An alpha-olefin-cycloolefin copolymer, a method for preparing the same, and an application thereof

Abstract

The present application provides a method for preparing alpha-olefin-cycloolefin copolymer using non-metallocene complex and co-catalyst, and alpha-olefin-cycloolefin copolymer with high Tg prepared thereby and its application. The alpha-olefin-cycloolefin copolymer can be prepared at low cost and high efficiency without using aluminoxane co-catalyst by the preparation method of the present application. And the alpha-olefin-cycloolefin copolymer of the present application has high content of cycloolefin unit, thus the copolymer has excellent transparency and high glass transition temperature, and is widely used in industry. The higher the content of cycloolefin, the higher the Tg of the copolymer. The COC copolymer with high glass transition temperature has high product purity, transparency and high heat distortion temperature, and is used in health-related fields, in which cleanliness and high-temperature sterilization operation are required, and in optical data storage such as CD and CD-ROM, in which low birefringence and high molding repeatability are important requirements.

Description

Technical Field

[0001] This invention provides an α-olefin-cycloolefin copolymer, its preparation method, and its application. More specifically, it provides a method for preparing an α-olefin-cycloolefin copolymer using a non-metallocene complex and a cocatalyst, as well as the resulting α-olefin-cycloolefin copolymer with high Tg and its application. Background Technology

[0002] Cyclic-Olefin copolymers (COCs) are a class of high-value-added thermoplastic engineering plastics synthesized by the addition copolymerization of cyclic olefins. They have attracted considerable attention due to their high transparency, high glass transition temperature (Tg), and high chemical resistance. The glass transition temperature is controlled by the proportion of comonomers; the higher the content of cyclic olefin units, the higher the Tg of the copolymer. COC copolymers with high glass transition temperatures exhibit high product purity, transparency, and high heat distortion temperature, making them suitable for applications in the healthcare field, where cleanliness and resistance to high-temperature sterilization are required, and for optical data storage such as CDs and CD-ROMs, where low birefringence and high molding repeatability are important requirements.

[0003] Early cycloolefin copolymerization used Ziegler-Natta catalysts, but these catalysts have multiple active centers, resulting in low polymerization activity and poor resistance to polar groups, limiting their application. With the emergence of metallocene catalysts with higher polymerization activity, research on them has become increasingly active. Chinese patent application CN101125901A discloses a method for preparing cycloolefin copolymers with narrow compositional distribution using a metallocene catalyst; Chinese patent CN102702433B discloses a method for preparing high molecular weight ethylene-norbornene copolymers using a semi-metallocene catalyst; Chinese patent CN102286126A provides a method for preparing high-transparency cycloolefin copolymers with low cycloolefin content using a metallocene catalyst; and Chinese patent CN101613437B discloses a method for preparing cycloolefin copolymers with polar groups using a metallocene catalyst. Compared with traditional Ziegler-Natta catalysts, metallocene catalysts allow for control of the molecular weight, stereoregularity, and comonomer reactivity of the copolymer based on the structure of the catalyst and ligands.

[0004] In recent years, non-metallocene single-active-site catalysts have attracted widespread attention due to their different properties compared to metallocene catalysts and their ease of synthesis. Compared with metallocene compounds, non-metallocene compounds can provide more electrophilic active sites and more open coordination spaces, thus potentially exhibiting higher cyclic olefin monomer insertion efficiency. They can catalyze the copolymerization of norbornene with high monomer ratios, and the spatial structure of the copolymers also differs, resulting in certain variations in product performance. Chinese patent application CN1887925A discloses a type of non-metallocene catalyst that can catalyze the copolymerization of ethylene with cyclic olefins such as cyclopentadiene and norbornene using a low amount of co-catalyst. The ethylene-cyclic olefin copolymers obtained by this non-metallocene catalyst have higher strength and modulus compared to ethylene-cyclic olefin copolymers prepared by conventional metallocene catalysis, which greatly expands the application range of the copolymers, for example, in packaging materials where uprightness and stiffness are required. However, compared with conventional metallocene-catalyzed ethylene-cyclic olefin copolymerization, the polymerization activity of this non-metallocene catalyst is relatively low, requiring the use of alkylaluminoxanes as co-catalysts for solution polymerization. On the other hand, the extensive use of expensive co-catalysts such as MAO (methylaluminoxane), MMAO (modified methylaluminoxane), or dMAO (dry methylaluminoxane) greatly increases production costs and significantly increases the metal content in the polymer, which is detrimental to its industrial application.

[0005] Therefore, the following technical problem exists in the prior art: it is difficult to prepare ethylene-cycloolefin copolymers exhibiting excellent properties in a low-cost and industrially advantageous manner using catalysts with high polymerization activity. Summary of the Invention

[0006] In view of the above-mentioned technical problems, the inventors conducted in-depth research and discovered that by using a catalytic system formed from a non-ceramic catalyst with a specific structure and alkylaluminum and boron compounds, α-olefin-cycloolefin copolymers can be prepared with high polymerization activity even without using the expensive aluminoxane cocatalysts required in existing technologies. Furthermore, the prepared α-olefin-cycloolefin copolymers exhibit high Tg and high transparency, demonstrating excellent application prospects.

[0007] Without being limited by any theory, the inventors hypothesize that by using organoborides and alkylaluminum as cocatalysts to form a single-center catalytic system with non-metallocene complexes, alkylaluminoxanes can be replaced. This not only avoids reducing the polymerization activity of the catalyst system but also significantly reduces production costs. Furthermore, by adding an appropriate amount of chain transfer agent, the molecular weight of the polymerization product can be adjusted, avoiding the formation of gel products with high cyclic olefin concentrations during polymerization.

[0008] The α-olefin-cycloolefin copolymers prepared by the method of this invention exhibit high glass transition temperatures (Tg) and high transparency, leading to wider applications in industry. Furthermore, the method of this invention allows the use of alkanes or similar solvents for solution polymerization, resulting in mild polymerization conditions and high copolymerization activity, which significantly reduces manufacturing costs. This solves the technical problems existing in the prior art.

[0009] Specifically, the present invention provides a method for preparing an α-olefin-cycloolefin copolymer, which includes the following steps: copolymerizing α-olefins and cycloolefins in the presence of a non-metallocene complex and a co-catalyst.

[0010] Furthermore, the present invention provides an α-olefin-cycloolefin copolymer, which is prepared by the preparation method of the α-olefin-cycloolefin copolymer of the present invention.

[0011] Furthermore, the present invention provides a polymer composition comprising at least the α-olefin-cycloolefin copolymer of the present invention.

[0012] In addition, the present invention also provides the application of the α-olefin-cycloolefin copolymer of the present invention or the polymer composition of the present invention in the manufacture of optical components, packaging materials, electronic components, and medical devices.

[0013] Technical effect

[0014] The method for preparing α-olefin-cycloolefin copolymers according to the present invention allows for the low-cost and efficient preparation of α-olefin-cycloolefin copolymers without the use of aluminoxane-based cocatalysts. Furthermore, the molecular weight can be easily controlled by adjusting the proportion of alkylaluminum in the preparation method, thereby allowing for the adjustment of the copolymer morphology. Additionally, the method for preparing α-olefin-cycloolefin copolymers according to the present invention can be carried out in an inert organic solvent, preventing explosive polymerization during polymerization, resulting in mild polymerization conditions and reduced requirements on production equipment.

[0015] Furthermore, the α-olefin-cycloolefin copolymer of the present invention has a high content of cycloolefin units, and the copolymer has excellent transparency and a high glass transition temperature, making it widely applicable in industry. Attached Figure Description

[0016] Figure 1 The typical NMR spectrum of COC is used to illustrate the calculation of cyclic olefin content in α-olefin-cyclic olefin copolymers. Detailed Implementation

[0017] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0018] In the context of this invention, unless otherwise explicitly defined or the meaning is beyond the understanding of those skilled in the art, hydrocarbon or hydrocarbon derivative groups with three or more carbon atoms (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) have the same meaning when not prefixed with "n-" as when prefixed with "n-". For example, propyl is generally understood as n-propyl, and butyl is generally understood as n-butyl, unless otherwise explicitly stated.

[0019] Furthermore, any implementation described herein may be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and shall not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

[0020] Furthermore, in this invention, the endpoint values ​​of multiple sets of numerical ranges describing the same physical property can be arbitrarily combined. Those skilled in the art can confirm that such combinations are obviously part of the original disclosure or original record of this invention, and should not be regarded as new content not disclosed or anticipated herein.

[0021] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, unless being based on weight would not be in accordance with the common understanding of those skilled in the art.

[0022] The method for preparing the α-olefin-cycloolefin copolymer of the present invention includes the following steps: copolymerizing α-olefins and cycloolefins in the presence of a non-metallocene complex and a co-catalyst. Thus, the α-olefin-cycloolefin copolymer is prepared.

[0023] In this invention, the α-olefin is an olefin represented by the following formula (a).

[0024] R-CH=CH2 (a)

[0025] Where R represents H or C 1-8 Straight-chain or branched alkyl groups, preferably H or C 1-4 Straight-chain or branched alkyl groups, more preferably H, methyl or ethyl.

[0026] In one embodiment of the invention, the α-olefin can be exemplified by C0. 2-10 Straight-chain or branched olefins, preferably C 2-6 Straight-chain or branched olefins, more preferably C 2-3 Alkenes, more preferably ethylene or propylene.

[0027] In one embodiment of the invention, these α-olefins may be used alone or in combination of two or more.

[0028] In this invention, the cyclic olefin refers to an olefin that is monocyclic or polycyclic and has double bonds on the ring.

[0029] In one embodiment of the present invention, cycloolefins can specifically be exemplified by C. 3-20 Cyclic olefins. As the C... 3-20 Cyclic alkenes, specifically, include monocyclic cyclic alkenes such as cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctatetraene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadene, pentacyclohexadecene, and 8-ethyltetracyclododecene, as well as dicyclopentadiene, norbornene, and norbornene. , , and Spirocyclic, bridged, or fused-ring bicyclic or polycyclic olefins. As the C... 3-20 Cycloolefins, preferably cyclopentene, cyclopentadiene, norbornene, dicyclopentadiene, norbornene, vinyl norbornene, ethylidene norbornene, or tetracyclododecene.

[0030] In one embodiment of the present invention, C 3-20 The cycloolefin may optionally be further divided by one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1) C-members. 1-10 Straight-chain or branched hydrocarbon groups are substituted at appropriate positions. As the C 1-10 Straight-chain or branched hydrocarbon groups, preferably C 1-10 Straight-chain or branched alkyl or C 2-10 Straight-chain or branched alkenyl groups, preferably C 1-4 Straight-chain or branched alkyl or C 2-4 Straight-chain or branched alkenyl groups, more preferably methyl, ethyl, vinyl, or ethylidene groups.

[0031] In one embodiment of the present invention, as C 3-20 Cyclic alkenes, for example, can be further exemplified by compounds represented by formula (Y).

[0032] (Y).

[0033] In formula (Y), the groups Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh can be the same or different, and each can be independently selected from hydrogen, C, and C. 1-10 Straight-chain or branched hydrocarbon groups. As the C... 1-10 Straight-chain or branched hydrocarbon groups, preferably selected from C 1-10 Straight-chain or branched alkyl or C 2-10 Straight-chain or branched alkenyl groups, preferably C 1-4 Straight-chain or branched alkyl or C2-4 Straight-chain or branched alkenyl groups.

[0034] In one embodiment of the present invention, in formula (Y), the groups Ra to Rh can be the same or different, and each is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl groups and C 2-4 Straight-chain or branched alkenyl groups, such as C 2-3 Straight-chain or branched alkenyl groups, wherein each is preferably selected independently from hydrogen, methyl, ethyl, vinyl or ethylidene groups.

[0035] In one embodiment of the invention, n in formula (Y) is an integer from 0 to 6, preferably 0 or 1.

[0036] In one embodiment of the invention, in formula (Y), the symbol... It represents a single bond or a double bond.

[0037] In one embodiment of the present invention, the compound represented by formula (Y) is preferably norbornene, ethylidene norbornene, vinyl norbornene, norbornediene, or 5-methyl norbornene, and more preferably norbornene, ethylidene norbornene, or vinyl norbornene.

[0038] In one embodiment of the present invention, the cycloolefin can be used alone or in combination of two or more.

[0039] In this invention, the non-metallocene complex is selected from compounds represented by formula (I).

[0040] (I).

[0041] In one embodiment of the present invention, in formula (I), groups R1, R2, R3, and R4 may be the same or different, and each is independently selected from hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups, preferably each independently selected from hydrogen and C. 1-6 The alkyl group is either straight-chain or branched, and more preferably each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl. In one embodiment of the invention, R1 and R3 represent hydrogen. In one embodiment of the invention, R2 and R4 are each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl, and preferably each is independently selected from hydrogen and tert-butyl.

[0042] In one embodiment of the present invention, in formula (I), groups R6, R7, R8, and R9 may be the same or different, and each is independently selected from hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups, preferably each independently selected from hydrogen and C. 1-6The alkyl group is either straight-chain or branched, more preferably selected independently from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl. In one embodiment of the invention, R7 and R9 represent hydrogen. In one embodiment of the invention, R6 and R8 are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, preferably selected independently from hydrogen and tert-butyl.

[0043] In one embodiment of the invention, in formula (I), group R5 represents hydrogen or C. 1-12 Straight-chain or branched hydrocarbon groups, preferably hydrogen or C 1-6 Straight-chain or branched alkyl or C 6-10 Aryl, more preferably hydrogen, C 1-3 Straight-chain or branched alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl or isopropyl.

[0044] In one embodiment of the present invention, in formula (I), R 10 Indicates hydrogen or C 1-6 Straight-chain or branched hydrocarbon groups, preferably hydrogen or C 1-6 Straight-chain or branched alkyl groups, more preferably hydrogen, methyl and ethyl, more preferably hydrogen.

[0045] In one embodiment of the present invention, the symbol It represents a single bond or a double bond. When it represents a double bond, the H on N does not exist. When it represents a single bond, the H on N exists.

[0046] In one embodiment of the invention, in formula (I), the group Y is O or S, preferably O.

[0047] In one embodiment of the invention, in formula (I), group A is S or O, preferably S.

[0048] In one embodiment of the present invention, in formula (I), the group M is selected from metal elements of Group III to Group VI of the periodic table, preferably Group IVB metal elements such as titanium, zirconium and hafnium, and more preferably titanium.

[0049] In one embodiment of the invention, in formula (I), group X is a halogen, including fluorine, chlorine, bromine and iodine, wherein chlorine or bromine is preferred.

[0050] In one embodiment of the present invention, in formula (I), the symbol ------ represents a coordinate bond.

[0051] In one embodiment of the invention, n is 1, 2, 3, 4 or 5, depending on the valence state of the central metal atom M, and preferably n is 2, 3 or 4.

[0052] In one embodiment of the present invention, the non-metallocene complex represented by formula (I) is selected from at least one of 3-tert-butylsalicylene-2-methylthioaniline titanium trichloride, salicylene-2-methylthioaniline titanium trichloride, salicylene-2-phenylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-mercaptoaniline titanium trichloride, salicylene-2-mercaptoaniline titanium trichloride, salicylene-2-methylthioaniline titanium trichloride, salicylene-2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-methylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-methylthioaniline titanium trichloride, and 3,5-di-tert-butylsalicylene-2-propylthioaniline titanium trichloride.

[0053] In one embodiment of the present invention, the non-metallocene complex shown in formula (I) can be used alone or in combination in any proportion.

[0054] In this invention, the non-metallocene complex represented by formula (I) can be synthesized by methods known in the art or obtained through commercial means.

[0055] In one embodiment of the present invention, the compound represented by formula (I) can be manufactured, for example, by the following manufacturing method.

[0056] The manufacturing method includes, for example, a step of coordinating a compound of formula (IA) with a compound of formula (X) to obtain the compound of formula (I) (hereinafter referred to as coordination step A).

[0057] (IA)

[0058] MX4 (X).

[0059] In this invention, the definitions and preferred embodiments of each group in formula (IA) are the same as those in formula (I) above. In formula (IA), when... When representing a single bond, p represents 2, and H exists on N. When representing a double bond, p represents 1, and H on N does not exist.

[0060] In this invention, in formula (X), the group M is selected from metal elements of Groups III to VI of the periodic table, preferably Group IVB metal elements such as titanium, zirconium and hafnium, and more preferably titanium.

[0061] According to the present invention, in formula (X), the group X is a halogen, including fluorine, chlorine, bromine and iodine, wherein chlorine or bromine is preferred.

[0062] According to the present invention, when performing the coordination step A, the molar ratio of the compound represented by formula (X) to the compound represented by formula (IA) is generally 0.7-1.5:1, preferably 0.9-1.3:1, and more preferably 1-1.2:1.

[0063] According to the present invention, the coordination step A can be carried out in the presence of a solvent. The present invention does not particularly limit the solvent, as long as it can dissolve the compound represented by formula (X) and the compound represented by formula (IA) without interfering with the coordination reaction. Specifically, C can be cited as an example of the solvent. 5-20 Alkanes, C 6-20 Aromatic hydrocarbons and C 4-20 Alicyclic hydrocarbons, etc., with C being the preferred choice. 6-12 Aromatic hydrocarbons, preferably toluene, xylene, and trimethylbenzene. These solvents can be used alone or in combination in any proportion.

[0064] According to the present invention, there is no particular limitation on the amount of solvent used. Any amount that is conducive to the coordination reaction can be used. For example, the molar ratio of the solvent to the compound represented by formula (IA) can be 5-200, preferably 10-100, but it is not limited thereto.

[0065] According to the present invention, the reaction temperature of the coordination step A is generally -80-100°C, preferably -50-70°C, and more preferably -30-50°C.

[0066] According to the present invention, the reaction pressure of the coordination step A can be any pressure suitable for the coordination reaction to proceed, but for ease of implementation, it is generally atmospheric pressure to 0.2 MPa.

[0067] According to the present invention, the reaction time of the coordination step A is generally 0.1-72 hours, preferably 0.2-48 hours, and more preferably 1-24 hours.

[0068] According to the present invention, if necessary, in order to promote the reaction, the coordination reaction of the coordination step A can be carried out under stirring (e.g., stirring speed of 100-1000 rpm).

[0069] According to the present invention, the coordination reaction in coordination step A can be carried out under a protective gas atmosphere, as needed. Examples of such a protective gas include inert gases such as nitrogen.

[0070] According to the present invention, after the coordination reaction in the coordination step A is completed, the compound represented by formula (I) can be separated from the mixture obtained by the reaction as a reaction product by conventional separation methods. Examples of such separation methods include filtration or filtration followed by washing, and optionally further drying. Alternatively, the obtained reaction product can be purified by recrystallization, column chromatography, or preparative chromatography, as needed.

[0071] According to the present invention, there are no particular limitations on the methods of filtration, washing, and drying; those conventionally used in the art can be used as needed. The washing is generally performed 1-6 times, preferably 2-3 times, as needed. The solvent used for washing is preferably the same as the solvent used in the coordination reaction, but it can also be different. As for drying, examples include inert gas drying, vacuum drying, or vacuum heating drying, with inert gas drying or vacuum heating drying being preferred, and vacuum heating drying being the most preferred. In this case, the drying temperature range is generally from room temperature to 140°C, and the drying time is generally 2-20 hours, but is not limited to these.

[0072] In this invention, the cocatalyst is a mixture of an organoboron compound and at least one alkylaluminum derivative selected from alkylaluminum, alkylaluminum hydrolysate, and haloalkylaluminum.

[0073] In one embodiment of the present invention, the preparation method does not use aluminum oxane cocatalysts.

[0074] In one embodiment of the present invention, the organoboron compound is at least one selected from alkylboron, arylboron, and borate.

[0075] In this invention, the alkylboron and arylboron can be compounds having the following general formula (B-1):

[0076] B(R)3 (B-1)

[0077] In this configuration, each of the three R groups may be the same as or different from the others, and each R is independently selected from C. 1-6 Straight-chain or branched alkyl groups and C 6-12 aryl groups, each optionally bonded by one or more halogen atoms or halogenated carbons. 1-6 The alkyl or branched alkyl group is substituted with a phenoxy group. R is preferably selected from methyl, ethyl, propyl, butyl, isobutyl, phenyl, tolyl, trifluoromethylphenyl, and pentafluorophenyl. Specific examples of alkylboron include trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron. Specific examples of arylboron include tris(pentafluorophenyl)boron and tris[3,5-bis(trifluoromethyl)phenyl]boron.

[0078] In this invention, the borate can be a compound having the following general formula (B-2):

[0079] [L] + [BE4] m - (B-2)

[0080] Where L is a cationic group, and each E can be the same or different, and each is independently selected from halogen atoms, C 6-12 aryl group, wherein the aryl group is optionally surrounded by one or more halogen atoms, C 1-6 Straight-chain or branched alkyl groups, halogenated C 1-6 Straight-chain or branched alkyl groups, C 1-6 The group is substituted with a straight-chain or branched alkoxy or phenoxy group. The E group is preferably selected from fluorine, phenyl, trifluoromethylphenyl, and pentafluorophenyl. m represents the numerical value of the valence of the group in the L portion.

[0081] [L] + Some of these can be cations common in borates, for example, Li can be listed. + Na + K + Ca 2+ Mg 2+ [Fe(C5H5)2] + (Ferrocene group), etc. Additionally, the L moiety can also be an organic amine, in which case the L moiety can be represented as N(R')3, where each R' is independently selected from H, C, etc. 1-6 Straight-chain or branched alkyl groups and C 6-12 aryl, but not both H; or two R' and N can bond together to form an optional C 1-6 A straight-chain or branched alkyl-substituted 5-7 membered nitrogen-containing heterocycle, preferably in which each R' is independently selected from H, C 1-4 Straight-chain or branched alkyl and phenyl groups, but not both H; or two R' and N can be bonded together to form an optional C-shaped group. 1-4 Straight-chain or branched alkyl-substituted 5-7 member nitrogen-containing heterocyclic aromatic or heterocyclic hydrocarbons. Examples include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, imidazole, 1-butyl-3-methylimidazolium, pyridine, piperidine, etc. [L] + Some can also be groups carrying carbocations, such as triphenylmethyl carbocations.

[0082] Specific examples of borates include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o-,p-dimethylphenyl)borate, triethylammonium tetra(o-,p-dimethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetraphenylborate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylmethyl tetra(pentafluorophenyl)borate, 1-butyl-3-methylimidazolium tetrafluoroborate, and ferrocene tetrafluoroborate.

[0083] In this invention, compounds represented by the following formula (D) can be cited as examples of alkylaluminum:

[0084] Al(R 11 )3 (D)

[0085] In formula (D), group R 11 Whether they are the same or different, each is independently selected from C. 1-8 Alkyl groups, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and isohexyl.

[0086] In one embodiment of the present invention, the preferred alkylaluminum types are trimethylaluminum (Al(CH3)3), triethylaluminum (Al(CH2CH3)3), tri-n-propylaluminum (Al(C3H7)3), triisobutylaluminum (Al(i-C4H9)3), tri-n-butylaluminum (Al(C4H9)3), and triisopentylaluminum (Al(i-C5H7)3). 11 )3) Tri-n-pentyl aluminum (Al(C5H) 11 )3) Tri-n-hexyl aluminum (Al(C6H) 13 )3) Triisohexylaluminum (Al(i-C6H) 13 )3) Diethylmethylaluminum (Al(CH3)(CH3CH2)2) and dimethylethylaluminum (Al(CH3CH2)(CH3)2), etc., more preferably trimethylaluminum, triethylaluminum, tri-n-propylaluminum and triisobutylaluminum, further preferably triethylaluminum and triisobutylaluminum, and most preferably triisobutylaluminum.

[0087] In one embodiment of the invention, these alkylaluminum compounds may be used alone or in combination in any proportion.

[0088] In this invention, the alkylaluminum hydrolysate can be exemplified by the hydrolysate obtained by reacting the aforementioned alkylaluminum with water. In this reaction, the molar ratio of the alkylaluminum to water is generally 0.5-4:1, preferably 1-3:1.

[0089] In one embodiment of the invention, these alkyl aluminum hydrolysates can be used alone or in combination in any proportion.

[0090] In this invention, compounds of formula (E) can be cited as examples of the haloalkylaluminum:

[0091] Al(R 11 ) n X 3-n (E)

[0092] In formula (E), group R 11 Whether they are the same or different, each is independently selected from C. 1-8 Alkyl group, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and isohexyl, most preferably methyl or ethyl; group X is a halogen, such as fluorine, chlorine, bromine, or iodine, preferably chlorine. n is an integer of 1 or 2.

[0093] In one embodiment of the present invention, specific examples of the haloalkylaluminum include, for instance, dichlorodimethylaluminum (Al(CH3)2Cl), dichloromethylaluminum (Al(CH3)Cl2), dichlorodiethylaluminum (Al(CH3CH2)2Cl), dichloroethylaluminum (Al(CH3CH2)Cl2), dichlorodipropylaluminum (Al(C3H7)2Cl), dichloropropylaluminum (Al(C3H7)Cl2), dichlorodi-n-butylaluminum (Al(C4H9)2Cl), dichlorodi-n-butylaluminum (Al(C4H9)Cl2), dichlorodiisobutylaluminum (Al(i-C4H9)2Cl), dichloroisobutylaluminum (Al(i-C4H9)Cl2), and dichlorodi-n-pentylaluminum (Al(C5H9)Cl2). 11 )2Cl), dichloro-n-pentyl aluminum (Al(C5H) 11 Cl2), diisopentylaluminum chloride (Al(i-C5H) 11 )2Cl), dichloroisopentylaluminum (Al(i-C5H) 11 Cl2), di-n-hexyl aluminum chloride (Al(C6H) 13 )2Cl), dichloro-n-hexyl aluminum (Al(C6H) 13 Cl2), aluminum monochlorodiisohexyl (Al(i-C6H) 13 )2Cl), dichloroisohexylaluminum (Al(i-C6H) 13The preferred materials are diethylaluminum chloride (Al(CH3)(CH3CH2)Cl), diethylaluminum chloride (Al(CH3)(C3H7)Cl), diethylaluminum chloride (Al(CH3)(C4H9)Cl), diethylaluminum chloride (Al(CH3)(i-C4H9)Cl), diethylaluminum chloride (Al(CH2CH3)(C3H7)Cl), diethylaluminum chloride (Al(CH2CH3)(C4H9)Cl), and diethylaluminum chloride (Al(CH2CH3)(i-C4H9)Cl), among which diethylaluminum chloride, diethylaluminum chloride, diethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, and dihexylaluminum chloride are preferred, diethylaluminum chloride, diethylaluminum chloride, and dihexylaluminum chloride are further preferred, and diethylaluminum chloride is the most preferred.

[0094] In one embodiment of the invention, these alkyl halogenated aluminum halide can be used alone or in combination in any proportion.

[0095] In one embodiment of the present invention, the method for preparing α-olefin-cycloolefin can independently prepare a catalytic system comprising a non-metallocene complex and a cocatalyst, and then use it for copolymerization of α-olefins and cycloolefins; alternatively, the non-metallocene complex and the cocatalyst can be added sequentially to the reaction system during the copolymerization reaction. The order in which the non-metallocene complex and the cocatalyst are added is not particularly limited. Furthermore, the order in which organoboron compounds, alkylaluminum derivatives selected from at least one of alkylaluminum, alkylaluminum hydrolysates, and haloalkylaluminum are added to the catalyst is also not particularly limited.

[0096] In one embodiment of the present invention, the non-metallocene complex, organoboron compound, and alkylaluminum derivative can be used directly or separately in solutions. In this invention, "direct use" means that each compound is directly added to the solvent used to prepare the above-mentioned catalytic system; or directly added to the solvent in the reaction system during the copolymerization reaction. Preferably, each compound is used separately in solutions.

[0097] As a solvent for preparing the catalytic system and / or for formulating solutions, various inert organic solvents known in the art can be used, such as C 5-20 Alkanes, C 6-30 Aromatic hydrocarbons, C 5-30 Alicyclic hydrocarbons, C 1-20 Halogenated alkanes, C 3-20 Halogenated alicyclic hydrocarbons and C 6-30Halogenated aromatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, toluene, xylene, chlorobenzene, dichlorotoluene, etc., are preferred, among which pentane, hexane, decane, cyclohexane, toluene, and xylene are preferred. These solvents can be used alone or in combination in any proportion.

[0098] In one embodiment of the present invention, when preparing the catalytic system independently, the non-metallocene complex can be contacted with the co-catalyst for 60-360 minutes (hereinafter referred to as contact reaction) to obtain the catalytic system.

[0099] In one embodiment of the present invention, when preparing the catalytic system independently, to ensure sufficient contact between the non-metallocene complex, the organoboron compound, and the alkylaluminum derivative, the solution containing the non-metallocene complex, the organoboron compound, and the alkylaluminum derivative can be stirred (e.g., at a stirring speed of 100-1000 rpm). In one embodiment of the present invention, when preparing the catalytic system independently, the content of the non-metallocene complex, the organoboron compound, and the alkylaluminum derivative in the catalytic system is as follows, or in the case of a copolymerization reaction, after adding the non-metallocene complex, the organoboron compound, and the alkylaluminum derivative to the reaction system, the content of each compound is as follows: the molar ratio of the alkylaluminum derivative calculated as Al to the non-metallocene complex calculated as metal element M is 50-5000:1, preferably 100-4000:1, more preferably 500-2000:1; the molar ratio of the organoboron compound calculated as B to the non-metallocene complex calculated as metal element M is 0.1-20:1, preferably 0.5-10:1, more preferably 0.8-5:1.

[0100] It should be noted that, unless otherwise specified in this specification, the molar amount of non-metallocene complexes is usually expressed as metal element M, the molar amount of alkyl aluminum derivatives is usually expressed as metal element Al, and the molar amount of organoboron compounds is usually expressed as element B.

[0101] In one embodiment of the present invention, the reaction method of the copolymerization method is not particularly limited, and those known in the art can be used, such as solution method, bulk method, etc., with solution method being preferred.

[0102] In one embodiment of the present invention, the copolymerization method can be carried out in the presence of an inert organic solvent as the copolymerization solvent, as needed. Examples of copolymerization solvents commonly used in the art for copolymerizing olefins and cycloolefins can be cited, and the amount used can be referenced from conventional amounts in the prior art, without particular limitation. Specifically, for example, C1 can be cited as the copolymerization solvent. 5-20 Alkanes, C 6-30 Aromatic hydrocarbons, C 5-20 Alicyclic hydrocarbons, C 1-20 Halogenated alkanes, C 3-20 Halogenated alicyclic hydrocarbons and C 6-30 Halogenated aromatic hydrocarbons, etc., with C being the preferred option. 5-12 Straight-chain or branched-chain alkanes, C 5-12 Cycloalkanes, C 6-12 Aromatics, C 1-12 Straight-chain or branched haloalkanes, C 3-12 Halogenated cycloalkanes and C 6-12 Halogenated aromatics, more preferably C 6-9 Straight-chain or branched-chain alkanes, C 6-9 Cycloalkanes, C 6-10 Aromatics, C 1-8 Straight-chain or branched haloalkanes, C 3-8 Halogenated cycloalkanes and C 6-10 Halogenated aromatic hydrocarbons, preferably pentane, hexane, heptane, cyclohexane, cyclooctane, toluene, or xylene. These copolymerization solvents can be used alone or in combination in any proportion.

[0103] In one embodiment of the invention, the copolymerization reaction can be carried out in a stirred tower or batch reactor, preferably a batch reactor. The reactor volume is 0.05-1000L, preferably 0.1-100L.

[0104] In one embodiment of the invention, the reaction pressure (total pressure) of the copolymerization method is 0.1-5.0 MPa, preferably 0.1-3.0 MPa, more preferably 0.1-2.0 MPa, but is not limited thereto.

[0105] In one embodiment of the present invention, the reaction temperature of the copolymerization method is 40-100°C, preferably 60-100°C, more preferably 70-90°C, but is not limited thereto.

[0106] In one embodiment of the present invention, during the copolymerization reaction, the molar ratio of the cyclic olefin to the nonmetallocene complex (calculated as metal element M) in the reaction system is 10. 5 -10 7 :1, preferably 5×10 5 -5×10 6 :1, more preferably 7×105 -2×10 6 :1, but not limited to this.

[0107] In the copolymerization method of the present invention, the polymerization time is related to the amount of catalyst and the reaction temperature. The more catalyst used and the higher the reaction temperature, the faster the reaction rate and the shorter the reaction time. The reaction time is generally 0.1-10h, preferably 0.1-5h, more preferably 15min-2h, but is not limited thereto.

[0108] In one embodiment of the present invention, during the copolymerization reaction, a chain transfer agent can be further added to the catalytic system to adjust the weight-average molecular weight, molecular weight distribution, and content of cyclic olefin units of the copolymer. Other metal alkyl compounds besides the cocatalyst of the present invention can be listed as chain transfer agents, such as one or more of n-butyllithium, diethylzinc, dipropylzinc, dibutylzinc, diisobutylzinc, diethylmagnesium, dibutylmagnesium, or n-butylethylmagnesium. The molar ratio of the chain transfer agent (calculated as a metal element) to the non-metallocene complex (calculated as a metal element M) is 5–500:1, preferably 10–100:1, more preferably 10–50:1. When using a chain transfer agent, it can be added to a separately prepared catalyst system, or it can be added to the reaction system when adding the non-metallocene complex or cocatalyst during the copolymerization reaction. Furthermore, the order of addition of the chain transfer agent is not particularly limited. The chain transfer agent can be used directly or prepared as a solution before use. When preparing the solution, the solvents listed above in this invention for preparing solutions of non-metallocene complexes, organoboron compounds, alkylaluminum derivatives, etc., can be used.

[0109] It should be noted that, unless otherwise specified, the molar amount of the chain transfer agent in this specification is based on the molar amount of the metal element in the chain transfer agent. For example, when diethylzinc is used as the chain transfer agent, the molar amount of the chain transfer agent is based on zinc.

[0110] In one embodiment of the present invention, α-olefin-cycloolefin copolymers can be prepared in a single reactor using a single polymerization reactor device in a continuous or intermittent polymerization manner.

[0111] In one embodiment of the present invention, the copolymerization method of the α-olefin and cycloolefin of the present invention can be carried out as follows: At a temperature of 40-100°C and a pressure of 0.1-5.0 MPa, a copolymerization solvent, α-olefin, and cycloolefin are added to a reactor; after the α-olefin and cycloolefin are dissolved to saturation in the copolymerization solvent, a non-metallocene complex solution, an alkylaluminum derivative solution, an organoboron compound solution, and an optional chain transfer agent are added sequentially, such that the molar ratio of the cycloolefin to the non-metallocene complex (calculated as metal element M) is 10. 5 -107 :1, the molar ratio of the alkylaluminum derivative (calculated as Al) to the non-metallocene complex (calculated as metal element M) is 50-5000:1, the molar ratio of the organoboron compound (calculated as B) to the non-metallocene complex (calculated as metal element M) is 0.1-20:1, and the molar ratio of the chain transfer agent (calculated as metal element) to the non-metallocene complex (calculated as metal element M) is 5-500:1; during the reaction, α-olefins are introduced to maintain the pressure inside the reactor, and the polymerization reaction is kept at a constant temperature for 15 min to 2 h. Thus, α-olefin-cycloolefin copolymers can be prepared.

[0112] In one embodiment of the present invention, after the reaction is completed, the obtained copolymer is precipitated in acidified ethanol. Specifically, the obtained post-polymerization solution is poured into acidified ethanol for precipitation and then dried, preferably under vacuum at 60°C for 24 hours, thereby obtaining the purified α-olefin-cycloolefin copolymer. The acidified ethanol is prepared by mixing concentrated hydrochloric acid and ethanol, wherein the volume percentage of concentrated hydrochloric acid relative to ethanol can be 1v / v%-25v / v%, or 10v / v%-20v / v%, for example, 15v / v.

[0113] In one embodiment of the present invention, during the copolymerization reaction, the concentration of the non-metallocene complex, calculated as metal element M, in the reaction solution is 0.1 × 10⁻⁶. -5 mol / L~50×10 -5 mol / L, preferably 0.5×10 -5 mol / L~20×10 -5 mol / L, more preferably 1×10 -5 mol / L~10×10 -5 mol / L.

[0114] In one embodiment of the present invention, during the copolymerization reaction, the concentration of the cycloolefin in the reaction solution is 1 to 100 mol / L, preferably 10 to 50 mol / L.

[0115] In one embodiment of the invention, during the copolymerization reaction, the concentration of the organoboron compound (calculated as B) in the solution during the reaction is 1 × 10⁻⁶. -6 mol / L~100×10 -5 mol / L, preferably 5×10 -6 mol / L~50×10 - 5 mol / L.

[0116] In one embodiment of the invention, during the copolymerization reaction, the concentration of the alkylaluminum derivative, calculated as Al, in the reaction solution is 1 × 10⁻⁶.-3 mol / L~200×10 -3 mol / L, preferably 10×10 -3 mol / L~150×10 -3 mol / L.

[0117] In one embodiment of the present invention, during the copolymerization reaction, the concentration of the chain transfer agent in the solution, calculated as a metal element, is 0–500 × 10⁻⁶. -5 mol / L, preferably 10×10 -5 mol / L~300×10 -5 mol / L.

[0118] In one embodiment of the invention, the copolymerization method can be carried out in the presence of hydrogen or in the absence of hydrogen. In the presence of hydrogen, the partial pressure of hydrogen can be 0.01-99% of the aforementioned reaction pressure, preferably 0.01-50%, but is not always limited to this.

[0119] In one embodiment of the invention, the copolymerization method can be carried out in the presence of an inert gas or in the absence of an inert gas. When an inert gas is present, the partial pressure of the inert gas can be 0.01-99% of the aforementioned reaction pressure, preferably 0.01-50%, but is not always limited to this. Examples of inert gases include nitrogen, helium, or argon. These inert gases can be used individually or in combination in any proportion as needed.

[0120] The present invention also provides a polymer composition comprising at least the α-olefin-cycloolefin copolymer of the present invention.

[0121] In the polymer composition of this invention, other additives known in the art may be further added as needed, without prejudice to the purpose of this invention, such as processing heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, colorants, antistatic agents, flame retardants, water repellents, waterproofing agents, hydrophilic agents, conductive agents, thermally conductive agents, electromagnetic shielding agents, light transmittance modifiers, fluorescent agents, slip agents, transparency agents, anti-caking agents, metal deactivators, antibacterial agents, fillers, etc., but not limited thereto.

[0122] The present invention also relates to the use of α-olefin-cycloolefin copolymers in the manufacture of the polymer compositions.

[0123] In manufacturing optical components, packaging materials, electronic components, and medical devices, commonly used techniques in the field can be employed as needed. Examples include extrusion molding, injection molding, calendering, blow molding, and thermoforming, but these are not limited to these methods. Thus, optical components, packaging materials, electronic components, and medical devices can be manufactured using these molding methods, utilizing the α-olefin-cycloolefin copolymer of the present invention or the polymer composition of the present invention.

[0124] Therefore, the present invention also provides the use of the α-olefin-cycloolefin copolymer in the manufacture of optical components, packaging materials, electronic components, and medical devices. The present invention also provides the use of the polymer composition in the manufacture of optical components, packaging materials, electronic components, and medical devices. Example

[0125] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0126] In the following examples, the cyclic olefin content in the copolymer was determined using nuclear magnetic resonance (NMR).

[0127] Specifically, such as Figure 1 As shown, taking norbornene as an example, the content (NB%) of norbornene units in the sample was determined using an AVANCE III HD nuclear magnetic resonance spectrometer at a test temperature of 120℃. The copolymer sample was dissolved in deuterated o-dichlorobenzene to prepare a solution of approximately 20 wt%, and the sample was scanned 6000 times at 120℃ to obtain the sample's... 13 C10 NMR spectrum. The main characteristic NMR signal peaks in the figure can be attributed to the following four groups: signals between 45 and 55 ppm belong to C2 / C3, signals between 37 and 44 ppm belong to C1 / C4, signals between 32 and 36 ppm belong to C7, and signals below 31.5 ppm belong to C5 / C6 and the methylene signal of the ethylene unit. The content of norbornene units in the copolymer is determined according to... 13 The peak areas of each assigned signal peak in the C-NMR spectrum are calculated.

[0128] .

[0129] Methods for determining Mη molecular weight and PDI

[0130] The molecular weight and distribution of the copolymer were determined using a Polymer Laboratories PL-220 gel permeation chromatograph with 1,2,4-trichlorobenzene as the mobile phase, polystyrene as the standard, a differential detector, a flow rate of 1.0 mL / min, a measurement temperature of 150 °C, and a sample concentration of 2.0 mg / mL.

[0131] Determination of the glass transition temperature of copolymers.

[0132] The thermal properties of the copolymer were determined using a differential scanning calorimeter (Perkin-Elmer DSC 7). The sample size was 3-5 mg, and the atmosphere was nitrogen. The sample was first heated from 30 °C to 180 °C at a rate of 20 °C / min, held for 3 min, then cooled to 20 °C at a rate of 20 °C / min, held for 3 min, and then heated back to 180 °C at a rate of 20 °C / min. The second heating curve was used for analysis.

[0133] Example 1:

[0134] In a 1L stainless steel batch reactor, 15.6 mol of refined norbornene was dissolved in 500 ml of refined toluene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The solution was saturated with ethylene by repeated pressurization (1 MPa). Under conditions of 90°C, 1 MPa, and stirring, 30 ml of a 1 mol / L toluene solution of triisobutylaluminum, 40 μmol of triphenylmethyltetra(pentafluorophenyl)borate, and 20 μmol of 3-tert-butylsalicyl-2-methylthioaniline titanium trichloride were added in one step. During the polymerization process, ethylene was added in a metered manner to maintain the pressure at 1 MPa.

[0135] After reacting for 15 min, a gel was formed. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 300 mL hydrochloric acid and 2000 mL ethanol) to precipitate the product. The precipitate was then filtered, and the filter cake was washed with 1000 mL of ethanol and dried (at 60 °C to constant weight) to obtain 14 g of copolymer. The catalyst activity was 2.8 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0136] Example 2:

[0137] This embodiment uses a 2L batch reactor. 24 mol of refined ethylene norbornene was dissolved in 1000 ml of refined cyclohexane to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (1 MPa) to saturate the solution. Under conditions of 55°C, 1 MPa, and stirring, 80 ml of a 1 mol / L toluene solution of tri-n-butylaluminum, 0.8 ml of a 1 mol / L toluene solution of diethylzinc, 120 μmol of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, and 60 μmol of 3,5-di-tert-butylsalicylic acid 2-propanethioaniline titanium trichloride were added in a single step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 1 MPa.

[0138] After reacting for 0.5 h, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 450 mL hydrochloric acid and 3000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with 1000 mL of ethanol and dried (at 60 °C to constant weight) to obtain 30 g of copolymer. The catalyst activity was 1.0 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0139] Example 3:

[0140] This embodiment uses a 2L batch reactor. 30 mol of refined vinyl norbornene was dissolved in 1000 ml of refined xylene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (1 MPa) to saturate the solution. Under conditions of 75°C, 1 MPa, and stirring, 40 ml of a 1 mol / L triisopentylaluminum toluene solution, 2 ml of a 1 mol / L diethylzinc toluene solution, 40 μmol of 1-butyl-3-methylimidazolium tetrafluoroborate, and 40 μmol of salicyl-2-methylthioaniline titanium trichloride were added in a single step. Ethylene was added metered up during the polymerization process, and the pressure was controlled at 1 MPa.

[0141] After reacting for 1 hour, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 600 mL hydrochloric acid and 4000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 48 g of copolymer. The catalyst activity was 1.2 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0142] Example 4:

[0143] This embodiment uses a 1L batch reactor. 16 mol of refined norbornene was dissolved in 500 ml of refined xylene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (1 MPa) to saturate the solution. Under conditions of 70°C, 1 MPa, and stirring, 10 ml of a 1 mol / L tri-n-hexylaluminum toluene solution, 0.4 ml of a 1 mol / L diethylzinc toluene solution, 20 μmol of ferrocene tetrafluoroborate, and 20 μmol of salicylyl-2-phenylthioaniline titanium trichloride were added in one step. Ethylene was added metered during the polymerization process, and the pressure was controlled at 1 MPa.

[0144] After reacting for 15 minutes, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 7 g of copolymer. The catalyst activity was 1.4 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0145] Example 5:

[0146] In a 5L stainless steel batch reactor, 90 mol of refined vinyl norbornene was dissolved in 2500 ml of refined cyclooctane to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The solution was saturated with ethylene by repeatedly pressurizing it (2 MPa). Under conditions of 65°C, 2 MPa, and stirring, 50 ml of a 1 mol / L toluene solution of triisohexylaluminum, 200 μmol of triphenylmethyltetra(pentafluorophenyl)borate, 2 ml of a 1 mol / L diethylzinc toluene solution, and 200 μmol of salicylyl-2-phenylthioaniline titanium trichloride were added in one step. During the polymerization process, ethylene was added in a metered manner, and the pressure was controlled at 2 MPa.

[0147] After reacting for 2 hours, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 750 mL hydrochloric acid and 5 L ethanol) to precipitate. After filtration, the filter cake was washed with ethanol (2 L) and dried (at 60 °C to constant weight) to obtain 600 g of copolymer. The catalyst activity was 1.5 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0148] Example 6:

[0149] This embodiment uses a 1L batch reactor. 21 mol of refined ethylene norbornene was dissolved in 500 ml of a mixed solution of refined toluene and xylene. This solution was added to a reactor that had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (2 MPa) to saturate the solution. Under conditions of 80°C, 2 MPa, and stirring, 20 ml of a 1 mol / L diethylmethylaluminum toluene solution, 60 μmol of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, 0.4 ml of a 1 mol / L diethylzinc toluene solution, and 20 μmol of 3,5-di-tert-butylsalicylic acid 2-propanethioaniline titanium trichloride were added in a single step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 2 MPa.

[0150] After reacting for 0.5 h, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 11 g of copolymer. The catalyst activity was 1.1 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0151] Example 7:

[0152] This embodiment uses a 0.5L batch reactor. 9 mol of refined ethylene norbornene was dissolved in 250 ml of refined toluene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (2 MPa) to saturate the solution. Under conditions of 50°C, 2 MPa, and stirring, 15 ml of a 1 mol / L dimethylethylaluminum toluene solution, 0.2 ml of a 1 mol / L diethylzinc toluene solution, 10 μmol of 1-butyl-3-methylimidazolium tetrafluoroborate, and 10 μmol of 3-tert-butylsalicylic acid-2-propanethioaniline titanium trichloride were added in a single step. Ethylene was added metered up during the polymerization process, and the pressure was controlled at 2 MPa.

[0153] After reacting for 0.5 h, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 14 g of copolymer. The catalyst activity was 2.8 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0154] Example 8:

[0155] This embodiment uses a 0.5L batch reactor. 10 mol of refined vinyl norbornene was dissolved in 300 ml of refined cyclooctane to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (2 MPa) to saturate the solution. Under conditions of 40°C, 2 MPa, and stirring, 40 ml of a 1 mol / L tri-n-propylaluminum toluene solution, 1 ml of a 1 mol / L diethylzinc toluene solution, 20 μmol of ferrocene tetrafluoroborate, and 10 μmol of 3,5-di-tert-butylsalicylic acid 2-mercaptoaniline titanium trichloride were added in a single step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 2 MPa.

[0156] After reacting for 1.5 hours, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 12 g of copolymer. The catalyst activity was 0.8 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0157] Example 9:

[0158] In a 1L stainless steel batch reactor, 13.5 mol of refined norbornene was dissolved in 500 ml of refined toluene and cyclohexane to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The solution was saturated with ethylene by repeated pressurization (1.5 MPa). Under conditions of 55℃, 1.5 MPa, and stirring, 5 ml of a 1 mol / L toluene solution of triisohexylaluminum, 5 μmol of triphenylmethyltetra(pentafluorophenyl)borate, 0.2 ml of a 1 mol / L diethylzinc toluene solution, and 10 μmol of 3-tert-butylsalicyl-2-methylthioaniline titanium trichloride were added in one step. Ethylene was added in a metered manner during the polymerization process, and the pressure was controlled at 1.5 MPa.

[0159] After reacting for 15 minutes, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60°C to constant weight) to obtain 5 g of copolymer. The catalyst activity was 2 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0160] Example 10:

[0161] This embodiment uses a 1L batch reactor. 18 mol of refined vinyl norbornene was dissolved in 500 ml of refined toluene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (3 MPa) to saturate the solution. Under conditions of 95°C, 3 MPa, and stirring, 20 ml of a 1 mol / L toluene solution of triisobutylaluminum, 1 ml of a 1 mol / L toluene solution of diethylzinc, 40 μmol of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, and 20 μmol of 3,5-di-tert-butylsalicylic acid 2-propanethioaniline titanium trichloride were added in a single step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 3 MPa.

[0162] After reacting for 15 minutes, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 300 mL hydrochloric acid and 2000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 15 g of copolymer. The catalyst activity was 3 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0163] Example 11:

[0164] This embodiment uses a 10L batch reactor. 225 mol of refined ethylene norbornene was dissolved in 5L of refined xylene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (3 MPa) to saturate the solution. Under conditions of 40°C, 3 MPa, and stirring, 200 ml of a 1 mol / L toluene solution of triisobutylaluminum, 10 ml of a 1 mol / L toluene solution of diethylzinc, 800 μmol of 1-butyl-3-methylimidazolium tetrafluoroborate, and 200 μmol of 3,5-di-tert-butylsalicylic acid-2-propanethioaniline titanium trichloride were added in a single step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 3 MPa.

[0165] After reacting for 1 hour, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 1.5 L hydrochloric acid and 10 L ethanol) to precipitate. The precipitate was then filtered, and the filter cake was washed with ethanol (3 L) and dried (at 60 °C to constant weight) to obtain 52 g of copolymer. The catalyst activity was 0.26 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0166] Example 12:

[0167] This embodiment uses a 2.5L batch reactor. 54 mol of refined norbornene was dissolved in 1.5L of refined cyclohexane to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (3 MPa) to saturate the solution. Under conditions of 85°C, 1 MPa, and stirring, 80 ml of a 1 mol / L triisopentylaluminum toluene solution, 0.8 ml of a 1 mol / L diethylzinc toluene solution, 160 μmol of ferrocene tetrafluoroborate, and 50 μmol of 3,5-di-tert-butylsalicylic acid 2-mercaptoaniline titanium trichloride were added in a single step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 3 MPa.

[0168] After reacting for 1 hour, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 3000 mL hydrochloric acid and 20 L ethanol) to precipitate. After filtration, the filter cake was washed with ethanol (3 L) and dried (at 60 °C to constant weight) to obtain 200 g of copolymer. The catalyst activity was 4 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0169] Comparative Example 1:

[0170] This embodiment uses a 1L batch reactor. 16 mol of refined norbornene was dissolved in 500 ml of refined xylene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (1 MPa) to saturate the solution. Under conditions of 70°C, 1 MPa, and stirring, 0.4 ml of a 1 mol / L diethylzinc toluene solution, 20 ml of a 1.5 mol / L modified methylaluminoxane toluene solution, and 20 μmol of salicylyl-2-phenylthioaniline titanium trichloride were added in one step. Ethylene was added metered during the polymerization process, and the pressure was controlled at 1 MPa.

[0171] After reacting for 15 minutes, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 8 g of copolymer. The catalyst activity was 1.6 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0172] Comparative Example 2:

[0173] In a 5L stainless steel batch reactor, 90 mol of refined vinyl norbornene was dissolved in 2500 ml of refined cyclooctane to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The solution was saturated with ethylene by repeatedly pressurizing it (2 MPa). Under conditions of 65°C, 2 MPa, and stirring, 30 ml of a 1.9 mol / L toluene solution of methylaluminoxane, 2 ml of a 1 mol / L diethylzinc toluene solution, and 200 μmol of salicylyl-2-phenylthioaniline titanium trichloride were added in one step. During the polymerization process, ethylene was added in a metered manner, and the pressure was controlled at 2 MPa.

[0174] After 2 hours of reaction, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 750 mL hydrochloric acid and 5 L ethanol) to precipitate. The precipitate was then filtered, and the filter cake was washed with ethanol (2 L) and dried (at 60 °C to constant weight) to obtain 675 g of copolymer. The catalyst activity was 1.7 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0175] Comparative Example 3:

[0176] This embodiment uses a 1L batch reactor. 21 mol of refined ethylene norbornene was dissolved in 500 ml of a mixed solution of refined toluene and xylene. This solution was added to a reactor that had been pre-purged with nitrogen. The reactor was repeatedly pressurized with ethylene (2 MPa) to saturate the solution. Under conditions of 80°C, 2 MPa, and stirring, 20 ml of a 1.9 mol / L toluene solution of methylaluminoxane, 0.4 ml of a 1 mol / L diethylzinc toluene solution, and 20 μmol of 3,5-di-tert-butylsalicylic acid-2-propanethioaniline titanium trichloride were added in one step. Ethylene was added metered in during the polymerization process, and the pressure was controlled at 2 MPa.

[0177] After reacting for 0.5 h, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 150 mL hydrochloric acid and 1000 mL ethanol) to precipitate the copolymer. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 10 g of copolymer. The catalyst activity was 1.0 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0178] Comparative Example 4:

[0179] In a 1L stainless steel batch reactor, 15.6 mol of refined norbornene was dissolved in 200 ml of refined toluene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The solution was saturated with ethylene by repeated pressurization (1 MPa). Under conditions of 90°C, 1 MPa, and stirring, 10 ml of a 1.9 mol / L toluene solution of methylaluminoxane and 10 μmol of 3-tert-butylsalicylene-2-methylthioaniline titanium trichloride were added at one time. During the polymerization process, ethylene was added in a metered manner, and the pressure was controlled at 1 MPa.

[0180] After reacting for 15 min, the reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 300 mL hydrochloric acid and 2000 mL ethanol) to precipitate. The precipitate was then filtered, and the filter cake was washed with 1000 mL of ethanol and dried (at 60°C to constant weight) to obtain 6 g of copolymer. The catalyst activity was 1.2 × 10⁻⁶. 6 g / (molM·h). The properties of the copolymer are shown in Table 1.

[0181] Comparative Example 5

[0182] In a 250 ml glass reactor, 0.013 mol of refined norbornene was dissolved in 50 ml of refined toluene to prepare a solution. This solution was added to the reactor, which had been pre-purged with nitrogen. The solution was saturated with ethylene (0.1 MPa) by repeated pressurization. Under conditions of 70 °C, 0.1 MPa, and stirring, 1.03 ml of a 1.94 mol / L modified methylaluminoxane (MMAO) solution in methylcyclohexane and 2 μmol of rac-vinylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride were added sequentially, with the pressure controlled at 0.1 MPa.

[0183] After reacting for 0.5 h, the reaction was stopped. The reaction solution was poured into ethanol containing 15% (v / v%) hydrochloric acid (composed of 15 mL hydrochloric acid and 100 mL ethanol) to precipitate. The precipitate was then filtered, and the filter cake was washed with ethanol (300 mL) and dried (at 60 °C to constant weight) to obtain 5.37 g of copolymer. The catalyst activity was 5.37 × 10⁻⁶. 6 g / (mol·h). The properties of the copolymer are shown in Table 1.

[0184] Table 1 Catalyst activity and copolymer properties

[0185]

[0186] The embodiments of the present invention demonstrate that, without the use of aluminoxane-based cocatalysts, α-olefin-cycloolefin copolymers can be prepared cost-effectively and efficiently using a non-metallocene catalytic system comprising alkylaluminum derivatives and organoboron compounds as cocatalysts. The copolymerization activity is comparable to or even superior to that using aluminoxane-based cocatalysts, and the properties of the resulting copolymers are also comparable to or even superior. In particular, the non-metallocene catalytic system of the present invention exhibits superior activity and the properties of the resulting copolymers are also superior compared to that using metallocene catalytic systems.

[0187] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A method for preparing an α-olefin-cycloolefin copolymer, comprising the following steps: In the presence of non-metallocene complexes and co-catalysts, α-olefins and cycloolefins can be copolymerized. The cocatalyst is a mixture of an organoboron compound and at least one alkylaluminum derivative selected from alkylaluminum, alkylaluminum hydrolysates, and haloalkylaluminum. The non-metallocene complex is selected from at least one of the following: 3-tert-butylsalicylene-2-methylthioaniline titanium trichloride, salicylene-2-methylthioaniline titanium trichloride, salicylene-2-phenylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-mercaptoaniline titanium trichloride, salicylene-2-mercaptoaniline titanium trichloride, salicylene-2-methylthioaniline titanium trichloride, salicylene-2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-methylthioaniline titanium trichloride, 3,5-di-tert-butylsalicylene-2-methylthioaniline titanium trichloride, and 3,5-di-tert-butylsalicylene-2-propylthioaniline titanium trichloride. The organoboron compound is selected from trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, tris(pentafluorophenyl)boron, tri[3,5-bis(trifluoromethyl)phenyl]boron, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, and triethylammonium tetra(o,p-dimethylphenyl)borate. At least one of the following: borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetraphenylborate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetra(pentafluorophenyl)borate, diethylammonium tetra(pentafluorophenyl)borate, triphenylmethyltetra(pentafluorophenyl)borate, 1-butyl-3-methylimidazolium tetrafluoroborate, and ferrocene tetrafluoroborate. The cyclic olefin is selected from at least one of norbornene, ethylidene norbornene, vinyl norbornene, norbornediene, 5-methyl norbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadene, pentacyclohexadecene, and 8-ethyltetracyclododecene.

2. The preparation method according to claim 1, wherein, The alkylaluminum is a compound represented by formula (D); the haloalkylaluminum is a compound represented by formula (E); Al(R 11 3 (D) Al(R 11 ) n X 3-n (AND) In formulas (D) and (E), the group R 11 Whether they are the same or different, each is independently selected from C. 1-8 alkyl; In equation (E), X is a halogen and n is an integer of 1 or 2.

3. The preparation method according to claim 2, wherein, In formulas (D) and (E), the group R 11 They may be the same as or different from each other, and are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.

4. The preparation method according to claim 1, wherein, The molar ratio of the cyclic olefin to the nonmetallocene complex (calculated as metal element M) in the reaction system is 10. 5 ~10 7 :1; the molar ratio of the alkylaluminum derivative (calculated as Al) to the non-metallocene complex (calculated as metal element M) is 50 to 5000:1; the molar ratio of the organoboron compound (calculated as B) to the non-metallocene complex (calculated as metal element M) is 0.1 to 20:

1.

5. The preparation method according to claim 1, wherein, During the copolymerization reaction, a chain transfer agent is further added; the chain transfer agent is selected from one or more of n-butyllithium, diethylzinc, dipropylzinc, dibutylzinc, diisobutylzinc, diethylmagnesium, dibutylmagnesium, and n-butylethylmagnesium; the molar ratio of the chain transfer agent (calculated as metal element) to the non-metallocene complex (calculated as metal element M) is 5 to 500:

1.

6. The preparation method according to claim 5, wherein, The concentration of the non-metallocene complex, calculated as metal element M, in the reaction solution is 0.1 × 10⁻⁶. -5 mol / L~50×10 -5 mol / L; the concentration of the cycloalkene in the reaction solution is 1–100 mol / L; the concentration of the organoboron compound in the solution, calculated as B, is 1 × 10⁻⁶ mol / L. -6 mol / L~100×10 -5 mol / L; the concentration of the alkylaluminum derivative, calculated as Al, in the solution during the reaction is 1 × 10⁻⁶ mol / L. -3 mol / L~200×10 -3 mol / L; the concentration of the chain transfer agent in the solution during the reaction, calculated as metal element, is 0–500 × 10⁻⁶ mol / L. -5 mol / L.

7. The preparation method according to claim 1, wherein, The reaction pressure, measured by a total pressure gauge, is 0.1-5.0 MPa; the reaction temperature is 40-100℃.

8. The preparation method according to claim 1, further comprising the step of precipitating the copolymer in acidified ethanol.

9. The preparation method according to any one of claims 1-8, wherein it satisfies at least one of the following conditions: The molar ratio of the cyclic olefin to the nonmetallocene complex (calculated as metal element M) in the reaction system is 7 × 10⁻⁶. 5 ~2×10 6 :1; The molar ratio of the alkylaluminum derivative (calculated as Al) to the non-metallocene complex (calculated as metal element M) is 500–2000:1; The molar ratio of the organoboron compound (calculated as B) to the non-metallocene complex (calculated as metal element M) is 0.8–5:1; During the copolymerization reaction, a chain transfer agent is further added; the chain transfer agent is selected from one or more of n-butyllithium, diethylzinc, dipropylzinc, dibutylzinc, diisobutylzinc, diethylmagnesium, dibutylmagnesium and n-butylethylmagnesium; the molar ratio of the chain transfer agent (calculated as metal element) to the nonmetallocene complex (calculated as metal element M) is 10 to 50:1; The concentration of the non-metallocene complex, calculated as metal element M, in the reaction solution is 1 × 10⁻⁶. -5 mol / L~10×10 -5 mol / L; the concentration of the cycloalkene in the reaction solution is 10–50 mol / L; the concentration of the organoboron compound in the solution, calculated as B, is 5 × 10⁻⁶ mol / L. -6 mol / L~50×10 -5 mol / L; the concentration of the alkylaluminum derivative, calculated as Al, in the solution during the reaction is 10 × 10⁻⁶ mol / L. -3 mol / L~150×10 -3 mol / L; the concentration of the chain transfer agent in the solution during the reaction, calculated as metal element, is 10 × 10⁻⁶. -5 mol / L~300×10 -5 mol / L; The reaction pressure, measured by a total pressure gauge, is 0.1-2.0 MPa; the reaction temperature is 70-90℃.

10. An α-olefin-cycloolefin copolymer, obtained by any one of claims 1-9.

11. A polymer composition comprising at least the α-olefin-cycloolefin copolymer of claim 10 and optional additives.

12. Use of the α-olefin-cycloolefin copolymer of claim 10 or the polymer composition of claim 11 in the manufacture of optical components, packaging materials, electronic components, and medical devices.

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