Functionalized cycloolefin copolymer and preparation method thereof

Abstract

The invention provides a functional cycloolefin copolymer and a preparation method thereof, and particularly relates to a functional cycloolefin copolymer with controllable glass transition temperature and controllable polar group content and a preparation method thereof. The functionalized cycloolefin copolymer comprises a structural unit as shown in a formula I, a structural unit as shown in a formula II and a structural unit as shown in a formula III, the preparation method of the functionalized cycloolefin copolymer comprises the following steps: in the presence of a main catalyst and a cocatalyst, carrying out polymerization reaction on functionalized cycloolefin, unmodified cycloolefin and alpha-olefin, and then adding a chain terminator to terminate the polymerization reaction to obtain the functionalized cycloolefin copolymer. By designing the structure of the functional cycloolefin copolymer, the functional cycloolefin copolymer with excellent comprehensive performance, controllable glass transition temperature and controllable polar group content is prepared, and the preparation method of the functional cycloolefin copolymer is simple and suitable for industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of cycloolefin copolymer materials, and specifically relates to a functionalized cycloolefin copolymer and a preparation method thereof, and in particular to a functional cycloolefin copolymer with controllable glass transition temperature and controllable polar group content and a preparation method thereof. Background Art

[0002] Cyclic Olefin Copolymer (COC) has excellent heat resistance, chemical corrosion resistance, high strength and rigidity, UV-Vis transparency and extremely low hygroscopicity, and is widely used in the fields of optical lenses, medical packaging materials, etc. Metallocene catalysts have been a research hotspot in metal organic chemistry, catalysis, polymer chemistry and materials science in recent decades.

[0003] The introduction of polar functional groups can effectively improve the adhesion, coating, printability and compatibility of cycloolefin 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 disadvantage of the latter two methods is that the molecular weight, molecular weight distribution and structural composition of the copolymer cannot be accurately controlled. The direct copolymerization method is simple and feasible, and the efficiency is relatively high. It is the most direct and effective method for preparing functionalized polyolefins.

[0004] Late transition metal catalysts have good tolerance to polar monomers and can catalyze the copolymerization of some cycloolefin derivatives, such as 5-norbornene-2-methanol, 5-norbornene-2-yl acetate, 5-norbornene-2-carboxylic acid methyl ester, 2-(methoxycarbonyl)norbornene, and 2-(acetoxymethyl)norbornene. However, the polymerization activity is generally low, which limits its further expansion and application.

[0005] The former transition metal catalyst has high affinity for oxygen and poor tolerance to polar monomers. To avoid poisoning, the polar comonomer needs to be protected before copolymerization. The common protection method is to use alkylaluminoxane (for example: methylaluminoxane MAO) or alkylaluminum (for example: triisobutylaluminum TIBA) to react with polar groups (hydroxyl groups) to form "inert" functional groups. After the polymerization reaction is completed, the polar groups are released by hydrolysis or alcoholysis. Such methods generally have the problems of low polar group insertion rate and low reaction activity, and require a large amount of alkylaluminum or alkylaluminoxane, which greatly increases the production cost. CN116925275A discloses a system for preparing polar ethylene-cycloolefin copolymers and their applications, polar ethylene-cycloolefin copolymers and polymerization methods thereof. The system includes the following components: a) at least one metallocene compound; b) at least one alkylaluminoxane; c) at least one organic aluminum compound AlR'mX3-m; d) ethylene; e) monomers shown in formula I; the metallocene compound is selected from compounds described in formula II and / or formula III. The polar ethylene-cycloolefin copolymer provided by this technical solution requires a large amount of alkyl aluminum or alkyl aluminoxane, which greatly increases the production cost.

[0006] Therefore, how to provide a cycloolefin copolymer with a simple preparation method, high polymerization activity, and low production cost, and how to make the glass transition temperature and polar group content of the cycloolefin copolymer controllable has become a technical problem that needs to be solved urgently. Summary of the invention

[0007] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a functionalized cycloolefin copolymer and a preparation method thereof, and in particular to a functionalized cycloolefin copolymer with controllable glass transition temperature and controllable polar group content and a preparation method thereof. The present invention designs the structure of the functionalized cycloolefin copolymer to prepare a functionalized cycloolefin copolymer with excellent comprehensive performance, controllable glass transition temperature and controllable polar group content, and the preparation method of the functionalized cycloolefin copolymer is simple and suitable for industrial production.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a functionalized cycloolefin copolymer, wherein the functionalized cycloolefin copolymer comprises structural units having structures shown in the following formulas I, II and III:

[0010]

[0011] Among them, “*” indicates the connection site;

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

[0013] n is 0 or 1;

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

[0015] The present invention designs the structure of the functional cycloolefin copolymer to prepare a copolymer with excellent comprehensive performance, controllable glass transition temperature, controllable polar groups (i.e., wherein * represents a connection site) content, and the preparation method of the functionalized cycloolefin copolymer is simple and suitable for industrial production.

[0016] The functional cycloolefin copolymer with controllable glass transition temperature and controllable polar group content provided by the present invention has excellent performance and is helpful to improve the adhesion, coating, printability and compatibility of the cycloolefin copolymer.

[0017] In the present 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. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0021] As a preferred technical solution of the present invention, in the functionalized cycloolefin copolymer, the molar ratio of the structural unit of formula I, the structural unit of formula II and the structural unit of 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, 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 the present invention, a functionalized cycloolefin copolymer with excellent comprehensive performance is prepared by controlling the molar ratio of the structural unit of formula I, the structural unit of formula II and the structural unit of formula III in the functionalized cycloolefin copolymer within a specific range. If the molar content of the structural unit of formula I is too small, the effect of improving the adhesion, coating, printability and compatibility of the cycloolefin copolymer is not good; if the molar content of the structural unit of formula I is too large, the production cost of the cycloolefin copolymer will be increased.

[0023] In the present invention, the molar contents of the structural units of formula I, formula II and formula III in the functionalized cycloolefin copolymer can be obtained by using carbon nuclear magnetic resonance spectroscopy.

[0024] As a preferred technical solution of the present invention, the 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 technical solution of the present invention, the weight average molecular weight of the functionalized cycloolefin 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 the preferred weight average molecular weight is 20,000-120,000 g / mol.

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

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

[0029] Preferably, the glass transition temperature of the functionalized cycloolefin copolymer is 60-200°C, for example, it may be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, etc.

[0030] In the present invention, the glass transition temperature of the functionalized cycloolefin copolymer can be measured by using a differential calorimeter.

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

[0032] In the presence of a main catalyst and a co-catalyst, functionalized cycloolefin, unmodified cycloolefin and alpha-olefin are polymerized, and then a chain terminator is added thereto to terminate the polymerization reaction, thereby obtaining the functionalized cycloolefin copolymer.

[0033] As a preferred technical solution of the present invention, the main catalyst includes a metallocene compound.

[0034] Preferably, the metallocene catalyst is selected from rac-Et(Ind)2ZrCl2 (ethylene bridged diindenyl zirconium dichloride), rac-Et(H4Ind)2ZrCl2 (ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride), rac-Me2Si(Ind)2ZrCl2 (bis(2,4,6-trimethylindenyl) zirconium dichloride), Ph2C(Flu)(Cp)ZrCl2 (diphenylmethylene(cyclopentadiene)(9-fluorenyl) zirconium dichloride), i Pr(Flu)(Cp)ZrCl2(isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride), rac- i Any one or a combination of at least two of Pr(Ind)2ZrCl2 (isopropylidene bridged bisindenyl zirconium dichloride), wherein "Et" represents "ethyl", "Me" represents "methyl", "Ph" represents "phenyl", i "Pr" means "isopropyl", "Cp" means "cyclopentadienyl" and "Flu" means "fluorenyl".

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

[0036] Preferably, the alkyl aluminum is selected from any one of trimethyl aluminum, triethyl aluminum or triisobutyl aluminum, or a combination of at least two thereof.

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

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

[0039] Preferably, the borate catalyst is triphenylmethyltetrakis(pentafluorophenyl)borate and / or N,N-dimethylaniliniumtetrakis(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 alkyl aluminum, and the molar ratio of the main catalyst to the alkyl aluminoxane are each independently 1:(50-1000), for example, they can be 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, they can be 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 cycloolefin 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 cycloolefin copolymer reaction system provided by the present invention, and the functionalized cycloolefin copolymer claimed to be protected by the present invention can be prepared efficiently.

[0044] As a preferred technical solution of the present invention, the functionalized cycloolefin has a structure as shown in the following formula I-1:

[0045]

[0046] Wherein, m is 0 or 1, and x is an integer of 0-6 (for example, 0, 1, 2, 3, 4, 5 or 6).

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

[0048] Cyclopentadiene reacts with α-olefin dimethyl chlorosilane to obtain the target compound.

[0049] Preferably, the reaction comprises a DA reaction, ie a Diels-Alder reaction.

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

[0051] Cyclopentadiene reacts with α-olefin dimethyl chlorosilane to obtain an intermediate product, and the intermediate product reacts with cyclopentadiene again to obtain a target compound.

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

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

[0054] As a preferred technical solution of the present invention, the unmodified cycloolefin 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 of methanol, ethanol, isopropanol or tert-butanol, or a combination of at least two thereof, and more preferably methanol.

[0058] As a preferred technical solution of the present invention, the molar ratio of the functionalized cycloolefin compound, the unmodified cycloolefin 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, 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 cycloolefin 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 have any special restrictions on the amount of the main catalyst, and the commonly used preparation methods in the art can be used.

[0061] As a preferred technical solution of the present invention, the raw materials for preparing the functionalized cycloolefin copolymer further include a chain transfer agent.

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

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

[0064] Preferably, the straight-chain aliphatic hydrocarbon illustratively includes but is not limited to: n-hexane, n-heptane and the like.

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

[0066] Preferably, the aromatic hydrocarbons illustratively include but are not limited to: toluene, xylene and the like.

[0067] As a preferred technical solution of the present invention, the polymerization reaction temperature is 80-160°C (for example, it can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or 160°C, etc.), the pressure is 0.2-2.0MPa (for example, it can be 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa or 2.0MPa, etc.), and the time is 1-30min (for example, it can be 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) The present invention uses a functionalized cycloolefin having a single Si-Cl functional group to provide a polar group while avoiding the occurrence of local cross-linking reactions of double Si-Cl or triple Si-Cl groups during alcoholysis, thereby affecting the performance of the functionalized cycloolefin copolymer.

[0070] (2) By designing the structure of the functional cycloolefin copolymer, a functional cycloolefin copolymer with excellent comprehensive performance, controllable glass transition temperature, and controllable polar group content is prepared, and the preparation method of the functionalized cycloolefin copolymer is simple and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 is the H NMR spectrum of the functionalized cycloolefin A provided in Preparation Example 1 of the present invention;

[0072] Figure 2 is the H NMR spectrum of the functionalized cycloolefin B provided in Preparation Example 2 of the present invention;

[0073] Figure 3 is the H NMR spectrum of the functionalized cycloolefin C provided in Preparation Example 3 of the present invention;

[0074] Figure 4 is the H NMR spectrum of the functionalized cycloolefin D provided in Preparation Example 4 of the present invention;

[0075] Figure 5 This is the carbon nuclear magnetic resonance spectrum of the functionalized cycloolefin copolymer A provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0076] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0077] Preparation Example 1

[0078] This preparation example provides a functionalized cycloolefin A and a preparation method thereof. The functionalized cycloolefin A is The preparation method is as follows:

[0079] 6.6 g (0.1 mol) of cyclopentadiene was added into a reactor filled with nitrogen, and 14.5 g (0.12 mol) of vinyldimethylsilyl chloride 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 a crude product, which was then distilled under reduced pressure to obtain functionalized cycloolefin A.

[0080] The functionalized cycloolefin A was characterized by H NMR spectroscopy. The characterization results are as follows: Figure 1 As shown. Figure 1 It can be seen that the functionalized cycloolefin A was successfully prepared.

[0081] Preparation Example 2

[0082] This preparation example provides a functionalized cycloolefin B and a preparation method thereof. The functionalized cycloolefin B is The preparation method is as follows:

[0083] 6.6 g (0.1 mol) of cyclopentadiene was added into a reactor filled with nitrogen, and 17.8 g (0.12 mol) of 3-butenyldimethylsilyl chloride 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 a crude product, which was then distilled under reduced pressure to obtain functionalized cycloolefin B.

[0084] The functionalized cycloolefin B was characterized by H NMR spectroscopy. The characterization results are as follows: Figure 2 As shown. Figure 2 It can be seen that the functionalized cycloolefin B was successfully prepared.

[0085] Preparation Example 3

[0086] This preparation example provides a functionalized cycloolefin C and a preparation method thereof. The functionalized cycloolefin C is The 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 allylpalladium (II) chloride dimer and 0.131 g (0.5 mmol) of triphenylphosphine were added in sequence, and then 8.5 g (0.09 mol) of dimethylchlorosilane was added dropwise at 0°C. After the addition was completed, stirring was continued at 0°C for 2 h, and then stirring was continued at room temperature for 120 h. After vacuum distillation, 7-octenyldimethylchlorosilane was obtained;

[0088] 6.6 g (0.1 mol) of cyclopentadiene was added into a reactor filled with nitrogen, and 24.6 g (0.12 mol) of 3-butenyldimethylsilyl chloride 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 a crude product, which was subjected to reduced pressure distillation to obtain functionalized cycloolefin C.

[0089] The functionalized cycloolefin C was characterized by H NMR spectroscopy. Figure 3 As shown. Figure 3 It can be seen that the functionalized cycloolefin C was successfully prepared.

[0090] Preparation Example 4

[0091] This preparation example provides a functionalized cycloolefin D and a preparation method thereof. The functionalized cycloolefin D is The preparation method is as follows:

[0092] Functionalized cycloolefin A was prepared by referring to the method provided in Preparation Example 1.

[0093] 6.6 g (0.1 mol) of cyclopentadiene was added into a reactor filled with nitrogen, 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 a crude product, which was then distilled under reduced pressure to obtain functionalized cycloolefin D.

[0094] The functionalized cycloolefin D was characterized by H NMR spectroscopy. Figure 4 As shown. Figure 4 It can be seen that the functionalized cycloolefin D was successfully prepared.

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

[0096] Catalytic activity = mass of cycloolefin copolymer / (molar amount of catalyst x polymerization time).

[0097] Example 1

[0098] This embodiment provides a functionalized cycloolefin copolymer A, wherein the functionalized cycloolefin copolymer A comprises structural units having structures shown in the following formulas IA, II-A and III-A:

[0099]

[0100] The preparation method of the functionalized cycloolefin copolymer A is as follows:

[0101] In a 300 mL autoclave 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 in sequence. The reaction system was heated to 130 °C. Under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA), 0.5 μmol of i Pr(Flu)(Cp)ZrCl2 and 2μmol triphenylmethyltetrakis(pentafluorophenyl)borate, ethylene was added by supplementary metering during the polymerization process, and the ethylene partial pressure was observed and controlled at 0.8MPa by a flow meter;

[0102] After the polymerization reaction was carried out for 15 min, the polymerization reaction was stopped, the reaction solution was poured into methanol for precipitation and then filtered, the filter cake was washed with methanol and dried (dried to constant weight at 80° C.) to obtain a functionalized cycloolefin copolymer A (7.1 g), wherein the catalytic activity of the catalyst in the reaction system of this embodiment was 5.7×10 7 g / (molCat.·h).

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

[0104] Example 2

[0105] This embodiment provides a functionalized cycloolefin copolymer B, wherein the functionalized cycloolefin copolymer B comprises structural units having structures shown in the following formulas IB, II-B and III-B:

[0106]

[0107] The preparation method of the functionalized cycloolefin copolymer B is as follows:

[0108] In a 300 mL autoclave 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 in sequence. The reaction system was heated to 120 °C and, under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA), 0.5 μmol of rac-i Pr(Ind)2ZrCl2 and 2μmol triphenylmethyltetrakis(pentafluorophenyl)borate, ethylene was added by supplementary metering during the polymerization process, and the ethylene partial pressure was observed and controlled at 0.5MPa by a flow meter;

[0109] After the polymerization reaction was carried out for 30 min, the polymerization reaction was stopped, the reaction solution was poured into methanol for precipitation and then filtered, the filter cake was washed with methanol and dried (dried to constant weight at 80 ° C) to obtain a functionalized cycloolefin copolymer B (6.8 g), wherein the catalytic activity of the catalyst in the reaction system of this embodiment is 2.7×10 7 g / (molCat.·h).

[0110] Example 3

[0111] This embodiment provides a functionalized cycloolefin copolymer C, wherein the functionalized cycloolefin copolymer C includes structural units having structures shown in the following formula IC, formula II-C and formula III-C:

[0112]

[0113] The preparation method of the functionalized cycloolefin copolymer C is as follows:

[0114] In a 300mL autoclave reactor, 0.01mol of functionalized cycloolefin C, 0.1mol of norbornene, 100mL of toluene and 2.4mg of hydrogen were added in sequence, the reaction system was heated to 100°C, and under stirring at 500rpm, 0.3mmol of triisobutylaluminum (TIBA), 1.5μmol of rac-Et(Ind)2ZrCl2 and 6μmol of triphenylmethyltetrakis(pentafluorophenyl)borate were added in sequence. During the polymerization process, ethylene was added by supplementary metering, and the ethylene partial pressure was observed and controlled at 1.2MPa by a flowmeter.

[0115] After the polymerization reaction was carried out for 10 min, the polymerization reaction was stopped, the reaction solution was poured into methanol for precipitation and then filtered, the filter cake was washed with methanol and dried (dried to constant weight at 80° C.) to obtain a functionalized cycloolefin copolymer C (13.8 g), wherein the catalytic activity of the catalyst in the reaction system of this embodiment was 5.5×10 7 g / (molCat.·h).

[0116] Example 4

[0117] This embodiment provides a functionalized cycloolefin copolymer D, wherein the functionalized cycloolefin copolymer D comprises structural units having structures shown in the following formula ID, formula II-D and formula III-D:

[0118]

[0119] The preparation method of the functionalized cycloolefin copolymer D is as follows:

[0120] In a 300 mL autoclave reactor, 0.01 mol of functionalized cycloolefin D, 0.1 mol of tetracyclododecene, 100 mL of toluene and 2.4 mg of hydrogen were added in sequence. The reaction system was heated to 130 °C. Under stirring at 500 rpm, 0.1 mmol of triisobutylaluminum (TIBA), 0.5 μmol of i Pr(Flu)(Cp)ZrCl2 and 6μmol triphenylmethyltetrakis(pentafluorophenyl)borate, ethylene was added by supplementary metering during the polymerization process, and the ethylene partial pressure was observed and controlled at 1.0MPa by a flow meter;

[0121] After the polymerization reaction was carried out for 15 min, the polymerization reaction was stopped, the reaction solution was poured into methanol for precipitation and then filtered, the filter cake was washed with methanol and dried (dried to constant weight at 80 ° C) to obtain a functionalized cycloolefin copolymer D (10.6 g), wherein the catalytic activity of the catalyst in the reaction system of this embodiment is 8.5×10 7 g / (molCat.·h).

[0122] Example 5

[0123] This embodiment provides a functionalized cycloolefin copolymer E, wherein the functionalized cycloolefin copolymer E comprises structural units having structures shown in the following formulas IE, II-E and III-E:

[0124]

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

[0126] Comparative Example 1

[0127] This comparative example provides a functionalized cycloolefin copolymer 1, wherein the functionalized cycloolefin copolymer 1 comprises structural units having structures shown in the following formula II-1 and formula III-1:

[0128]

[0129] The preparation method of the functionalized cycloolefin copolymer 1 is as follows:

[0130] In a 300 mL autoclave reactor, 0.2 mol of norbornene, 100 mL of toluene and 2.4 mg of hydrogen were added in sequence. The reaction system was heated to 130 °C and stirred at 500 rpm. 0.1 mmol of triisobutylaluminum (TIBA), 0.5 μmol of iPr(Flu)(Cp)ZrCl2 and 2μmol triphenylmethyltetrakis(pentafluorophenyl)borate, ethylene was added by supplementary metering during the polymerization process, and the ethylene partial pressure was observed and controlled at 1.0MPa by a flow meter;

[0131] After the polymerization reaction was carried out for 15 min, the polymerization reaction was stopped, and the reaction solution was poured into an acid alcohol (a hydrochloric acid solution with a mass concentration of 1%, and the solvent was ethanol) for precipitation and then filtered. The filter cake was washed with ethanol and dried (dried to constant weight at 80° C.) to obtain a functionalized cycloolefin copolymer 1 (7.6 g). The catalytic activity of the catalyst in the reaction system of this comparative example was 6.1×10 7 g / (molCat.·h).

[0132] The performance of the functionalized cycloolefin copolymers provided in the above examples and comparative examples was tested, and the specific testing method is as follows:

[0133] The molar content of cycloolefins was calculated by NMR carbon spectrum. The calculation method is based on the following references: Macromolecules 2001, 34, 5770-5777; Pure Appl. Chem., Vol. 77, No. 5, pp. 801–814, 2005.

[0134] Polar group content: calculated by NMR carbon spectrum results, polar group molar content = I SiCH3 / I CH2

[0135] Weight average molecular weight (Mw), molecular weight distribution index (PDI): obtained by high temperature gel permeation chromatography (GPC) test, the instrument is Polymer Char GPC-IR, the chromatographic column is Agilent PL1110-6400, 1,2,4-trichlorobenzene is used as the eluent, polystyrene is used as the reference, and the elution is performed at 160°C with a flow rate of 1.00 mL / min;

[0136] Glass transition temperature (Tg): measured by differential calorimetry (DSC, NETZSCH DSC204F1) in the scanning temperature range of 30-230°C, with both the heating and cooling rates being 15 K / min. Tg was determined at the second heating stage.

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

[0138] Table 1

[0139]

[0140] From the above data, it can be seen that the functionalized cycloolefin copolymers prepared using cycloolefin monomers containing polar groups in the present invention (provided in Examples 1-5) and the functionalized cycloolefin copolymers prepared without using cycloolefin monomers containing polar groups (provided in Comparative Example 1) have similar glass transition temperatures, indicating that the use of cycloolefin monomers containing polar groups has no adverse effect on polymerization activity, molecular weight and Tg.

[0141] The functional cycloolefin copolymer provided by the present invention has the properties of controllable glass transition temperature and controllable polar group content (1-30 mol%), which helps to improve the adhesion, coating, printability and compatibility of the cycloolefin copolymer.

[0142] In summary, the present invention designs the structure of the functional cycloolefin copolymer to prepare a functional cycloolefin copolymer with excellent comprehensive performance, controllable glass transition temperature, and controllable polar group content, and the preparation method of the functional cycloolefin copolymer is simple and suitable for industrial production.

[0143] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A functionalized cycloolefin copolymer, characterized in that: The functionalized cycloolefin copolymer includes structural units having structures shown in the following formulas I, II and III: Wherein, "*" indicates the connection site; m is 0 or 1, x is an integer from 0 to 6, and R is selected from a C1-C10 alkyl group; n is 0 or 1; R1 is H or a C1-C6 alkyl group.

2. The functionalized cycloolefin copolymer according to claim 1, characterized in that In the functionalized cycloolefin copolymer, the molar ratio of the structural unit of formula I, the structural unit of formula II and the structural unit of formula III is (0.017-1):1:(0.33-3.95).

3. The functionalized cycloolefin copolymer according to claim 1, characterized in that The R is selected from any one of methyl, ethyl, isopropyl or tert-butyl; Preferably, R1 is selected from any one of H, methyl, ethyl, butyl or hexyl, and more preferably H or methyl.

4. The functionalized cycloolefin copolymer according to claim 1, characterized in that The weight average molecular weight of the functionalized cycloolefin copolymer is 10,000-200,000 g / mol; The molecular weight distribution index of the functionalized cycloolefin copolymer is 2.0-3.0; Preferably, the glass transition temperature of the functionalized cycloolefin copolymer is 60-200°C.

5. A method for preparing a functionalized cycloolefin copolymer according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: In the presence of a main catalyst and a co-catalyst, functionalized cycloolefin, unmodified cycloolefin and alpha-olefin are polymerized, and then a chain terminator is added thereto to terminate the polymerization reaction, thereby obtaining the functionalized cycloolefin copolymer.

6. The preparation method according to claim 5, characterized in that: The main catalyst includes a metallocene compound; Preferably, the metallocene catalyst is selected from rac-Et(Ind)2ZrCl2, rac-Et(H4Ind)2ZrCl2, rac-Me2Si(Ind)2ZrCl2, Ph2C(Flu)(Cp)ZrCl2, i Pr(Flu)(Cp)ZrCl2、rac- i Any one or a combination of at least two of Pr(Ind)2ZrCl2; Preferably, the co-catalyst is selected from any one or a combination of at least two of alkyl aluminum, alkyl aluminoxane, borane catalyst or borate catalyst; Preferably, the alkyl aluminum is selected from any one or a combination of at least two of trimethyl aluminum, triethyl aluminum or triisobutyl aluminum; Preferably, the alkylaluminoxane is selected from methylaluminoxane and / or modified methylaluminoxane; Preferably, the borane catalyst is selected from any one or a combination of at least two of triphenylborane, tri(pentafluorophenyl)borane or triperfluorobiphenylborane; Preferably, the borate catalyst is triphenylmethyltetrakis(pentafluorophenyl)borate and / or N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate; Preferably, the molar ratio of the main catalyst to the co-catalyst is 1:(1-1000); Preferably, the molar ratio of the main catalyst to the alkyl aluminum, and the molar ratio of the main catalyst to the alkyl aluminoxane are each independently 1:(50-1000); 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).

7. The preparation method according to claim 5, characterized in that: The functionalized cycloolefin has a structure as shown in the following formula I-1: Wherein, m is 0 or 1, and x is an integer from 0 to 6; Preferably, when m is 0, the functionalized cycloolefin of formula I-1 is prepared by the following method, which comprises the following steps: Cyclopentadiene reacts with α-olefin dimethyl chlorosilane to obtain the target compound; Preferably, when m is 1, the functionalized cycloolefin of formula I-1 is prepared by the following method, which comprises the following steps: Cyclopentadiene reacts with α-olefin dimethyl chlorosilane to obtain an intermediate product, and the intermediate product reacts with cyclopentadiene again to obtain a target compound; Preferably, the reaction temperature is 70-160°C and the reaction time is 13-16h; Preferably, the reaction is carried out in a protective gas atmosphere.

8. The preparation method according to claim 5, characterized in that: The unmodified cyclic olefin is selected from norbornene and / or tetracyclododecene; 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; Preferably, the chain terminator is selected from any one of methanol, ethanol, isopropanol or tert-butanol, or a combination of at least two thereof, and more preferably methanol.

9. The preparation method according to claim 5, characterized in that: The molar ratio of the functionalized cycloolefin compound, the unmodified cycloolefin and the α-olefin is (0.017-1):1:(0.33-3.95); Preferably, the molar ratio of the functionalized cycloolefin compound to the chain terminator is 1:(1.2-10).

10. The preparation method according to claim 5, characterized in that: The polymerization reaction temperature is 80-160° C., the pressure is 0.2-2.0 MPa, and the time is 1-30 min.

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