A functionalized cycloolefin copolymer and its preparation method

Abstract

This invention provides a functionalized cyclic olefin copolymer and its preparation method, particularly relating to a functionalized cyclic olefin copolymer with controllable glass transition temperature and controllable polar group content, and its preparation method. The functionalized cyclic olefin copolymer comprises structural units of Formula I, Formula II, and Formula III. The preparation method of the functionalized cyclic olefin copolymer includes the following steps: in the presence of a main catalyst and a co-catalyst, a functionalized cyclic olefin, an unmodified cyclic olefin, and an α-olefin undergo a polymerization reaction; then, a chain terminator is added to terminate the polymerization reaction, yielding the functionalized cyclic olefin copolymer. This invention, through the design of the structure of the functionalized cyclic olefin copolymer, prepares a functionalized cyclic olefin copolymer with excellent comprehensive performance, controllable glass transition temperature, and controllable polar group content. Furthermore, the preparation method of this functionalized cyclic olefin copolymer is simple and suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of cyclic olefin copolymer materials technology, specifically relating to a functionalized cyclic olefin copolymer and its preparation method, and particularly to a functionalized cyclic olefin copolymer with controllable glass transition temperature and controllable polar group content and its preparation method. Background Technology

[0002] Cyclic olefin copolymers (COCs) are widely used in optical lenses and pharmaceutical packaging materials due to their excellent heat resistance, chemical corrosion resistance, high strength and rigidity, UV-Vis transparency, and extremely low hygroscopicity. Metallocene catalysts have been a research hotspot in organometallic chemistry, catalysis, polymer chemistry, and materials science for decades.

[0003] The introduction of polar functional groups can effectively improve the adhesion, coatability, printability, and compatibility of cyclic olefin copolymers. Theoretically, there are generally three methods for introducing polar functional groups into polyolefin materials: (a) direct copolymerization, (b) post-functionalization, and (c) reactive group functionalization. In comparison, the main drawback of the latter two methods is the inability to precisely control the molecular weight, molecular weight distribution, and structural composition of the copolymer. Direct copolymerization is simple, feasible, and relatively efficient, making it the most direct and effective method for preparing functionalized polyolefins.

[0004] Post-transition metal catalysts exhibit good tolerance to polar monomers and can catalyze the copolymerization of some cyclic olefin derivatives, such as 5-norbornene-2-methanol, 5-norbornene-2-yl acetate, methyl 5-norbornene-2-carboxylate, 2-(methoxycarbonyl)norbornene, and 2-(acetoxymethyl)norbornene. However, their polymerization activity is generally low, limiting their further expansion and application.

[0005] Pre-transition metal catalysts have high oxygen affinity and poor tolerance to polar monomers. To avoid poisoning, polar comonomers need to be protected before copolymerization. Common protection methods involve reacting alkylaluminoxanes (e.g., methylaluminoxane MAO) or alkylaluminum (e.g., triisobutylaluminum TIBA) with polar groups (hydroxyl groups) to form "inert" functional groups. After polymerization, these polar groups are released through hydrolysis or alcoholysis. These methods generally suffer from low polar group insertion rates and low reactivity, and require large quantities of alkylaluminum or alkylaluminoxanes, significantly increasing production costs. CN116925275A discloses a system for preparing polar ethylene-cycloolefin copolymers and their applications, as well as a method for polymerizing polar ethylene-cycloolefin copolymers. The system comprises the following components: a) at least one metallocene compound; b) at least one alkylaluminoxane; c) at least one organoaluminum compound AlR'mX3-m; d) ethylene; e) a monomer of formula I; wherein the metallocene compound is selected from compounds of formula II and / or formula III. The polar ethylene-cycloolefin copolymer provided by this technical solution requires the extensive use of alkylaluminum or alkylaluminoxane, which significantly increases production costs.

[0006] Therefore, how to provide a cyclic olefin copolymer that is simple to prepare, has high polymerization activity, and low production cost, and whose glass transition temperature and polar group content are controllable, has become an urgent technical problem to be solved. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a functionalized cyclic olefin copolymer and its preparation method, particularly a functionalized cyclic olefin copolymer with controllable glass transition temperature and controllable polar group content, and its preparation method. By designing the structure of the functionalized cyclic olefin copolymer, the present invention prepares a functionalized cyclic olefin copolymer with excellent comprehensive performance, controllable glass transition temperature, and controllable polar group content. Furthermore, the preparation method of this functionalized cyclic olefin copolymer is simple and suitable for industrial production.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a functionalized cyclic olefin copolymer, said functionalized cyclic olefin copolymer comprising structural units having the structures shown in Formula I, Formula II and Formula III as follows:

[0010]

[0011] Wherein, "*" represents a connection site;

[0012] m is 0 or 1, x is an integer from 0 to 6, and R is selected from C1-C10 alkyl groups;

[0013] n is 0 or 1;

[0014] R1 is H or a C1-C6 alkyl group.

[0015] This invention, through the design of the structure of functional cyclic olefin copolymers, prepares a product with excellent comprehensive performance, controllable glass transition temperature, and controllable polar groups (i.e., in the structural unit of Formula I). The * indicates the content of the functionalized cyclic olefin copolymer (where * represents the linkage site), and the preparation method of the functionalized cyclic olefin copolymer is simple and suitable for industrial production.

[0016] The functional cyclic olefin copolymers with controllable glass transition temperature and controllable polar group content provided by this invention have excellent properties and help improve the adhesion, coatability, printability and compatibility of cyclic olefin copolymers.

[0017] In this invention, x is 0-6 and can be 0, 1, 2, 3, 4, 5 or 6.

[0018] C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0019] C1-C6 can be C1, C2, C3, C4, C5, or C6.

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0021] As a preferred embodiment of the present invention, in the functionalized cyclic olefin copolymer, the molar ratio of structural units of Formula I, Formula II and Formula III is (0.017-1):1:(0.33-3.95), wherein 0.017-1 can be 0.017, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc., and 0.33-3.95 can be 0.33, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 3.95, etc.

[0022] In this invention, by controlling the molar ratio of Formula I, Formula II, and Formula III structural units within a specific range in the functionalized cyclic olefin copolymer, a functionalized cyclic olefin copolymer with excellent comprehensive performance was prepared. If the molar content of Formula I structural units is too low, the effect on improving the adhesion, coatability, printability, and compatibility of the cyclic olefin copolymer will be poor; if the molar content of Formula I structural units is too high, it will increase the production cost of the cyclic olefin copolymer.

[0023] In this invention, the molar contents of structural units of Formula I, Formula II and Formula III in the functionalized cyclic olefin copolymer can be obtained by nuclear magnetic resonance carbon spectroscopy.

[0024] As a preferred embodiment of the present invention, R is selected from any one of methyl, ethyl, isopropyl or tert-butyl.

[0025] Preferably, R1 is selected from any one of H, methyl, ethyl, butyl or hexyl, and more preferably H or methyl.

[0026] As a preferred embodiment of the present invention, the weight-average molecular weight of the functionalized cyclic olefin copolymer is 10,000-200,000 g / mol, for example, it can be 10,000 g / mol, 20,000 g / mol, 40,000 g / mol, 60,000 g / mol, 80,000 g / mol, 100,000 g / mol, 120,000 g / mol, 140,000 g / mol, 160,000 g / mol, 180,000 g / mol or 200,000 g / mol, etc., and preferably the weight-average molecular weight is 20,000-120,000 g / mol.

[0027] The molecular weight distribution index of the functionalized cyclic olefin copolymer is 2.0-3.0, for example, it can be 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0, etc., and preferably the molecular weight distribution index is 2.2-2.7.

[0028] In this invention, the weight-average molecular weight and molecular weight distribution index of the functionalized cyclic olefin copolymer can be obtained by high-temperature gel permeation chromatography (GPC).

[0029] Preferably, the glass transition temperature of the functionalized cyclic olefin copolymer is 60-200℃, for example, it can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃.

[0030] In this invention, the glass transition temperature of the functionalized cyclic olefin copolymer can be obtained by differential calorimetry.

[0031] In a second aspect, the present invention provides a method for preparing a functionalized cyclic olefin copolymer as described in the first aspect, the method comprising the following steps:

[0032] In the presence of a main catalyst and a co-catalyst, functionalized cyclic olefins, unmodified cyclic olefins, and α-olefins undergo polymerization, and then a chain terminator is added to terminate the polymerization reaction to obtain the functionalized cyclic olefin copolymer.

[0033] As a preferred embodiment of the present invention, the main catalyst comprises a metallocene compound.

[0034] Preferably, the metallocene catalyst is selected from rac-Et(Ind)2ZrCl2 (ethylene-bridged diindene zirconium dichloride), rac-Et(H4Ind)2ZrCl2 (ethylene di(4,5,6,7-tetrahydro-1-indene) zirconium dichloride), rac-Me2Si(Ind)2ZrCl2 (bis(2,4,6-trimethylindene) zirconium dichloride), and Ph2C(Flu)(Cp)ZrCl2 (diphenylmethylene(cyclopentadiene)(9-fluorenyl) zirconium dichloride). i Pr(Flu)(Cp)ZrCl2 (isopropylidene(cyclopentadiene)(9-fluorenyl)zirconium dichloride), rac- i Pr(Ind)2ZrCl2 (isopropylidene-bridged bis(indene)zirconium dichloride), wherein "Et" represents "ethyl", "Me" represents "methyl", and "Ph" represents "phenyl". i "Pr" represents "isopropyl", "Cp" represents "cyclopentadienyl", and "Flu" represents "fluorenyl".

[0035] Preferably, the co-catalyst is selected from any one or a combination of at least two of alkylaluminum, alkylaluminoxane, borane catalysts or borate catalysts.

[0036] Preferably, the alkylaluminum is selected from any one or a combination of at least two of trimethylaluminum, triethylaluminum, or triisobutylaluminum.

[0037] Preferably, the alkylaluminoxane is selected from methylaluminoxane (MAO) and / or modified methylaluminoxane (MMAO).

[0038] Preferably, the borane catalyst is selected from any one or a combination of at least two of triphenylborane, tri(pentafluorophenyl)borane, or triperfluorobiphenylborane.

[0039] Preferably, the borate catalyst is triphenylmethyltetra(pentafluorophenyl)borate and / or N,N-dimethylanilinetetra(pentafluorophenyl)borate.

[0040] Preferably, the molar ratio of the main catalyst to the co-catalyst is 1:(1-1000), for example, it can be 1:1, 1:10, 1:20, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, etc.

[0041] Preferably, the molar ratio of the main catalyst to the alkylaluminum and the molar ratio of the main catalyst to the alkylaluminoxane are each independently 1:(50-1000), for example, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, etc.

[0042] Preferably, the molar ratio of the main catalyst to the borane catalyst and the molar ratio of the main catalyst to the borate catalyst are each independently 1:(1-10), for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0043] The preparation process of the functionalized cyclic olefin copolymer provided by the present invention is applicable to the above-mentioned catalytic system, and the above-mentioned catalytic system has high catalytic activity in the functionalized cyclic olefin copolymer reaction system provided by the present invention, and can efficiently prepare the functionalized cyclic olefin copolymer claimed by the present invention.

[0044] As a preferred embodiment of the present invention, the functionalized cyclic olefin has the structure shown in Formula I-1:

[0045]

[0046] Where m is 0 or 1, and x is an integer from 0 to 6 (for example, it can be 0, 1, 2, 3, 4, 5 or 6).

[0047] Preferably, when m is 0, the functionalized cyclic olefin of formula I-1 is prepared by the following method, which includes the following steps:

[0048] The target compound was obtained by reacting cyclopentadiene with α-olefinic dimethylchlorosilane.

[0049] Preferably, the reaction includes a DA reaction, i.e., a Diels-Alder reaction.

[0050] Preferably, when m is 1, the functionalized cyclic olefin of formula I-1 is prepared by the following method, which includes the following steps:

[0051] Cyclopentadiene reacts with α-olefinic dimethylchlorosilane to give an intermediate product, which then reacts with cyclopentadiene again to give the target compound.

[0052] Preferably, the reaction temperature is 70-160℃ (e.g., 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃ or 160℃), and the time is 13-16h (e.g., 13h, 14h, 15h or 16h, etc.).

[0053] Preferably, the reaction is carried out in a protective atmosphere, the protective atmosphere including nitrogen.

[0054] As a preferred embodiment of the present invention, the unmodified cyclic olefin is selected from norbornene and / or tetracyclododecene.

[0055] Preferably, the α-olefin is selected from any one or a combination of at least two of ethylene, propylene, 1-butene, 1-hexene or 1-octene, more preferably ethylene or propylene, and even more preferably ethylene.

[0056] Preferably, the chain transfer agent comprises hydrogen.

[0057] Preferably, the chain terminator is selected from any one or a combination of at least two of methanol, ethanol, isopropanol or tert-butanol, and more preferably methanol.

[0058] As a preferred embodiment of the present invention, the molar ratio of the functionalized cyclic olefin compound, the unmodified cyclic olefin, and the α-olefin is (0.017-1):1:(0.33-3.95), wherein 0.017-1 can be 0.017, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1, etc., and 0.33-3.95 can be 0.33, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 3.95, etc.

[0059] Preferably, the molar ratio of the functionalized cyclic olefin compound to the chain terminator is 1:(1.2-10), for example, it can be 1:1.2, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0060] It should be noted that the present invention does not impose any special restrictions on the amount of the main catalyst, and all commonly used preparation methods in the field are used.

[0061] As a preferred embodiment of the present invention, the raw materials for preparing the functionalized cyclic olefin copolymer also include a chain transfer agent.

[0062] Preferably, the chain transfer agent comprises hydrogen.

[0063] As a preferred embodiment of the present invention, the polymerization reaction is carried out in the presence of an organic solvent, wherein the organic solvent is selected from any one or a combination of at least two of straight-chain aliphatic hydrocarbons, branched-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons or aromatic hydrocarbons.

[0064] Preferably, the straight-chain aliphatic hydrocarbons include, but are not limited to, n-hexane, n-heptane, etc.

[0065] Preferably, the cyclic aliphatic hydrocarbons include, but are not limited to, cyclohexane, cyclooctane, and decahydronaphthalene.

[0066] Preferably, the aromatic hydrocarbons include, but are not limited to, toluene, xylene, etc.

[0067] As a preferred embodiment of the present invention, the polymerization reaction is carried out at a temperature of 80-160℃ (e.g., 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, or 160℃, etc.), a pressure of 0.2-2.0MPa (e.g., 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, or 2.0MPa, etc.), and a time of 1-30min (e.g., 1min, 3min, 6min, 9min, 12min, 15min, 18min, 20min, 22min, 25min, 27min, or 30min, etc.).

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] (1) By using functionalized cyclic olefins with single Si-Cl functional groups, this invention provides polar groups while avoiding the local crosslinking reaction of double Si-Cl or triple Si-Cl groups during alcoholysis, which would affect the performance of functionalized cyclic olefin copolymers.

[0070] (2) By designing the structure of the functional cyclic olefin copolymer, a functional cyclic olefin copolymer with excellent comprehensive performance, controllable glass transition temperature and controllable polar group content was prepared. Moreover, the preparation method of the functional cyclic olefin copolymer is simple and suitable for industrial production. Attached Figure Description

[0071] Figure 1 This is the 1H NMR spectrum of the functionalized cyclic olefin A provided in Example 1 of this invention;

[0072] Figure 2 This is the 1H NMR spectrum of the functionalized cyclic olefin B provided in Example 2 of this invention;

[0073] Figure 3 This is the 1H NMR spectrum of the functionalized cyclic olefin C provided in Example 3 of this invention;

[0074] Figure 4 This is the 1H NMR spectrum of the functionalized cyclic olefin D provided in Example 4 of this invention;

[0075] Figure 5 This is the carbon NMR spectrum of the functionalized cyclic olefin copolymer A provided in Example 1 of the present invention. Detailed Implementation

[0076] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof.

[0077] Preparation Example 1

[0078] This preparation example provides a functionalized cyclic olefin A and its preparation method, wherein the functionalized cyclic olefin A is... Its preparation method is as follows:

[0079] 6.6 g (0.1 mol) of cyclopentadiene was added to a nitrogen-filled reactor, and 14.5 g (0.12 mol) of vinyldimethylchlorosilane was slowly added. The mixture was reacted at 80 °C for 3 h, then heated to 150 °C for 13 h, and then cooled to 80 °C for 10 h to obtain the crude product. The crude product was then distilled under reduced pressure to obtain functionalized cycloolefin A.

[0080] The functionalized cyclic olefin A was characterized using 1H NMR spectroscopy, and the characterization results are as follows: Figure 1 As shown. By Figure 1 It can be seen that the functionalized cyclic olefin A was successfully prepared.

[0081] Preparation Example 2

[0082] This preparation example provides a functionalized cyclic olefin B and its preparation method, wherein the functionalized cyclic olefin B is... Its preparation method is as follows:

[0083] 6.6 g (0.1 mol) of cyclopentadiene was added to a nitrogen-filled reactor, and 17.8 g (0.12 mol) of 3-butenyldimethylchlorosilane was slowly added. The reaction was carried out at 80 °C for 3 h, then the temperature was raised to 120 °C for 1 h, and then the temperature was lowered to 80 °C for 10 h to obtain the crude product. The functionalized cycloolefin B was obtained by vacuum distillation.

[0084] The functionalized cyclic olefin B was characterized using 1H NMR spectroscopy, and the characterization results are as follows: Figure 2 As shown. By Figure 2 It can be seen that the functionalized cyclic olefin B was successfully prepared.

[0085] Preparation Example 3

[0086] This preparation example provides a functionalized cyclic olefin C and its preparation method, wherein the functionalized cyclic olefin C is... Its preparation method is as follows:

[0087] Under nitrogen protection, 11.0 g (0.1 mol) of 1,7-octadiene, 0.092 g (0.25 mmol) of allyl palladium(II) chloride dimer and 0.131 g (0.5 mmol) of triphenylphosphine were added sequentially. Then, 8.5 g (0.09 mol) of dimethylchlorosilane was added dropwise at 0 °C. After the addition was complete, the mixture was stirred at 0 °C for 2 h, and then stirred at room temperature for 120 h. After vacuum distillation, 7-octenyl dimethylchlorosilane was obtained.

[0088] 6.6 g (0.1 mol) of cyclopentadiene was added to a nitrogen-filled reactor, and 24.6 g (0.12 mol) of 3-butenyldimethylchlorosilane was slowly added. The mixture was reacted at 80 °C for 3 h, then heated to 120 °C for 1 h, and then cooled to 80 °C for 10 h to obtain the crude product. The crude product was then distilled under reduced pressure to obtain functionalized cycloolefin C.

[0089] The functionalized cyclic olefin C was characterized using 1H NMR spectroscopy. The characterization results are as follows: Figure 3 As shown. By Figure 3 It can be seen that the functionalized cyclic olefin C was successfully prepared.

[0090] Preparation Example 4

[0091] This preparation example provides a functionalized cyclic olefin D and its preparation method, wherein the functionalized cyclic olefin D is... Its preparation method is as follows:

[0092] Functionalized cyclic olefin A was prepared according to the method provided in Preparation Example 1.

[0093] 6.6 g (0.1 mol) of cyclopentadiene was added to a nitrogen-filled reactor, and 22.4 g (0.12 mol) of functionalized cycloolefin A was slowly added. The reaction was carried out at 80 °C for 3 h, then the temperature was raised to 120 °C for 1 h, and then the temperature was lowered to 80 °C for 10 h to obtain the crude product. The functionalized cycloolefin D was obtained by vacuum distillation.

[0094] The functionalized cyclic olefin D was characterized using 1H NMR spectroscopy, and the characterization results are as follows: Figure 4 As shown. By Figure 4 It can be seen that the functionalized cyclic olefin D was successfully prepared.

[0095] In the following examples and comparative examples, the catalytic activity of the catalyst in the reaction system was calculated using the following method:

[0096] Catalytic activity = mass of cyclic olefin copolymer / (molar amount of catalyst × polymerization time).

[0097] Example 1

[0098] This embodiment provides a functionalized cyclic olefin copolymer A, which comprises structural units having the structures shown in Formula IA, Formula II-A and Formula III-A as follows:

[0099]

[0100] The preparation method of the above-mentioned functionalized cyclic olefin copolymer A is as follows:

[0101] In a 300 mL batch reactor, 0.1 mol of functionalized cycloolefin A, 0.1 mol of norbornene, 100 mL of toluene, and 2.4 mg of hydrogen were added sequentially. The reaction system was heated to 130 °C, and under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA) and 0.5 μmol of [unspecified substance] were added sequentially. i Pr(Flu)(Cp)ZrCl2 and 2 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added to the polymerization process by supplementing and metering ethylene, and the partial pressure of ethylene was observed and controlled at 0.8 MPa using a flow meter.

[0102] After the polymerization reaction was carried out for 15 minutes, the polymerization was stopped, the reaction solution was poured into methanol to precipitate, filtered, the filter cake was washed with methanol and dried (drying at 80°C to constant weight) to obtain functionalized cyclic olefin copolymer A (7.1 g). The catalytic activity of the catalyst in the reaction system of this example was 5.7 × 10⁻⁶. 7 g / (molCat.·h).

[0103] The functionalized cyclic olefin copolymer A was characterized using carbon nuclear magnetic resonance spectroscopy. The characterization results are as follows: Figure 5 As shown. By Figure 5 It can be seen that the functionalized cyclic olefin copolymer A was successfully prepared.

[0104] Example 2

[0105] This embodiment provides a functionalized cyclic olefin copolymer B, which includes structural units having the structures shown in Formula IB, Formula II-B, and Formula III-B as follows:

[0106]

[0107] The preparation method of the above-mentioned functionalized cyclic olefin copolymer B is as follows:

[0108] In a 300 mL batch reactor, 0.1 mol of functionalized cycloolefin B, 0.1 mol of norbornene, 100 mL of toluene, and 2.4 mg of hydrogen were added sequentially. The reaction system was heated to 120 °C, and under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA) and 0.5 μmol of rac- were added sequentially.i Pr(Ind)2ZrCl2 and 2 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added to the polymerization process by supplementing with ethylene in a metered manner, and the partial pressure of ethylene was observed and controlled at 0.5 MPa using a flow meter.

[0109] After polymerization for 30 minutes, the polymerization reaction was stopped. The reaction solution was poured into methanol to precipitate, then filtered. The filter cake was washed with methanol and dried (at 80°C to constant weight) to obtain functionalized cyclic olefin copolymer B (6.8 g). In this example, the catalytic activity of the catalyst in the reaction system was 2.7 × 10⁻⁶. 7 g / (molCat.·h).

[0110] Example 3

[0111] This embodiment provides a functionalized cyclic olefin copolymer C, which comprises structural units having the structures shown in Formula I, Formula II-C and Formula III-C:

[0112]

[0113] The preparation method of the above-mentioned functionalized cyclic olefin copolymer C is as follows:

[0114] In a 300 mL batch reactor, 0.01 mol of functionalized cyclic olefin C, 0.1 mol of norbornene, 100 mL of toluene, and 2.4 mg of hydrogen were added sequentially. The reaction system was heated to 100 °C, and under stirring at 500 rpm, 0.3 mmol of triisobutylaluminum (TIBA), 1.5 μmol of rac-Et(Ind)2ZrCl2, and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added sequentially. Ethylene was added in a metered manner during the polymerization process, and the partial pressure of ethylene was observed and controlled to be 1.2 MPa using a flow meter.

[0115] After the polymerization reaction was carried out for 10 minutes, the polymerization was stopped, the reaction solution was poured into methanol to precipitate, filtered, the filter cake was washed with methanol and dried (drying at 80°C to constant weight) to obtain functionalized cyclic olefin copolymer C (13.8 g). The catalytic activity of the catalyst in the reaction system of this example was 5.5 × 10⁻⁶. 7 g / (molCat.·h).

[0116] Example 4

[0117] This embodiment provides a functionalized cyclic olefin copolymer D, which includes structural units having the structures shown in Formulas ID, II-D, and III-D as follows:

[0118]

[0119] The preparation method of the above-mentioned functionalized cyclic olefin copolymer D is as follows:

[0120] In a 300 mL batch reactor, 0.01 mol of functionalized cyclic olefin D, 0.1 mol of tetracyclododecene, 100 mL of toluene, and 2.4 mg of hydrogen were added sequentially. The reaction system was heated to 130 °C, and under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA) and 0.5 μmol of [unspecified substance] were added sequentially. i Pr(Flu)(Cp)ZrCl2 and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added to the polymerization process by supplementing with ethylene in a metered manner, and the partial pressure of ethylene was observed and controlled at 1.0 MPa using a flow meter.

[0121] After the polymerization reaction was carried out for 15 minutes, the polymerization was stopped, the reaction solution was poured into methanol to precipitate, filtered, the filter cake was washed with methanol and dried (drying at 80°C to constant weight) to obtain functionalized cyclic olefin copolymer D (10.6 g). The catalytic activity of the catalyst in the reaction system of this example was 8.5 × 10⁻⁶. 7 g / (molCat.·h).

[0122] Example 5

[0123] This embodiment provides a functionalized cyclic olefin copolymer E, which comprises structural units having the structures shown in Formula IE, Formula II-E and Formula III-E as follows:

[0124]

[0125] The preparation method of the functionalized cyclic olefin copolymer can refer to the preparation method provided in Example 1, except that ethylene in Example 1 is replaced with propylene.

[0126] Comparative Example 1

[0127] This comparative example provides a functionalized cyclic olefin copolymer 1, which comprises structural units having the structures shown in Formula II-1 and Formula III-1 as follows:

[0128]

[0129] The preparation method of the above-mentioned functionalized cyclic olefin copolymer 1 is as follows:

[0130] In a 300 mL batch reactor, 0.2 mol norbornene, 100 mL toluene, and 2.4 mg hydrogen were added sequentially. The reaction system was heated to 130 °C, and under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA) and 0.5 μmol of [unspecified substance] were added sequentially. iPr(Flu)(Cp)ZrCl2 and 2 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added to the polymerization process by supplementing with ethylene in a metered manner, and the partial pressure of ethylene was observed and controlled at 1.0 MPa using a flow meter.

[0131] After polymerization for 15 min, the polymerization was stopped. The reaction solution was poured into an acid-alcohol mixture (1% hydrochloric acid solution, ethanol as solvent), and the precipitate was filtered. The filter cake was washed with ethanol and dried (at 80°C to constant weight) to obtain functionalized cyclic olefin copolymer 1 (7.6 g). The catalytic activity of the catalyst in this comparative reaction system was 6.1 × 10⁻⁶. 7 g / (molCat.·h).

[0132] The properties of the functionalized cyclic olefin copolymers provided in the above embodiments and comparative examples were tested using the following specific test methods:

[0133] The molar content of cyclic olefins was calculated using carbon NMR spectroscopy results. The calculation method is referenced in: Macromolecules 2001, 34, 5770-5777; Pure Appl. Chem., Vol. 77, No. 5, pp. 801–814, 2005.

[0134] The content of polar groups: calculated from the results of carbon NMR spectroscopy, the molar content of polar groups = I SiCH3 / I CH2

[0135] Weight-average molecular weight (Mw) and molecular weight distribution index (PDI): These were determined by high-temperature gel permeation chromatography (GPC) using a Polymer Char GPC-IR instrument and an Agilent PL1110-6400 column. 1,2,4-trichlorobenzene was used as the eluent, and polystyrene was used as the reference. Elution was performed at 160℃ and a flow rate of 1.00 mL / min.

[0136] Glass transition temperature (Tg): The temperature range of 30-230℃ was scanned using a differential calorimeter (DSC, NETZSCH DSC204F1), with both heating and cooling rates of 15K / min. Tg was determined based on the second heating stage.

[0137] The performance test results are shown in Table 1 below:

[0138] Table 1

[0139]

[0140] As can be seen from the above data, the glass transition temperatures of the functionalized cyclic olefin copolymers prepared by using cyclic olefin monomers containing polar groups (provided in Examples 1-5) and the functionalized cyclic olefin copolymers prepared without using cyclic olefin monomers containing polar groups (provided in Comparative Example 1) are not significantly different, indicating that the use of cyclic olefin monomers containing polar groups does not have an adverse effect on polymerization activity, molecular weight, and Tg.

[0141] Furthermore, the functional cyclic olefin copolymers provided by this invention have controllable glass transition temperature and controllable polar group content (1-30 mol%), which helps to improve the adhesion, coatability, printability and compatibility of cyclic olefin copolymers.

[0142] In summary, this invention, through the design of the structure of functional cyclic olefin copolymers, has prepared functional cyclic olefin copolymers with excellent comprehensive performance, controllable glass transition temperature, and controllable polar group content. Furthermore, the preparation method of these functionalized cyclic olefin copolymers is simple and suitable for industrial production.

[0143] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A functionalized cyclic olefin copolymer, characterized in that, The functionalized cyclic olefin copolymer comprises structural units having the structures shown in Formula I, Formula II and Formula III as follows: Wherein, "*" represents a connection site; m is 0 or 1, x is an integer from 0 to 6, and R is selected from C1-C10 alkyl groups; n is 0 or 1; R1 is H or a C1-C6 alkyl group; In the functionalized cyclic olefin copolymer, the molar ratio of structural units of Formula I, Formula II and Formula III is (0.1-1):1:(0.33-3.95).

2. The functionalized cyclic olefin copolymer according to claim 1, characterized in that, R is selected from any one of methyl, ethyl, isopropyl, or tert-butyl.

3. The functionalized cyclic olefin copolymer according to claim 1, characterized in that, R1 is selected from any one of H, methyl, ethyl, butyl, or hexyl.

4. The functionalized cyclic olefin copolymer according to claim 3, characterized in that, R1 is selected from H or methyl.

5. The functionalized cyclic olefin copolymer according to claim 1, characterized in that, The weight-average molecular weight of the functionalized cyclic olefin copolymer is 10,000-200,000 g / mol; The molecular weight distribution index of the functionalized cyclic olefin copolymer is 2.0-3.

0.

6. The functionalized cyclic olefin copolymer according to claim 1, characterized in that, The glass transition temperature of the functionalized cyclic olefin copolymer is 60-200℃.

7. A method for preparing a functionalized cyclic olefin copolymer as described in any one of claims 1-6, characterized in that, The preparation method includes the following steps: In the presence of a main catalyst and a co-catalyst, functionalized cyclic olefins, unmodified cyclic olefins, ethylene and / or α-olefins undergo polymerization, and then a chain terminator is added to terminate the polymerization reaction to obtain the functionalized cyclic olefin copolymer.

8. The preparation method according to claim 7, characterized in that, The main catalyst includes metallocene compounds.

9. The preparation method according to claim 8, characterized in that, The metallocene catalyst is selected from rac-Et(Ind)₂ZrCl₂, rac-Et(H₄Ind)₂ZrCl₂, rac-Me₂Si(Ind)₂ZrCl₂, and Ph₂C(Flu)(Cp)ZrCl₂. i Pr(Flu)(Cp)ZrCl2、rac- i Any one or at least two combinations of Pr(Ind)2ZrCl2.

10. The preparation method according to claim 7, characterized in that, The co-catalyst is selected from any one or a combination of at least two of alkylaluminum, alkylaluminoxane, borane catalysts or borate catalysts.

11. The preparation method according to claim 10, characterized in that, The alkylaluminum is selected from any one or a combination of at least two of trimethylaluminum, triethylaluminum, or triisobutylaluminum.

12. The preparation method according to claim 10, characterized in that, The alkylaluminoxane is selected from methylaluminoxane and / or modified methylaluminoxane.

13. The preparation method according to claim 10, characterized in that, The boron-based catalyst is selected from any one or a combination of at least two of triphenylborane, tri(pentafluorophenyl)borane, or triperfluorobiphenylborane.

14. The preparation method according to claim 10, characterized in that, The borate catalyst is selected from triphenylmethyltetra(pentafluorophenyl)borate and / or N,N-dimethylanilinetetra(pentafluorophenyl)borate.

15. The preparation method according to claim 7, characterized in that, The molar ratio of the main catalyst to the co-catalyst is 1:(1-1000).

16. The preparation method according to claim 10, characterized in that, The molar ratio of the main catalyst to the alkylaluminum and the molar ratio of the main catalyst to the alkylaluminoxane are each independently 1:(50-1000).

17. The preparation method according to claim 10, characterized in that, The molar ratio of the main catalyst to the borane catalyst and the molar ratio of the main catalyst to the borate catalyst are each independently 1:(1-10).

18. The preparation method according to claim 7, characterized in that, The functionalized cyclic olefin has the structure shown in Formula I-1: Where m is 0 or 1, and x is an integer from 0 to 6.

19. The preparation method according to claim 18, characterized in that, When m is 0, the functionalized cyclic olefin of formula I-1 is prepared by the following method, which includes the following steps: The target compound was obtained by reacting cyclopentadiene with α-olefinic dimethylchlorosilane.

20. The preparation method according to claim 18, characterized in that, When m is 1, the functionalized cyclic olefin of formula I-1 is prepared by the following method, which includes the following steps: Cyclopentadiene reacts with α-olefinic dimethylchlorosilane to give an intermediate product, which then reacts with cyclopentadiene again to give the target compound.

21. The preparation method according to claim 19 or 20, characterized in that, The reaction is carried out at a temperature of 70-160℃ for 13-16 hours.

22. The preparation method according to claim 19 or 20, characterized in that, The reaction is carried out in a protective atmosphere.

23. The preparation method according to claim 7, characterized in that, The unmodified cyclic olefin is selected from norbornene and / or tetracyclododecene.

24. The preparation method according to claim 7, characterized in that, The α-olefin is selected from any one or a combination of at least two of propylene, 1-butene, 1-hexene or 1-octene.

25. The preparation method according to claim 24, characterized in that, The α-olefin is selected from ethylene or propylene.

26. The preparation method according to claim 25, characterized in that, The α-olefin is selected from ethylene.

27. The preparation method according to claim 7, characterized in that, The chain terminator is selected from any one or a combination of at least two of methanol, ethanol, isopropanol or tert-butanol.

28. The preparation method according to claim 27, characterized in that, The chain terminator is selected from methanol.

29. The preparation method according to claim 7, characterized in that, The molar ratio of the functionalized cyclic olefin compound, the unmodified cyclic olefin, and the α-olefin is (0.1-1):1:(0.33-3.95).

30. The preparation method according to claim 7, characterized in that, The molar ratio of the functionalized cyclic olefin compound to the chain terminator is 1:(1.2-10).

31. The preparation method according to claim 7, characterized in that, The polymerization reaction is carried out at a temperature of 80-160℃, a pressure of 0.2-2.0MPa, and a time of 1-30min.

Images