mixed solution containing norbornene, ethylene norbornene and phenyl norbornene;

[0051] (4) The main catalyst and the co-catalyst are pre-mixed and then added to a mixed solution containing ethylidene norbornene and phenyl norbornene.

[0052] According to some preferred embodiments, the concentrations of norbornene, phenylnorbornene, and ethylidene norbornene in the mixed solution are independently 0.1–3.0 mol / L (e.g., 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, or 3 mol / L), preferably 0.2–2.5 mol / L (e.g., 0.2 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, or 2.5 mol / L), and more preferably 0.5–2.0 mol / L (e.g., 0.5 mol / L, 1 mol / L, 1.5 mol / L, or 2 mol / L).

[0053] The solvent in the mixed solution is a solvent that does not contain active hydrogen, preferably at least one of C3-C10 saturated alkanes, C3-C10 cycloalkanes, C1-C5 haloalkanes, and C6-C15 aromatic hydrocarbons, more preferably at least one of propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane, toluene, xylene, dichloromethane, and 1,1,2,2-tetrachloroethane;

[0054] The copolymerization reaction temperature is -10℃ to 80℃ (e.g., -10℃, 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, or 80℃), preferably 0℃ to 70℃ (e.g., 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, or 70℃), more preferably 5℃ to 60℃ (e.g., 5℃, 10℃, 20℃, 30℃, 40℃, 50℃, or 60℃); and / or

[0055] The copolymerization reaction time is 0.5 to 48 hours (e.g., 0.5 hours, 1.5 hours, 5 hours, 8 hours, 10 hours, 15 hours, 18 hours, 20 hours, 25 hours, 28 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours, 42 hours, 45 hours, or 48 hours), preferably 1.0 to 36 hours (e.g., 1 hour, 1.5 hours, 5 hours, 8 hours, 10 hours, 15 hours, 18 hours, 20 hours, 25 hours, 28 hours, 30 hours, 32 hours, 35 hours, or 36 hours), and more preferably 1.5 to 24 hours (e.g., 1.5 hours, 5 hours, 8 hours, 10 hours, 15 hours, 18 hours, 20 hours, or 24 hours).

[0056] According to some preferred embodiments, the catalytic system is one of a nickel catalytic system and a palladium catalytic system;

[0057] The main catalyst of the nickel catalytic system is a nickel complex, preferably an α-diimine nickel complex; more preferably, the structural formula of the α-diimine nickel complex is shown below:

[0058]

[0059] In the formula, R 1 Each is independently hydrogen or methyl; R 2 R 3 R 4 R 5 R 6 Each is independently selected from at least one of hydrogen, C1-C15 alkyl, C3-C15 cycloalkyl, and halogen; X is independently chlorine or bromine; preferably, R 2 R 3 R 4 R 5 R 6 Each is independently at least one of hydrogen, methyl, ethyl, and isopropyl;

[0060] The main catalyst of the palladium catalytic system is a palladium complex, preferably an allyl palladium chloride or an α-diimine palladium complex, more preferably an allyl palladium chloride; and / or

[0061] The cocatalysts of the nickel catalytic system and the palladium catalytic system are independently at least one selected from alkylaluminum halides, alkylaluminoxanes, and boron compounds; preferably, the alkylaluminum halides have the general formula R. m AlX 3-m Wherein, R is at least one of C1-C10 alkyl, C3-C10 cycloalkyl, C7-C10 aralkyl, and C6-C10 aryl; m is 1, 1.5, 2, or 3; X is a halogen, preferably Cl or Br; the alkylaluminoxane is at least one of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; and / or, the boron compound is at least one of AgBF4, B(C6F5)3, and sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; more preferably, the molar ratio of nickel to aluminum in the main catalyst of the nickel catalytic system is 1:50-3. The molar ratio of palladium in the main catalyst to aluminum in the co-catalyst of the palladium catalytic system is 1:50 to 3000, preferably 1:80 to 2500, more preferably 1:100 to 2300; and / or, the molar ratio of palladium in the main catalyst to boron in the co-catalyst of the palladium catalytic system is 1:1 to 5 (for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5), preferably 1:1 to 3, more preferably 1:1 to 2.

[0062] In polymerization reactions, co-catalysts not only react with the main catalyst to form active centers, but also eliminate impurities in the polymerization system. Therefore, the amount of co-catalyst needs to be kept within a certain range to ensure the catalytic system is active. The inventors have found that further increasing the amount of co-catalyst component within the above range has little impact on catalytic activity, but increases catalyst cost. Therefore, when selecting a nickel-based or palladium-based catalytic system, the preferred molar ratio of nickel or palladium in the main catalyst to aluminum in the co-catalyst is 1:50 to 3000.

[0063] In some preferred embodiments of the present invention, the α-diimine nickel complex has the following structure, but is not limited to the following structure:

[0064]

[0065] In a third aspect, the present invention provides a modified polynorbornene, wherein the modified polynorbornene has polar groups introduced into the side chains of the polynorbornene described in the first aspect.

[0066] The polar group is at least one of sulfonic acid group, quaternary ammonium salt group, and -SX; wherein -X is at least one of aliphatic group containing hydroxyl group, aliphatic group containing carboxyl group, and aliphatic group containing ester group.

[0067] The modified polynorbornene provided by this invention introduces polar groups onto the side chains of polynorbornene. Specifically, -SX groups are attached to the side chains of ethylene norbornene units, while sulfonic acid groups and quaternary ammonium salt groups are attached to the side chains of phenyl norbornene units. Simultaneously, the norbornene units are nonpolar units, giving the modified polynorbornene both polar and nonpolar properties, as well as hydrophilic and oleophilic properties. Furthermore, different polar groups can be attached to the side chains of different units within the same molecular chain of the modified polynorbornene, allowing the polymer to possess more functions and effectively broadening its application range.

[0068] Existing nonpolar polynorbornene is mainly used in optical materials, membrane materials, syringes, and vaccine vials. Modified polynorbornene, with the introduction of polar groups, can also be used for bonding with metal and glass substrates, significantly broadening its application range. Furthermore, the introduction of sulfonic acid and quaternary ammonium salt groups into the structure imbues the modified polynorbornene with electrical conductivity, enabling its application in fuel cell membranes. In addition, the quaternary ammonium salt groups also provide antibacterial properties, allowing the modified polynorbornene to be used in applications requiring antibacterial properties.

[0069] The present invention provides, in a fourth aspect, a method for preparing the modified polynorbornene described in the third aspect, the method comprising:

[0070] An initiator and a mercapto reagent are added to a solution containing the polynorbornene described in the first aspect to carry out a first reaction. The resulting solution is then precipitated and dried to obtain the modified polynorbornene.

[0071] This invention involves adding an initiator and a thiol reagent (HS-X) to a solution of polynorbornene and reacting the mixture to introduce -SX groups into the side chains of the ethylene-based norbornene units, thereby obtaining modified polynorbornene (first modified polynorbornene) with -SX groups in the side chains; the reaction formula is shown below:

[0072]

[0073] According to some preferred embodiments, the initiator is at least one of azo initiators and organic peroxide initiators, preferably at least one of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, benzoyl peroxide, and methyl ethyl ketone peroxide;

[0074] The thiol reagent is a thiol containing different functional groups, preferably at least one of thiols containing hydroxyl groups, thiols containing carboxyl groups, and thiols containing ester groups, more preferably at least one of 3-mercapto-1-propanol, 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 2-mercaptoacetic acid, ethyl 2-mercaptoacetate, 3-mercaptopropionic acid, and ethyl 3-mercaptopropionate; and / or

[0075] The temperature of the first reaction is 20 to 100°C (e.g., 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C), and the time is 1 to 10 hours (e.g., 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours).

[0076] According to some preferred embodiments, after precipitation and drying, the process further includes: dissolving the dried first product in an organic solvent, adding acesulfonic acid to carry out a second reaction, and precipitating and drying the resulting solution; preferably, the temperature of the second reaction is -10 to 50°C (e.g., -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, or 50°C), and the time is 1 to 48 hours (e.g., 1 hour, 2 hours, 5 hours, 6 hours, 8 hours, 10 hours, 15 hours, 20 hours, 24 hours, 28 hours, 30 hours, 32 hours, 36 hours, 40 hours, 42 hours, or 48 hours).

[0077] Furthermore, this invention reacts modified polynorbornene with -SX groups attached to its side chains (first modified polynorbornene) with acetylsulonic acid to introduce sulfonic acid groups into the side chains of the phenylnorbornene units, thereby obtaining modified polynorbornene with side chains containing both -SX groups and sulfonic acid groups (second modified polynorbornene); the reaction formula is as follows:

[0078]

[0079] In the formula, -X is at least one of an aliphatic group containing a hydroxyl group, an aliphatic group containing a carboxyl group, and an aliphatic group containing an ester group.

[0080] According to some preferred embodiments, the process after precipitation and drying further includes:

[0081] The dried first product, trioxymethylene, and trimethylchlorosilane were dissolved in an organic solvent, and anhydrous tin chloride was added to carry out the third reaction. The solution after the reaction was precipitated and dried to obtain the third product.

[0082] The third product was dissolved in an organic solvent, and an amine was added to carry out the fourth reaction. The resulting solution was then precipitated and dried.

[0083] Preferably, the amine is a tertiary amine; in some preferred embodiments of the present invention, the tertiary amine is preferably at least one of trimethylamine, triethylamine, and tri-n-propylamine, but is not limited thereto.

[0084] The temperature of the third reaction is -10 to 50°C (e.g., -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, or 50°C), and the time is 1 to 48 hours (e.g., 1 hour, 2 hours, 5 hours, 6 hours, 8 hours, 10 hours, 15 hours, 20 hours, 24 hours, 28 hours, 30 hours, 32 hours, 36 hours, 40 hours, 42 hours, or 48 hours); the temperature of the fourth reaction is 25 to 60°C (e.g., 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C), preferably 40 to 60°C (e.g., 40°C, 45°C, 50°C, 55°C, or 60°C); and / or

[0085] The fourth reaction time is 1 to 24 hours (e.g., it can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours or 24 hours), preferably 3 to 10 hours (e.g., it can be 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours).

[0086] Furthermore, this invention involves reacting modified polynorbornene with -SX groups attached to its side chains (first modified polynorbornene) with trioxymethylene and trimethylchlorosilane under the catalysis of anhydrous tin chloride, introducing chloromethyl groups into the side chains of the phenylnorbornene units, and reacting the resulting product with an amine to finally introduce quaternary ammonium salt groups into the side chains of the phenylnorbornene units, thereby obtaining modified polynorbornene with both -SX groups and quaternary ammonium salt groups attached to its side chains (third modified polynorbornene); the reaction formula is as follows:

[0087]

[0088] In the formula, R1, R2, and R3 are alkyl groups. R1, R2, and R3 can be the same alkyl group or different alkyl groups.

[0089] To more clearly illustrate the technical solution and advantages of the present invention, the present invention will be further described below in conjunction with embodiments.

[0090] Weight-average molecular weight: Characterized by high-temperature gel permeation chromatography with trichlorobenzene as the mobile phase and a test temperature of 150℃.

[0091] Mass fraction of each structural unit in the copolymer: via 1 ¹H NMR characterization was performed based on the peak areas of the characteristic peaks on the double bond and benzene ring.

[0092] Example 1

[0093] Preparation of polynorbornene:

[0094] At 10°C, the following formula I was added sequentially to 10 mL of a toluene solution containing 0.5 mol / L ethylene norbornene (ENB), 0.5 mol / L norbornene (NB), and 0.5 mol / L phenyl norbornene (PNB). a The main catalyst (0.01 mmol) and co-catalyst sesquiethylaluminum chloride are shown, wherein the molar ratio of Al in sesquiethylaluminum chloride to Ni in the main catalyst is 200. After 5 hours of polymerization, a 5% (w / w) hydrochloric acid-ethanol solution is added to terminate the reaction. The resulting polymer is dried at 40 °C to constant weight to obtain 1.90 g of polynorbornene P (NB-co-ENB-co-PNB). The weight-average molecular weight (M) of this polynorbornene is... w The molecular weight distribution index (M) is 276,000 g / mol. w / M n The mass fraction of NB structural units in the copolymer is 1.5; the mass fraction of ENB structural units is 25%, the mass fraction of ENB structural units is 31%, and the mass fraction of PNB structural units is 44%.

[0095]

[0096] Preparation of modified polynorbornene:

[0097] (1) Modification with thiol reagents:

[0098] 1.1 g of the prepared polynorbornene was dissolved in 20 mL of toluene, and 0.017 mmol of azobisisobutyronitrile and 3.34 mmol of mercaptoethanol (2-mercaptoethanol) were added sequentially. The reaction was carried out at 60 °C for 6 h. The resulting solution was then added to 100 mL of ethanol, and the polymer precipitated. After washing and filtration with ethanol, the obtained polymer was dried at 40 °C to constant weight to obtain 1.2 g of mercapto-modified polynorbornene (first-modified polynorbornene). NMR analysis showed no characteristic peaks of double bonds at 5.05 and 5.25 ppm, indicating that the double bonds on the ENB structural unit were completely transformed. A characteristic peak of CH2 linked to a hydroxyl group appeared at 3.65 ppm. The structure of the first-modified polynorbornene is shown in the figure below.

[0099]

[0100] (2) Sulfonic acid group modification:

[0101] 1.0 g of the first modified polynorbornene obtained in (1) was dissolved in 20 mL of 1,2-dichloroethane. 5 mmol of acesulfonic acid was added at 0 °C. After reacting for 5 h at room temperature, the solution was poured into ethanol for precipitation. After drying, 1.1 g of polynorbornene co-modified with mercapto reagent and sulfonic acid group (second modified polynorbornene) was obtained. According to NMR analysis, the characteristic peak of the para H atom on the benzene ring at 7.25 ppm disappeared, while a new characteristic peak appeared at 7.75 ppm, indicating that the benzene ring on the PNB structural unit was completely sulfonated. The structure of the second modified polynorbornene is shown in the figure below.

[0102]

[0103] Example 2

[0104] Preparation of polynorbornene:

[0105] At 20°C, methylaluminoxane, a co-catalyst, and 0.015 mmol of the following formula I were sequentially added to 10 mL of a dichloromethane solution containing 1.5 mol / L ethylene norbornene (ENB), 0.5 mol / L norbornene (NB), and 0.3 mol / L phenyl norbornene (PNB). b The main catalyst shown has a molar ratio of Al in methylaluminoxane to Ni in the main catalyst of 1500. After polymerization for 10 hours, a 5% (w / w) hydrochloric acid-ethanol solution was added to terminate the reaction. The resulting polymer was dried at 40°C to constant weight to obtain 2.75 g of polynorbornene P (NB-co-ENB-co-PNB). The weight-average molecular weight (M) of this polynorbornene is... w The molecular weight distribution index (M) is 225,000 g / mol. w / Mn The mass fraction of NB structural units in the copolymer is 17%, the mass fraction of ENB structural units is 65%, and the mass fraction of PNB structural units is 18%.

[0106]

[0107] Preparation of modified polynorbornene:

[0108] (1) Modification with thiol reagents:

[0109] 1.6 g of the prepared polynorbornene was dissolved in 30 mL of tetrahydrofuran, and 0.061 mmol of azobisisoheptanenitrile and 12.2 mmol of mercaptoacetic acid were added sequentially. The reaction was carried out at 40 °C for 10 h. The resulting solution was then added to 150 mL of ethanol, and the polymer precipitated. After washing and filtration with ethanol, the obtained polymer was dried at 40 °C to constant weight to obtain 1.7 g of mercapto-modified polynorbornene (first-modified polynorbornene). NMR analysis showed no characteristic peaks of double bonds at 5.05 and 5.25 ppm, indicating that the double bonds on the ENB structural unit were completely transformed. A characteristic peak of CH2 linked to a carboxyl group appeared at 3.10 ppm, indicating that the structure of the obtained first-modified polynorbornene is shown in the figure below.

[0110]

[0111] (2) Quaternary ammonium salt group modification:

[0112] 1.5g of the first modified polynorbornene obtained in (1) was dissolved in chloroform along with 6mmol of trioxymethylene and 6mmol of trimethylchlorosilane. Then, 0.05g of anhydrous tin chloride was added, and the mixture was reacted at 50°C for 5h. The resulting solution was then precipitated in ethanol and dried to obtain a modified intermediate product. The modified intermediate product was then dissolved in chloroform, and 8mmol of trimethylamine was added. The mixture was stirred at 40°C for 3h, and the resulting polymer solution was then precipitated in ethanol and dried to obtain 1.68g of polynorbornene co-modified with mercapto reagent and quaternary ammonium salt group (third modified polynorbornene). According to NMR analysis, the characteristic peak of the para-H atom on the benzene ring at 7.25ppm disappeared, while a new characteristic peak appeared at 7.75ppm, indicating that the benzene ring on the PNB structural unit was completely functionalized. A characteristic peak of CH2 connected to nitrogen appeared at 4.50ppm, proving that the structure of the obtained third modified polynorbornene is shown in the figure below.

[0113]

[0114] Example 3

[0115] Preparation of polynorbornene:

[0116] 0.01 mmol of the following formula I b The α-diimine nickel complex (main catalyst) and sesquiethylaluminum chloride (co-catalyst) were mixed together, and 1 mL of dichloromethane was added to obtain an α-diimine nickel complex catalyst system solution; wherein the molar ratio of Al in sesquiethylaluminum chloride to Ni in the main catalyst was 800; at 50 °C, the above α-diimine nickel complex catalyst system solution was added to 10 mL of a toluene solution containing 0.5 mol / L ethylene norbornene (ENB), 1.0 mol / L norbornene (NB), and 0.3 mol / L phenyl norbornene (PNB), and the polymerization reaction was carried out for 3 hours. Then, a 5% (w / w) hydrochloric acid ethanol solution was added to terminate the reaction. The obtained polymer was dried at 40 °C to constant weight to obtain 2.5 g of polynorbornene P (NB-co-ENB-co-PNB). The weight-average molecular weight (M) of this polynorbornene is... w The molecular weight distribution index (M) is 358,000 g / mol. w / M n The mass fraction of the copolymer is 1.5; the mass fraction of NB structural units is 56%, the mass fraction of ENB structural units is 24%, and the mass fraction of PNB structural units is 20%.

[0117]

[0118]

[0119] Preparation of modified polynorbornene:

[0120] (1) Modification with thiol reagents:

[0121] 1.50 g of the prepared polynorbornene was dissolved in 30 mL of toluene, and 0.025 mmol of benzoyl peroxide and 5.0 mmol of ethyl mercaptoside were added sequentially. The mixture was reacted at 40 °C for 5 h. The resulting solution was then added to 150 mL of ethanol, causing the polymer to precipitate. After washing and filtration with ethanol, the polymer was dried at 40 °C to constant weight, yielding 1.59 g of mercaptoside-modified polynorbornene (first-modified polynorbornene). NMR analysis showed no characteristic peaks of double bonds at 5.05 and 5.25 ppm, indicating complete transformation of the double bonds on the ENB structural unit. A characteristic peak of CH2 linked to the ester group appeared at 3.00 ppm, confirming the structure of the first-modified polynorbornene as shown in the figure below.

[0122]

[0123] (2) Quaternary ammonium salt group modification:

[0124] 1.5 g of the first modified polynorbornene obtained in (1) was dissolved in chloroform along with 6 mmol of trioxymethylene and 6 mmol of trimethylchlorosilane. Then, 0.05 g of anhydrous tin chloride was added. After reacting at 40 °C for 10 h, the resulting solution was precipitated in ethanol and dried to obtain a modified intermediate product. The obtained modified intermediate product was dissolved in 20 mL of chloroform, and then 8 mmol of triethylamine was added. After stirring at 60 °C for 1 h, the resulting polymer solution was precipitated in ethanol and dried to obtain 1.75 g of polynorbornene co-modified with mercapto reagent and quaternary ammonium salt group (third modified polynorbornene). NMR analysis showed that the characteristic peak of the para-H atom on the benzene ring at 7.25 ppm disappeared, while a new characteristic peak appeared at 7.75 ppm, indicating that the benzene ring on the PNB structural unit was completely functionalized. A characteristic peak of CH2 connected to nitrogen appeared at 4.50 ppm, proving that the structure of the obtained third modified polynorbornene is shown in the figure below.

[0125]

[0126] Example 4

[0127] Preparation of polynorbornene:

[0128] At 30°C, 0.05 mmol of allyl palladium chloride (main catalyst) and 0.05 mmol of AgBF4 (co-catalyst) were added sequentially to 10 mL of a dichloromethane solution containing 1.0 mol / L ethylene norbornene (ENB), 1.0 mol / L norbornene (NB), and 0.3 mol / L phenyl norbornene (PNB). After polymerization for 10 hours, the reaction was terminated by adding a 5% (w / w) hydrochloric acid-ethanol solution. The resulting polymer was dried at 40°C to constant weight to obtain 2.55 g of polynorbornene (P(NB-co-ENB-co-PNB)). The weight-average molecular weight (M) of this polynorbornene is... w The molecular weight distribution index (M) is 49500 g / mol. w / M n The mass fraction of the copolymer is 1.1; the mass fraction of NB structural units is 35%, the mass fraction of ENB structural units is 46%, and the mass fraction of PNB structural units is 19%.

[0129] Preparation of modified polynorbornene:

[0130] (1) Modification with thiol reagents:

[0131] 1.65 g of the prepared polynorbornene was dissolved in 30 mL of tetrahydrofuran, and 0.051 mmol of azobisisoheptanenitrile and 5.1 mmol of mercaptopropionic acid were added sequentially. The reaction was carried out at 40 °C for 5 h. The resulting solution was then added to 150 mL of ethanol, and the polymer precipitated. After washing and filtration with ethanol, the obtained polymer was dried at 40 °C to constant weight to obtain 1.72 g of mercapto-modified polynorbornene (first modified polynorbornene). NMR analysis showed no characteristic peaks of double bonds at 5.05 and 5.25 ppm, indicating that the double bonds on the ENB structural unit were completely transformed. A characteristic peak of CH2 linked to a carboxyl group appeared at 2.75 ppm, indicating that the structure of the obtained first modified polynorbornene is shown in the figure below.

[0132]

[0133] (2) Quaternary ammonium salt group modification:

[0134] 1.6 g of the first modified polynorbornene obtained in (1) was dissolved in chloroform along with 10 mmol of trioxymethylene and 10 mmol of trimethylchlorosilane. Then, 0.05 g of anhydrous tin chloride was added. After reacting at 60 °C for 3 h, the resulting solution was poured into ethanol for precipitation. After drying, a modified intermediate product was obtained. The modified intermediate product was dissolved in 20 mL of chloroform, and then 10 mmol of tri-n-propylamine was added. After stirring at 30 °C for 12 h, the polymer solution was poured into ethanol for precipitation. After drying, 1.68 g of polynorbornene co-modified with mercapto reagent and quaternary ammonium salt group (third modified polynorbornene) was obtained. By NMR analysis, the characteristic peak of the para-H atom on the benzene ring at 7.25 ppm disappeared, while a new characteristic peak appeared at 7.75 ppm, proving that the benzene ring on the PNB structural unit had undergone complete functionalization. A characteristic peak of CH2 connected to nitrogen appeared at 4.50 ppm, proving that the structure of the third modified polynorbornene was as shown in the figure below.

[0135]

[0136] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing modified polynorbornene, characterized in that, The preparation method includes: adding an initiator and a thiol reagent to a solution of polynorbornene to carry out a first reaction; precipitating and drying the solution after the reaction; dissolving the dried first product in an organic solvent and adding acesulfonic acid to carry out a second reaction; precipitating and drying the solution after the reaction to obtain the modified polynorbornene; wherein the thiol reagent is HSX; wherein -X is at least one of an aliphatic group containing a hydroxyl group, an aliphatic group containing a carboxyl group, and an aliphatic group containing an ester group; The preparation method of the polynorbornene includes: A mixed solution containing norbornene, ethylene norbornene, and phenyl norbornene was mixed with a catalytic system and copolymerized to obtain the polynorbornene. The concentrations of norbornene, phenyl norbornene, and ethylidene norbornene in the mixed solution are independently 0.1–3.0 mol / L; the solvent in the mixed solution is a solvent without active hydrogen and is at least one of C3–C10 saturated alkanes, C3–C10 cycloalkanes, C1–C5 haloalkanes, and C6–C15 aromatic hydrocarbons. The copolymerization reaction is carried out at a temperature of -10℃ to 80℃ for a time of 0.5 to 48 hours. The catalytic system is either a nickel catalytic system or a palladium catalytic system. The main catalyst of the nickel catalytic system is an α-diimine nickel complex. The main catalyst of the palladium catalytic system is allyl palladium chloride or an α-diimine palladium complex. The co-catalysts of the nickel catalytic system and the palladium catalytic system are independently at least one of alkylaluminum halides, alkylaluminoxanes, and boron compounds. The polynorbornene is a random copolymer of norbornene, ethylene norbornene, and phenyl norbornene; the weight-average molecular weight of the polynorbornene is 40,000 to 400,000 g / mol, and the molecular weight distribution index is not greater than 1.

8.

2. The preparation method according to claim 1, characterized in that, The temperature of the second reaction is -10 to 50°C, and the time is 1 to 48 hours.

3. A method for preparing modified polynorbornene, characterized in that, The preparation method includes: adding an initiator and a thiol reagent to a solution of polynorbornene to carry out a first reaction; precipitating and drying the solution after the reaction; dissolving the dried first product, trioxymethylene, and trimethylchlorosilane in an organic solvent, adding anhydrous tin chloride, carrying out a third reaction, and precipitating and drying the solution after the reaction to obtain a third product; dissolving the third product in an organic solvent, adding an amine to carry out a fourth reaction, and precipitating and drying the solution after the reaction to obtain the modified polynorbornene; wherein the thiol reagent is an HSX group; wherein -X is at least one of an aliphatic group containing a hydroxyl group, an aliphatic group containing a carboxyl group, and an aliphatic group containing an ester group; The preparation method of the polynorbornene includes: A mixed solution containing norbornene, ethylene norbornene, and phenyl norbornene was mixed with a catalytic system and copolymerized to obtain the polynorbornene. The concentrations of norbornene, phenyl norbornene, and ethylidene norbornene in the mixed solution are independently 0.1–3.0 mol / L; the solvent in the mixed solution is a solvent without active hydrogen and is at least one of C3–C10 saturated alkanes, C3–C10 cycloalkanes, C1–C5 haloalkanes, and C6–C15 aromatic hydrocarbons. The copolymerization reaction is carried out at a temperature of -10℃ to 80℃ for a time of 0.5 to 48 hours. The catalytic system is either a nickel catalytic system or a palladium catalytic system. The main catalyst of the nickel catalytic system is an α-diimine nickel complex. The main catalyst of the palladium catalytic system is allyl palladium chloride or an α-diimine palladium complex. The co-catalysts of the nickel catalytic system and the palladium catalytic system are independently at least one of alkylaluminum halides, alkylaluminoxanes, and boron compounds. The polynorbornene is a random copolymer of norbornene, ethylene norbornene, and phenyl norbornene; the weight-average molecular weight of the polynorbornene is 40,000 to 400,000 g / mol, and the molecular weight distribution index is not greater than 1.

8.

4. The preparation method according to claim 3, characterized in that, The amine is a tertiary amine; the temperature of the third reaction is -10 to 50°C, and the time is 1 to 48 hours; and / or The temperature of the fourth reaction is 25~60℃; the time of the fourth reaction is 1~24h.

5. The preparation method according to claim 4, characterized in that, The temperature of the fourth reaction is 40~60℃; the time of the fourth reaction is 3~10h.

6. The preparation method according to claim 1 or 3, characterized in that, The thiol reagent is at least one selected from 3-mercapto-1-propanol, 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 2-mercaptoacetic acid, ethyl 2-mercaptoacetic acid, 3-mercaptopropionic acid, and ethyl 3-mercaptopropionate; and / or The temperature of the first reaction is 20~100℃, and the time is 1~10h.

7. The preparation method according to claim 1 or 3, characterized in that, The weight-average molecular weight of the polynorbornene is 45,000 to 380,000 g / mol, and the molecular weight distribution index is not greater than 1.

5. The polynorbornene comprises 15-60 wt% norbornene structural units, 20-70 wt% ethylene norbornene structural units, and 15-45 wt% phenyl norbornene structural units.

8. The preparation method according to claim 1 or 3, characterized in that, The solvent in the mixed solution is at least one of propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane, toluene, xylene, dichloromethane, and 1,1,2,2-tetrachloroethane; The copolymerization reaction temperature is 0℃~70℃, and the copolymerization reaction time is 1.0~36h.

9. The preparation method according to claim 1 or 3, characterized in that, The concentrations of norbornene, phenyl norbornene, and ethylidene norbornene in the mixed solution are independently 0.2–2.5 mol / L; The copolymerization reaction is carried out at a temperature of 5°C to 60°C for 1.5 to 24 hours.

10. The preparation method according to claim 1 or 3, characterized in that, The concentrations of norbornene, phenyl norbornene, and ethylidene norbornene in the mixed solution are independently 0.5–2.0 mol / L.

11. The preparation method according to claim 1 or 3, characterized in that, The structural formula of the α-diimine nickel complex is shown below: In the formula, R 1 Each is independently hydrogen or methyl; R 2 R 3 R 4 R 5 R 6 Each is independently selected from at least one of hydrogen, C1-C15 alkyl, C3-C15 cycloalkyl, and halogen; X is independently chlorine or bromine; The main catalyst of the palladium catalytic system is allyl palladium chloride.

12. The preparation method according to claim 11, characterized in that, R 2 R 3 R 4 R 5 R 6 Each is independently at least one of hydrogen, methyl, ethyl, and isopropyl.

13. The preparation method according to claim 1 or 3, characterized in that, The general formula of the alkyl halide aluminum is R m AlX 3-m In this context, R is at least one of C1-C10 alkyl, C3-C10 cycloalkyl, C7-C10 aralkyl, and C6-C10 aryl, m is 1, 1.5, or 2, and X is a halogen. The alkylaluminoxane is at least one of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; and / or, the boron compound is at least one of AgBF4, B(C6F5)3, and sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

14. The preparation method according to claim 13, characterized in that, X is either Cl or Br.

15. The preparation method according to claim 1 or 3, characterized in that, The molar ratio of nickel to aluminum in the co-catalyst of the nickel catalytic system is 1:50~3000; the molar ratio of palladium to aluminum in the co-catalyst of the palladium catalytic system is 1:50~3000; and / or, the molar ratio of palladium to boron in the co-catalyst of the palladium catalytic system is 1:1~5.

16. The preparation method according to claim 15, characterized in that, In the nickel catalytic system, the molar ratio of nickel to aluminum in the co-catalyst is 1:80~2500 in the main catalyst; in the palladium catalytic system, the molar ratio of palladium to aluminum in the co-catalyst is 1:80~2500 in the main catalyst; and / or, The molar ratio of palladium in the main catalyst to boron in the co-catalyst of the palladium catalytic system is 1:1~3.

17. The preparation method according to claim 16, characterized in that, In the nickel catalytic system, the molar ratio of nickel to aluminum in the co-catalyst is 1:100~2300 in the main catalyst; in the palladium catalytic system, the molar ratio of palladium to aluminum in the co-catalyst is 1:100~2300 in the main catalyst; and / or, In the palladium catalytic system, the molar ratio of palladium in the main catalyst to boron in the co-catalyst is 1:1~2.

18. The preparation method according to claim 1 or 3, characterized in that, The initiator is at least one of azo initiators and organic peroxide initiators.

19. The preparation method according to claim 17, characterized in that, The initiator is at least one of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, benzoyl peroxide, and methyl ethyl ketone peroxide.

20. A modified polynorbornene, characterized in that, It is prepared by any one of the preparation methods according to claims 1 to 19.

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