CN114907509A - Alpha-olefin-cycloolefin copolymer and preparation method and application thereof - Google Patents

Alpha-olefin-cycloolefin copolymer and preparation method and application thereof Download PDF

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CN114907509A
CN114907509A CN202110176242.6A CN202110176242A CN114907509A CN 114907509 A CN114907509 A CN 114907509A CN 202110176242 A CN202110176242 A CN 202110176242A CN 114907509 A CN114907509 A CN 114907509A
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olefin
hydrogen
straight
alkyl
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汪文睿
郭峰
卞政
邢跃军
李传峰
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention provides a method for preparing alpha-olefin-cycloolefin copolymer by adopting non-metallocene complex and cocatalyst, alpha-olefin-cycloolefin copolymer with high Tg prepared by the method and application of the alpha-olefin-cycloolefin copolymer. The preparation method of the invention can prepare the alpha-olefin-cycloolefin copolymer with low cost and high efficiency under the condition of not using the aluminoxane cocatalyst. In addition, the α -olefin-cycloolefin copolymer according to the present invention has a high content of cycloolefin unit, so that the copolymer has excellent transparency and a high glass transition temperature, and is widely used in industry. The higher the cycloolefin content, the higher the Tg of the copolymer. COC copolymers with high glass transition temperatures have high product purity, transparency and high heat distortion temperatures, and are used in healthcare-related applications where cleanliness and high temperature sterilization procedures are required, and in optical data storage such as CD and CD-ROM where low birefringence and high molding repeatability are important requirements.

Description

Alpha-olefin-cycloolefin copolymer and preparation method and application thereof
Technical Field
The invention provides an alpha-olefin-cycloolefin copolymer and a preparation method and application thereof, and more particularly provides a method for preparing the alpha-olefin-cycloolefin copolymer by adopting a non-metallocene complex and a cocatalyst, the alpha-olefin-cycloolefin copolymer prepared by the method and having high Tg, and application thereof.
Background
Cyclic Olefin Copolymers (COC) are high value-added thermoplastic engineering plastics prepared by addition copolymerization of Cyclic olefins, and are concerned by the characteristics of high transparency, high glass transition temperature (Tg), high chemical resistance and the like. Wherein the glass transition temperature is controlled by the proportion of the comonomers, the higher the content of cycloolefin units and the higher the Tg of the copolymer. COC copolymers with high glass transition temperatures have high product purity, transparency and high heat distortion temperatures, and are used in applications in the healthcare field where cleaning and high temperature sterilization procedures are required, and in optical data storage such as CD and CD-ROM where low birefringence and high molding repeatability are important requirements.
The early cycloolefin copolymerization used a Ziegler-Natta catalyst, but the Ziegler-Natta catalyst has multiple active sites, low polymerization activity, and poor resistance to polar groups, which limits its application. With the advent of metallocene catalysts with higher polymerization activities, research on them has become active. Chinese patent application CN101125901A discloses a method for preparing cycloolefin copolymer with narrow composition distribution by using metallocene catalyst; chinese patent CN102702433B discloses a method for preparing high molecular weight copolymer of ethylene and norbornene by using half metallocene catalyst; chinese patent CN102286126A provides a method for preparing a high transparent cyclic olefin copolymer with low cyclic olefin content by using metallocene catalyst; chinese patent CN101613437B discloses a method for preparing cyclic olefin copolymer with polar group by using metallocene catalyst. Compared with the conventional Ziegler-Natta catalyst, the metallocene catalyst can control the molecular weight, tacticity, and comonomer reactivity of the copolymer according to the structures of the catalyst and the ligand.
In recent years, non-metallocene single site catalysts have received widespread attention because they have different performance from metallocene catalysts and are easy to synthesize. Compared with metallocene compounds, non-metallocene compounds can provide an active center with stronger electrophilicity and a more open coordination space, so that the non-metallocene compounds can have higher insertion efficiency of cycloolefin monomers, can catalyze the copolymerization of norbornenes with high monomer ratio, have different space structures of copolymers, and reflect certain changes in the performance of products. Chinese patent application CN1887925A discloses a non-metallocene catalyst, which can catalyze the copolymerization of ethylene and cyclic olefins such as cyclopentadiene and norbornene under the action of low amount of cocatalyst, and the ethylene-cyclic olefin copolymer obtained by the non-metallocene catalyst has higher strength and modulus compared with the ethylene-cyclic olefin copolymer prepared by general metallocene catalysis, which greatly expands the application range of the copolymer, for example, for the occasion with special requirements on the erection property and stiffness of the packaging material. However, the non-metallocene catalyst has relatively low polymerization activity compared to the conventional metallocene-catalyzed ethylene-cycloolefin copolymerization, and requires solution polymerization using alkylaluminoxane as a cocatalyst. On the other hand, the use of a large amount of expensive cocatalyst MAO (methylaluminoxane), MMAO (modified methylaluminoxane) or dMAO (dried methylaluminoxane) greatly increases the production cost, and greatly increases the metal content in the polymer, which is not favorable for the industrial application.
Therefore, the prior art has the following technical problems: it is difficult to prepare an ethylene-cycloolefin copolymer exhibiting excellent properties at a low cost with a catalyst having a high polymerization activity industrially advantageously.
Disclosure of Invention
The present inventors have intensively studied in view of the above-mentioned technical problems, and as a result, have found that an α -olefin-cycloolefin copolymer can be produced with high polymerization activity by using a catalyst system formed of a non-metallocene catalyst of a specific structure and an aluminum alkyl and a boron compound, even without using an aluminoxane-based cocatalyst which is necessary in the prior art and has a high price. In addition, the prepared alpha-olefin-cycloolefin copolymer has the characteristics of high Tg and high transparency, and shows excellent application prospects.
Without being bound by any theory, the present inventors speculate that the single-site catalytic system formed by the organic boride and the alkyl aluminum as the cocatalyst and the non-metallocene complex can replace the alkyl aluminoxane, thereby not only not reducing the polymerization activity of the catalyst system, but also greatly reducing the production cost. In addition, the molecular weight of the polymerization product can be adjusted by adding a proper amount of chain transfer agent, and gel products formed in the polymerization at a high cycloolefin concentration are avoided.
The α -olefin-cycloolefin copolymer prepared by the method of the present invention exhibits a high glass transition temperature (Tg) and high transparency, and is more widely used in the industry. In addition, in the method of the present invention, alkane or the like can be used as a solution polymerization solvent, and polymerization conditions are mild, and copolymerization activity is high, which significantly reduces the production cost of the method of the present invention. Thereby solving the technical problems existing in the prior art.
Specifically, the present invention provides a method for preparing an α -olefin-cycloolefin copolymer, comprising the steps of: copolymerizing an alpha-olefin and a cyclic olefin in the presence of a non-metallocene complex and a cocatalyst.
Further, the present invention provides an α -olefin-cycloolefin copolymer produced by the method for producing an α -olefin-cycloolefin copolymer according to the present invention.
Further, the present invention provides a polymer composition comprising at least the α -olefin-cycloolefin copolymer according to the present invention.
The present invention also provides the use of the α -olefin-cycloolefin copolymer according to the invention or the polymer composition according to the invention for producing optical parts, packaging materials, electronic parts, and medical devices.
Technical effects
The method for producing an alpha-olefin-cycloolefin copolymer according to the present invention can produce an alpha-olefin-cycloolefin copolymer at low cost and with high efficiency without using an aluminoxane cocatalyst. In addition, in the preparation method of the invention, the molecular weight can be conveniently controlled by controlling the proportion of the alkyl aluminum, so that the morphology of the copolymer can be adjusted. In addition, the preparation method of the alpha-olefin-cycloolefin copolymer can be carried out in an inert organic solvent, the phenomenon of implosion can not occur in polymerization, the polymerization condition is mild, and the requirement on production equipment is reduced.
In addition, the alpha-olefin-cycloolefin copolymer of the present invention has a high cycloolefin unit content, and the copolymer has excellent transparency and a high glass transition temperature, and thus has a wide industrial application range.
Drawings
FIG. 1 is a typical nuclear magnetic resonance spectrum of COC used to illustrate the calculation of cycloolefin content in an α -olefin-cycloolefin copolymer.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
In the context of the present invention, unless otherwise explicitly defined, or the meaning is beyond the understanding of those skilled in the art, a hydrocarbon or hydrocarbon derivative group of 3 or more carbon atoms (e.g., propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) has the same meaning when not headed "plus" as when headed "plus". For example, propyl is generally understood to be n-propyl, and butyl is generally understood to be n-butyl, unless otherwise specified.
In addition, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless the combination is considered obvious and unreasonable by one skilled in the art.
Furthermore, the endpoints of the sets of numerical ranges describing the same physical property can be combined arbitrarily in the present invention, and one of ordinary skill in the art can confirm that such combination is part of the original disclosure or original description of the present invention and should not be considered as a novel matter not disclosed or contemplated herein.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
The method for preparing the alpha-olefin-cycloolefin copolymer according to the present invention comprises the steps of: alpha-olefins and cyclic olefins are copolymerized in the presence of a non-metallocene complex and a cocatalyst. Thus, an α -olefin-cycloolefin copolymer was prepared.
In the present invention, the α -olefin is an olefin represented by the following formula (a).
R-CH=CH 2 　　　　　(a)
Wherein R represents H or C 1-8 Straight or branched alkyl, preferably H or C 1-4 Straight or branched chain alkyl, more preferably H, methyl or ethyl.
In one embodiment of the present invention, the alpha-olefin may be C 2-10 Linear or branched olefins, preferably C 2-6 Straight or branched chain olefins, more preferably C 2-3 The alkene is more preferably ethylene or propylene.
In one embodiment of the present invention, these α -olefins may be used alone, or two or more kinds may be used in combination.
In the present invention, the cycloolefin means an olefin which is monocyclic or polycyclic and has a double bond in the ring.
In one embodiment of the present invention, the cycloolefin specifically includes C 3-20 A cycloolefin. As said C 3-20 Specific examples of the cycloolefin include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctatetraene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadiene, pentacyclohexadecene, and 8-ethyltetracyclododecene, and dicyclopentadiene, norbornene, norbornadiene, and the like,
Figure 794371DEST_PATH_IMAGE001
、
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、
Figure 452065DEST_PATH_IMAGE003
And
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and spirocyclic, bridged or fused bicyclic or polycyclic cycloalkenes. As said C 3-20 Cycloolefins, preferably cyclopentene, cyclopentadiene, norbornadiene, dicyclopentadiene, norbornene, vinylnorbornene and ethylidenenorbornene or tetracyclododecene.
In one embodiment of the present invention, C 3-20 The cycloalkene is optionally further substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1) C 1-10 The linear or branched hydrocarbon group is substituted at a suitable position. As said C 1-10 Straight or branched chain hydrocarbon radicals, preferably C 1-10 Straight or branched alkyl or C 2-10 Straight or branched alkenyl, more preferably C 1-4 Straight or branched alkyl or C 2-4 Straight or branched alkenyl groups, of which methyl, ethyl, vinyl or ethylidene groups are more preferred.
In one embodiment of the present invention, C is 3-20 Examples of the cycloolefin further include a compound represented by the following formula (Y).
Figure 633965DEST_PATH_IMAGE005
　　　　　(Y)。
In formula (Y), the groups Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh may be the same or different and are each independently selected from hydrogen and C 1-10 Straight or branched chain hydrocarbon groups. As said C 1-10 Straight or branched chain hydrocarbon radicals, preferably selected from C 1-10 Straight or branched alkyl or C 2-10 Straight or branched alkenyl, more preferably C 1-4 Straight or branched alkyl or C 2-4 Straight-chain or branched alkenyl.
In one embodiment of the present invention, in formula (Y), the groups Ra to Rh may be the same or different and are each independently selected from hydrogen, C 1-4 Straight or branched alkyl and C 2-4 Straight or branched alkenyl radicals such as C 2-3 Straight or branched alkenyl, wherein preferably each is independently selected from hydrogen, methyl, ethyl, vinyl or ethylidene.
In one embodiment of the present invention, in formula (Y), n is an integer of 0 to 6, preferably 0 or 1.
In one embodiment of the present invention, in the formula (Y), the symbols
Figure 97308DEST_PATH_IMAGE006
Represents a single bond or a double bond.
In one embodiment of the present invention, the compound represented by the formula (Y) is preferably norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, or 5-methylnorbornene, and more preferably norbornene, ethylidene norbornene, or vinyl norbornene.
In one embodiment of the present invention, the cyclic olefins may be used alone or in combination of two or more.
In the invention, the non-metallocene complex is a compound selected from compounds shown in the following formula (I).
Figure 379384DEST_PATH_IMAGE007
　　　　　(I)。
In one embodiment of the present invention, in formula (I)Radical R 1 、R 2 、R 3 、R 4 May be the same or different and are each independently selected from hydrogen and C 1-6 A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C 1-6 Straight or branched chain alkyl, more preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl. In one embodiment of the invention, R 1 、R 3 Represents hydrogen. In one embodiment of the invention, R 2 、R 4 Each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl and tert-butyl, preferably each independently selected from hydrogen and tert-butyl.
In one embodiment of the invention, in formula (I), the radical R 6 、R 7 、R 8 、R 9 May be the same or different and are each independently selected from hydrogen and C 1-6 A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C 1-6 Straight or branched chain alkyl, more preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl. In one embodiment of the invention, R 7 、R 9 Represents hydrogen. In one embodiment of the invention, R 6 、R 8 Each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, preferably each independently selected from hydrogen and tert-butyl.
In one embodiment of the invention, in formula (I), the radical R 5 Represents hydrogen or C 1-12 Straight or branched chain hydrocarbon radicals, preferably hydrogen, C 1-6 Straight or branched alkyl or C 6-10 Aryl, more preferably hydrogen, C 1-3 Straight or branched chain alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl or isopropyl.
In one embodiment of the present invention, in formula (I), R 10 Represents hydrogen or C 1-6 Straight or branched hydrocarbon radicals, preferably hydrogen or C 1-6 Straight-chain or branched alkyl, more preferably hydrogen, methyl and ethyl, more preferably hydrogen.
In one embodiment of the inventionIn the mode of
Figure 142941DEST_PATH_IMAGE006
Represents a single bond or a double bond, and when a double bond is represented, H on N is not present, and when a single bond is represented, H on N is present.
In one embodiment of the invention, in formula (I), the group Y is O or S, preferably O.
In one embodiment of the invention, in formula (I), the group A is S or O, preferably S.
In one embodiment of the invention, in formula (I), the group M is selected from the group consisting of metal elements of groups III to VI of the periodic Table of the elements, preferably group IVB metal elements such as titanium, zirconium and hafnium, more preferably titanium.
In one embodiment of the invention, in formula (I), the group X is halogen, including fluorine, chlorine, bromine and iodine, with chlorine or bromine being preferred.
In one embodiment of the present invention, in formula (I), the symbol represents a coordinate bond.
In one embodiment of the present invention, n is 1,2, 3, 4 or 5, preferably n is 2, 3 or 4, depending on the valence of the central metal atom M.
In one embodiment of the present invention, the non-metallocene complex represented by the formula (I) is selected from the group consisting of 3-tert-butylsalicylidene-2-methylthioaniline titanium trichloride, salicyl 2-phenylthioaniline titanium trichloride, 3, 5-di-tert-butylsalicylidene-2-propylthioaniline titanium trichloride, 3, 5-di-tert-butylsalicylidene-2-mercaptoaniline titanium trichloride, salicylidene-2-methylthioaniline titanium trichloride, salicylidene-2-propylthioaniline titanium trichloride, 3, 5-di-tert-butylsalicylidene-2-methylthioaniline titanium trichloride, titanium trichloride, 3, 5-di-tert-butyl salicyl 2-propylsulfanylaniline titanium trichloride.
In one embodiment of the present invention, the non-metallocene complex represented by the formula (I) may be used singly or in combination of two or more in any ratio.
In the present invention, the non-metallocene complex represented by formula (I) can be synthesized by a method known in the art, or can be obtained by a commercially available route.
In one embodiment of the present invention, the compound represented by the formula (I) can be produced, for example, by the following production method.
The production method includes, for example, a step of obtaining a compound represented by the formula (I) by subjecting a compound represented by the formula (I-A) to a coordination reaction with a compound represented by the formula (X) (hereinafter referred to as coordination step A).
Figure 85227DEST_PATH_IMAGE009
　　　　　(I-A)
MX 4 　　　　　(X)。
In the present invention, the definitions and preferred embodiments of the respective groups in the formula (I-A) are the same as those in the above-mentioned formula (I) of the present invention. In the formula (I-A), when
Figure 770286DEST_PATH_IMAGE010
When represents a single bond, p represents 2, and H on N is present when
Figure 183950DEST_PATH_IMAGE010
When a double bond is represented, p represents 1, and H on N is absent.
In the present invention, in the formula (X), the group M is selected from metal elements of groups III to VI of the periodic Table of the elements, preferably group IVB metal elements such as titanium, zirconium and hafnium, with titanium being more preferred.
According to the invention, in formula (X), the group X is halogen, including fluorine, chlorine, bromine and iodine, with chlorine or bromine being preferred.
According to the invention, the molar ratio of the compound of formula (X) to the compound of formula (I-A) when carrying out the complexing step A is generally from 0.7 to 1.5:1, preferably from 0.9 to 1.3:1, more preferably from 1 to 1.2: 1.
According to the invention, the complexing step A may be carried out in a solventIn the presence of (a). The solvent is not particularly limited in the present invention as long as it can dissolve the compound represented by the formula (X) and the compound represented by the formula (I-A) without interfering with the coordination reaction. Specifically, the solvent includes, for example, C 5-20 Alkane, C 6-20 Aromatic hydrocarbons and C 4-20 Alicyclic hydrocarbons, etc., among which C is preferred 6-12 Aromatic hydrocarbons, most preferably toluene, xylene, trimethylbenzene. These solvents may be used singly or in combination in any ratio.
According to the present invention, the amount of the solvent is not particularly limited, and any amount may be used as long as it is favorable for the coordination reaction, and for example, the molar ratio of the solvent to the compound represented by the formula (I-A) is 5 to 200, preferably 10 to 100, but not limited thereto.
According to the invention, the reaction temperature of the complexing step A is generally from-80 to 100 ℃, preferably from-50 to 70 ℃ and more preferably from-30 to 50 ℃.
According to the present invention, the reaction pressure of the coordination step A may be any pressure suitable for the coordination reaction to proceed, but is generally from atmospheric pressure to 0.2MPa for convenience of implementation.
According to the invention, the reaction time of the complexing step A is generally between 0.1 and 72 hours, preferably between 0.2 and 48 hours, more preferably between 1 and 24 hours.
According to the present invention, the coordination reaction of the coordination step A can be performed under stirring (e.g., stirring at a rotation speed of 100-1000rpm) in order to promote the reaction, if necessary.
According to the present invention, the coordination reaction in the coordination step a may be performed in a protective gas atmosphere, if necessary. Examples of the protective gas include inert gases such as nitrogen.
According to the invention, after the coordination reaction in the coordination step A is finished, the compound shown in the formula (I) can be separated from the mixture obtained in the reaction as a reaction product by a conventional separation mode. Examples of the separation method include filtration, or filtration followed by washing, and optionally further drying. Alternatively, the obtained reaction product may be purified by recrystallization, column chromatography, preparative chromatography or the like, as required.
According to the present invention, the method of the filtration, washing and drying is not particularly limited, and those conventionally used in the art may be used as needed. The washing is generally carried out 1 to 6 times, preferably 2 to 3 times, as required. Among them, the washing solvent is preferably the same as the solvent used in the coordination reaction, but may be different. Examples of the drying include an inert gas drying method, a vacuum drying method, and a vacuum heat drying method, among which the inert gas drying method or the vacuum heat drying method is preferable, and the vacuum heat drying method is most preferable. In this case, the drying temperature is generally in the range of normal temperature to 140 ℃ and the drying time is generally 2 to 20 hours, but is not limited thereto.
In the present invention, the cocatalyst is a mixed system of an organoboron compound and at least one alkyl aluminum derivative selected from the group consisting of alkyl aluminum, alkyl aluminum hydrolysates, and halogenated alkyl aluminum.
In one embodiment of the invention, no aluminoxane based co-catalyst is used in the preparation process.
In one embodiment of the present invention, the organoboron compound is at least one selected from the group consisting of an alkylboron, an arylboron and a borate.
In the present invention, the alkyl boron and aryl boron may be compounds having the following general formula (B-1):
B(R) 3 　　　　　(B-1)
wherein each of the three R groups may be the same or different from each other, and each R is independently selected from C 1-6 Straight or branched alkyl and C 6-12 Aryl, each group being optionally substituted by one or more halogen atoms, halogeno C 1-6 Linear or branched alkyl or phenoxy substitution. Said R is preferably selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, phenyl, tolyl, trifluoromethylphenyl and pentafluorophenyl. Specific examples of the alkylboron include trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron.Specific examples of the arylboron include tris (pentafluorophenyl) boron, tris [3, 5-bis (trifluoromethyl) phenyl group]And boron.
In the present invention, the borate may be a compound having the following general formula (B-2):
[L] + [BE 4 ] m - 　　　　　(B-2)
wherein L is a cationic group, each E, which may be the same or different, is independently selected from a halogen atom, C 6-12 Aryl, said aryl being optionally substituted by one or more halogen atoms, C 1-6 Straight or branched alkyl, halo C 1-6 Straight or branched alkyl, C 1-6 Linear or branched alkoxy or phenoxy. Said E is preferably selected from the group consisting of fluoro, phenyl, trifluoromethylphenyl and pentafluorophenyl. m represents the number of valences of the group of the moiety L.
[L] + The moiety may be a cation commonly found in borates, and for example, Li may be mentioned + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、[Fe(C 5 H 5 ) 2 ] + (ferrocenyl) and the like. In addition, the L moiety may be an organic amine, in which case the L moiety may be N (R') 3 Each R' is independently selected from H, C 1-6 Straight or branched alkyl and C 6-12 Aryl, but not both H; or two R' and N may be bonded to each other to form optionally C 1-6 A straight or branched alkyl substituted 5-to 7-membered nitrogen containing heterocycle, preferably each R' is independently selected from H, C 1-4 Straight or branched chain alkyl and phenyl, but not both are H; or two R' and N may be bonded to each other to form optionally substituted C 1-4 A linear or branched alkyl substituted 5-7 membered nitrogen containing heteroaromatic ring or heterocyclic hydrocarbon. Examples thereof include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, N-dimethylaniline, N-diethylaniline, imidazole, 1-butyl-3-methylimidazole, pyridine, and piperidine. [ L ]] + The moiety may also be a carbocation-bearing group, such as a trityl carbocation.
Specific examples of the borate include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetraphenylborate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, trityltetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (pentafluorophenyl) borate, and the like, 1-butyl-3-methylimidazolium tetrafluoroborate, ferrocene tetrafluoroborate.
In the present invention, examples of the aluminum alkyl include compounds represented by the following formula (D):
Al(R 11 ) 3 　　　　　(D)
in the formula (D), the group R 11 Are the same or different from each other and are each independently selected from C 1-8 Alkyl, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
In one embodiment of the present invention, as the aluminum alkyl, trimethylaluminum (Al (CH) is preferable 3 ) 3 ) Triethylaluminum (Al (CH) 2 CH 3 ) 3 ) Tri-n-propylaluminum (Al (C) 3 H 7 ) 3 ) Triisobutylaluminum (Al (i-C) 4 H 9 ) 3 ) Tri-n-butylaluminum (Al (C) 4 H 9 ) 3 ) Triisopentylaluminum (Al (i-C) 5 H 11 ) 3 ) Tri-n-pentylaluminum (Al (C) 5 H 11 ) 3 ) Tri-n-hexylaluminum (Al (C) 6 H 13 ) 3 ) Triisohexylaluminum (Al (i-C) 6 H 13 ) 3 ) Diethyl methyl aluminum (Al (CH) 3 )(CH 3 CH 2 ) 2 ) And dimethylethylaluminum (Al (CH) 3 CH 2 )(CH 3 ) 2 ) Etc., more preferably trimethylaluminumTriethylaluminum, tri-n-propylaluminum and triisobutylaluminum, with triethylaluminum and triisobutylaluminum being further preferred, and triisobutylaluminum being most preferred.
In one embodiment of the present invention, these alkyl aluminum may be used singly or in combination of plural kinds in an arbitrary ratio.
In the present invention, examples of the aluminum alkyl hydrolysate include hydrolysates obtained by reacting the aluminum alkyl with water. In this reaction, the molar ratio of the aluminum alkyl to water is generally from 0.5 to 4:1, preferably from 1 to 3: 1.
In one embodiment of the present invention, these alkyl aluminum hydrolysates may be used singly or in combination of a plurality thereof in an arbitrary ratio.
In the present invention, examples of the halogenated alkylaluminum include compounds represented by the following formula (E):
Al(R 11 ) n X 3-n 　　　　　(E)
in the formula (E), the group R 11 Are the same or different from each other and are each independently selected from C 1-8 Alkyl, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl, most preferably methyl or ethyl; the radical X is halogen, for example fluorine, chlorine, bromine, iodine, preferably chlorine. n is an integer of 1 or 2.
In one embodiment of the present invention, the halogenated alkylaluminum may specifically include, for example, dimethylaluminum monochloride (Al (CH) 3 ) 2 Cl), dichloromethylaluminum (Al (CH) 3 )Cl 2 ) Aluminum diethyl monochloride (Al (CH)) 3 CH 2 ) 2 Cl), ethyl aluminum dichloride (Al (CH) 3 CH 2 )Cl 2 ) Aluminum monochlorodipropylate (Al (C) 3 H 7 ) 2 Cl), dichloropropylaluminum (Al (C) 3 H 7 )Cl 2 ) Aluminum di-n-butyl monochloride (Al (C)) 4 H 9 ) 2 Cl), n-butylaluminum dichloride (Al (C) 4 H 9 )Cl 2 ) Aluminum chlorodiisobutylaluminum (Al (i-C) 4 H 9 ) 2 Cl), isobutylaluminum dichloride (Al (i)-C 4 H 9 )Cl 2 ) Monochlorodin-pentylaluminum (Al (C) 5 H 11 ) 2 Cl), dichloro-n-pentylaluminum (Al (C) 5 H 11 )Cl 2 ) Aluminum (Al (i-C)) monochlorodiisoamyl 5 H 11 ) 2 Cl), isoamyl dichloride aluminum (Al (i-C) 5 H 11 )Cl 2 ) Aluminum di-n-hexyl monochloride (Al (C) 6 H 13 ) 2 Cl), dichloro-n-hexylaluminum (Al (C) 6 H 13 )Cl 2 ) Aluminum (Al (i-C)) monochlorodiisohexyl 6 H 13 ) 2 Cl), dichloroisohexylaluminum (Al (i-C) 6 H 13 )Cl 2 ) Chloromethyl ethyl aluminum (Al (CH) 3 )(CH 3 CH 2 ) Cl), monochloromethylpropyl aluminum (Al (CH) 3 )(C 3 H 7 ) Cl), chloromethyl n-butylaluminum (Al (CH) 3 )(C 4 H 9 ) Cl), chloromethyl isobutyl aluminum (Al (CH) 3 )(i-C 4 H 9 ) Cl), monochloroethylpropylaluminum (Al (CH) 2 CH 3 )(C 3 H 7 ) Cl), monochloroethyl n-butylaluminum (Al (CH) 2 CH 3 )(C 4 H 9 ) Cl) and monochloroethylisobutylaluminum (Al (CH) 2 CH 3 )(i-C 4 H 9 ) Cl), etc., among which diethylaluminum monochloride, ethylaluminum dichloroide, di-n-butylaluminum monochloride, n-butylaluminum dichloroide, diisobutylaluminum monochloride, isobutylaluminum dichloroide, di-n-hexylaluminum monochloride, n-hexylaluminum dichloroide are preferable, diethylaluminum monochloride, ethylaluminum dichloroide and di-n-hexylaluminum monochloride are further preferable, and diethylaluminum monochloride is most preferable.
In one embodiment of the present invention, these alkyl aluminum halides may be used singly or in combination of plural kinds in any ratio.
In one embodiment of the present invention, in the method for preparing an α -olefin-cyclic olefin according to the present invention, a catalytic system comprising a non-metallocene complex and a cocatalyst may be independently prepared and then used for copolymerization of an α -olefin and a cyclic olefin; or the non-metallocene complex and the cocatalyst can be added into the reaction system in sequence when the copolymerization reaction is carried out. The order of adding the non-metallocene complex and the cocatalyst is not particularly limited. The order of adding the organoboron compound and the alkyl aluminum derivative selected from at least one of alkyl aluminum, alkyl aluminum hydrolyzate and alkyl aluminum halide to the catalyst is not particularly limited.
In one embodiment of the present invention, the non-metallocene complex, the organoboron compound, and the alkylaluminum derivative may be used as they are or may be used after each is formulated into a solution. In the present invention, "directly used" means that each compound is directly added to the solvent used for preparing the above-mentioned catalytic system; or directly added to the solvent in the reaction system in which the copolymerization reaction is carried out. Preferably, each compound is used after being prepared into a solution.
As the solvent for preparing the catalyst system and/or the solvent used for preparing the solution, various inert organic solvents known in the art can be used, and for example, C can be mentioned 5-20 Alkane, C 6-30 Aromatic hydrocarbon, C 5-30 Alicyclic hydrocarbon, C 1-20 Halogenated alkanes, C 3-20 Halogenated alicyclic hydrocarbon and C 6-30 Examples of the halogenated aromatic hydrocarbon include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, toluene, xylene, chlorobenzene, and dichlorotoluene, and among them, pentane, hexane, decane, cyclohexane, toluene, and xylene are preferable. These solvents may be used singly or in combination in any ratio.
In one embodiment of the present invention, in separately preparing the catalytic system, the non-metallocene complex may be contacted with the cocatalyst for 60 to 360 minutes (hereinafter, referred to as a contact reaction), thereby obtaining the catalytic system.
In one embodiment of the present invention, in preparing the catalyst system independently, in order to bring the non-metallocene complex, the organoboron compound and the alkylaluminum derivative into sufficient contact, the solution containing the non-metallocene complex, the organoboron compound and the alkylaluminum derivative may be stirred (for example, at a stirring speed of 100-1000 rpm). In one embodiment of the present invention, in the case of separately preparing the catalytic system, the content ratio of the non-metallocene complex, the organoboron compound and the aluminum alkyl derivative in the catalytic system is made as follows, or in the case of conducting a copolymerization reaction, after adding the non-metallocene complex, the organoboron compound and the aluminum alkyl derivative to the reaction system, the content ratio of each compound is made as follows: the molar ratio of the alkyl aluminum derivative calculated by Al to the non-metallocene complex calculated by the metal element M is 50-5000: 1, preferably 100 to 4000: 1, more preferably 500 to 2000: 1; the molar ratio of the organoboron compound calculated by B to the non-metallocene complex calculated by the metal element M is 0.1-20: 1, preferably 0.5 to 10: 1, more preferably 0.8 to 5: 1.
in the present specification, unless otherwise specified, the molar amount of the non-metallocene complex is usually calculated as the metal element M, the molar amount of the alkyl aluminum derivative is usually calculated as the metal element Al, and the molar amount of the organoboron compound is usually calculated as the element B.
In one embodiment of the present invention, the reaction mode of the copolymerization method is not particularly limited, and those known in the art can be used, and examples thereof include a solution method and a bulk method, and among them, the solution method is preferable.
In one embodiment of the present invention, the copolymerization process may be carried out in the presence of an inert organic solvent as a copolymerization solvent, if necessary. The copolymerization solvent is not particularly limited, and may be any one conventionally used in the field of copolymerization of an alkene and a cycloolefin, and the amount of the solvent used may be any one conventionally used in the field. Specific examples of the solvent for copolymerization include C 5-20 Alkane, C 6-30 Aromatic hydrocarbon, C 5-20 Alicyclic hydrocarbon, C 1-20 Halogenated alkane, C 3-20 Halogenated alicyclic hydrocarbon and C 6-30 Halogenated aromatic hydrocarbons, etc., among which C is preferred 5-12 Straight or branched chain paraffin, C 5-12 Cycloalkanes, C 6-12 Aromatic hydrocarbon, C 1-12 Straight or branched chain halogenatedAlkane, C 3-12 Halogenated cycloalkanes and C 6-12 Halogenated aromatic hydrocarbons, more preferably C 6-9 Straight or branched chain paraffin, C 6-9 Cycloalkane, C 6-10 Aromatic hydrocarbon, C 1-8 Straight or branched halogenated alkanes, C 3-8 Halogenated cycloalkanes and C 6-10 Halogenated aromatic hydrocarbons, most preferably pentane, hexane, heptane, cyclohexane, cyclooctane, toluene or xylene. These copolymerization solvents may be used singly or in combination of two or more at an arbitrary ratio.
In one embodiment of the present invention, the copolymerization reaction may be carried out in a stirred column or tank reactor, preferably a tank reactor. The reactor volume is from 0.05 to 1000L, preferably from 0.1 to 100L.
In one embodiment of the present invention, the reaction pressure (total pressure) of the copolymerization method is 0.1 to 5.0MPa, preferably 0.1 to 3.0MPa, more preferably 0.1 to 2.0MPa, but is not limited thereto.
In one embodiment of the present invention, the reaction temperature of the copolymerization method is 40 to 100 ℃, preferably 60 to 100 ℃, more preferably 70 to 90 ℃, but is not limited thereto.
In one embodiment of the present invention, when the copolymerization is carried out, the molar ratio of the cycloolefin to the non-metallocene complex in terms of the metal element M in the reaction system is 10 5 -10 7 1, preferably 5X 10 5 -5×10 6 1, more preferably 7X 10 5 -2×10 6 1, but not limited thereto.
In the copolymerization method of the present invention, the polymerization time is related to the amount of the catalyst and the reaction temperature, and the more the amount of the catalyst, the higher the reaction temperature, the faster the reaction rate, and the shorter the reaction time, and the reaction time is generally from 0.1 to 10 hours, preferably from 0.1 to 5 hours, and more preferably from 15min to 2 hours, but not limited thereto.
In one embodiment of the present invention, a chain transfer agent may be further added to the catalyst system to adjust the weight average molecular weight, molecular weight distribution, content of cycloolefin units, and the like of the copolymer during the copolymerization reaction. The chain transfer agent may be a metal alkyl compound other than the cocatalyst of the present invention, and examples thereof include one or more of n-butyllithium, diethylzinc, dipropylzinc, dibutylzinc, diisobutylzinc, diethylmagnesium, dibutylmagnesium and n-butylethylmagnesium. The molar ratio of the chain transfer agent counted by metal elements to the non-metallocene complex counted by metal elements M is 5-500: 1, preferably 10 to 100: 1, more preferably 10 to 50: 1. when the chain transfer agent is used, the chain transfer agent may be added to a separately prepared catalyst system, or may be added when the non-metallocene complex and the cocatalyst are added to the reaction system during the copolymerization reaction. The order of adding the chain transfer agent is not particularly limited. The chain transfer agent may be used as it is or may be used after being prepared into a solution. In preparing the solution, the solvents of the present invention exemplified above for preparing the solution of the non-metallocene complex, the organoboron compound, the alkylaluminum derivative and the like can be used.
In the present specification, unless otherwise specified, the molar amount of the chain transfer agent is based on the molar amount of the metal element in the chain transfer agent, and for example, when diethyl zinc is used as the chain transfer agent, the molar amount of the chain transfer agent is based on zinc.
In one embodiment of the present invention, the α -olefin-cycloolefin copolymer can be prepared in a single reactor in a continuous or batch polymerization manner using a single polymerization reactor apparatus.
In one embodiment of the present invention, the copolymerization process of α -olefin and cycloolefin according to the present invention can be carried out, for example, as follows: adding a copolymerization solvent, alpha-olefin and cycloolefin into a reactor at the temperature of 40-100 ℃ and the pressure of 0.1-5.0 MPa; after the alpha-olefin and the cyclic olefin are dissolved to saturation in the copolymerization solvent, a non-metallocene complex solution, an alkyl aluminum derivative solution, an organic boron compound solution and an optional chain transfer agent are sequentially added, so that the molar ratio of the cyclic olefin to the non-metallocene complex calculated by the metal element M is 10 5 -10 7 1, the molar ratio of the alkyl aluminum derivative calculated by Al to the non-metallocene complex calculated by the metal element M is 50-5000: 1, said organoboron compound calculated as B and said organoboron compound calculated as metal element MThe mol ratio of the non-metallocene complex is 0.1-20: 1, the molar ratio of the chain transfer agent counted by metal elements to the non-metallocene complex counted by metal elements M is 5-500: 1; in the reaction process, alpha-olefin is introduced for keeping the pressure in the reactor, and the polymerization reaction time is kept for 15min-2h, so that the alpha-olefin-cycloolefin copolymer can be prepared.
In one embodiment of the invention, the copolymerization product obtained after the end of the reaction is precipitated in acidified ethanol. Specifically, the obtained polymerized solution is poured into acidified ethanol for precipitation and then dried, preferably, vacuum-dried at 60 ℃ for 24 hours, thereby obtaining a purified α -olefin-cycloolefin copolymer. The acidified ethanol is prepared by mixing concentrated hydrochloric acid and ethanol, wherein the volume percentage of the concentrated hydrochloric acid relative to the ethanol can be 1 v/v-25 v/v%, and can also be 10 v/v-20 v/v%, and can be 15v/v% for example.
In one embodiment of the present invention, the concentration of the non-metallocene complex in the reaction solution in terms of the metal element M in the reaction system at the time of copolymerization reaction is 0.1X 10 -5 mol/L～50×10 -5 mol/L, preferably 0.5X 10 -5 mol/L～20×10 -5 mol/L, more preferably 1X 10 -5 mol/L～10×10 -5 mol/L。
In one embodiment of the present invention, the concentration of the cycloolefin in the reaction solution during the copolymerization reaction is 1 to 100mol/L, preferably 10 to 50 mol/L.
In one embodiment of the present invention, the concentration of the organoboron compound in the reaction system in terms of B in the reaction solution at the time of copolymerization is 1X 10 -6 mol/L～100×10 -5 mol/L, preferably 5X 10 -6 mol/L～50×10 - 5 mol/L。
In one embodiment of the present invention, the concentration of the aluminum alkyl derivative in the reaction system in terms of Al in the reaction solution at the time of copolymerization reaction is 1X 10 -3 mol/L～200×10 -3 mol/L, preferably 10X 10 -3 mol/L～150×10 -3 mol/L。
In one aspect of the inventionIn one embodiment, the concentration of the chain transfer agent in the reaction system in terms of the metal element in the reaction solution during the copolymerization reaction is 0 to 500X 10 -5 mol/L, preferably 10X 10 -5 mol/L～300×10 -5 mol/L。
In one embodiment of the present invention, the copolymerization process may be carried out in the presence of hydrogen or in the absence of hydrogen. In the case where hydrogen is present, the partial pressure of hydrogen may be 0.01 to 99%, preferably 0.01 to 50% of the aforementioned reaction pressure, but is not limited thereto in some cases.
In one embodiment of the present invention, the copolymerization process may be carried out in the presence of an inert gas or in the absence of an inert gas. In the case where an inert gas is present, the partial pressure of the inert gas may be 0.01 to 99%, preferably 0.01 to 50% of the aforementioned reaction pressure, but is not limited thereto in some cases. Examples of the inert gas include nitrogen, helium, and argon. These inert gases may be used alone or in combination in any ratio as required.
The invention also provides a polymer composition comprising at least the alpha-olefin-cyclic olefin copolymer of the invention.
The polymer composition of the present invention may further contain, as necessary, other additives known in the art, such as processing heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, colorants, antistatic agents, flame retardants, water repellents, hydrophilicity imparting agents, electrical conductivity imparting agents, thermal conductivity imparting agents, electromagnetic shielding property imparting agents, light transmittance adjusting agents, fluorescent agents, slip property imparting agents, transparency imparting agents, anti-blocking agents, metal deactivators, antibacterial agents, fillers, and the like, as long as the object of the present invention is not impaired.
The invention also relates to the use of an alpha-olefin-cyclic olefin copolymer for the manufacture of said polymer composition.
When manufacturing optical parts, packaging materials, electronic parts, and medical instruments, techniques commonly used in the art may be employed as needed, and examples thereof include, but are not limited to, extrusion molding, injection molding, calender molding, blow molding, and thermoforming. Thus, optical parts, packaging materials, electronic parts, and medical devices can be produced by these molding methods using the α -olefin-cycloolefin copolymer according to the present invention or the polymer composition according to the present invention.
Therefore, the present invention also provides the use of the α -olefin-cycloolefin copolymer for manufacturing optical parts, packaging materials, electronic parts, and medical devices. The invention also provides the application of the polymer composition in manufacturing optical components, packaging materials, electronic components and medical devices.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
In the following examples, the cycloolefin content in the copolymers was determined by means of NMR spectroscopy.
Specifically, as shown in FIG. 1, the content (NB%) of norbornene units in a sample was measured by using an AVANCE III HD NMR spectrometer and the measurement temperature was 120 ℃. The copolymer sample is dissolved by deuterated o-dichlorobenzene to prepare a solution with the weight percent of about 20, and the solution is scanned 6000 times at 120 ℃ to obtain the sample 13 C NMR spectrum. The main nuclear magnetic resonance characteristic signal peaks in the figure can be classified into four groups: signals between 45 and 55ppm are assigned to C2/C3, signals between 37 and 44ppm are assigned to C1/C4, signals between 32 and 36ppm are assigned to C7, and signals below 31.5ppm are assigned to C5/C6 and methylene signals of ethylene units. The content of norbornene units in the copolymer is determined in accordance with 13 Calculating the peak area of each attribution signal peak in the C-NMR spectrum to obtain:
Figure 208538DEST_PATH_IMAGE011
。
method for measuring M eta molecular weight and PDI
The molecular weight and the distribution of the copolymer are tested by a PL-220 type gel permeation chromatograph of Polymer Laboratories, 1,2, 4-trichlorobenzene is taken as a mobile phase, polystyrene is taken as a standard sample, a differential detector is adopted, the flow rate is 1.0mL/min, the measurement temperature is 150 ℃, and the sample concentration is 2.0 mg/Ml.
Measurement of glass transition temperature of the copolymer.
The thermal properties of the copolymers were determined using a differential scanning calorimeter (Perkin-Elmer DSC 7). The sample amount tested was 3-5mg, and the atmosphere was nitrogen. The sample is first heated from 30 ℃ to 180 ℃ at a rate of 20 ℃/min, left for 3min, then cooled to 20 ℃ at a rate of 20 ℃/min, left for 3min, and then raised to 180 ℃ at a rate of 20 ℃/min. Analysis was performed using the second temperature rise curve.
Example 1:
in a 1L stainless steel kettle type reactor, 15.6mol refined norbornene is dissolved in 500ml refined toluene to prepare a solution, the solution is added into a reactor which is replaced by nitrogen in advance, ethylene (1MPa) is punched for a plurality of times to saturate the solution with ethylene, 30ml toluene solution with 1mol/L triisobutylaluminum, 40 mu mol trityl tetrakis (pentafluorophenyl) borate and 20 mu mol 3-tert-butylsalicylidene 2-methylthioaniline titanium trichloride are added at one time under the conditions of 90 ℃, 1MPa and stirring, ethylene is added through additional metering in the polymerization process, and the pressure is controlled to be 1 MPa.
After 15min of reaction, gel was produced, the reaction solution was poured into ethanol (consisting of 300mL hydrochloric acid and 2000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (1000mL), and dried (60 ℃ C. to constant weight) to obtain 14g of copolymer, catalyst activity 2.8X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 2:
A2L tank reactor was used in this example. 24mol of refined ethylidene norbornene is dissolved in 1000ml of refined cyclohexane to prepare a solution, the solution is added into a reactor which is replaced by nitrogen in advance, ethylene (1MPa) is punched for a plurality of times to saturate the solution with ethylene, 80ml of toluene solution with the concentration of 1mol/L tri-N-butyl aluminum, 0.8ml of toluene solution with 1mol/L diethyl zinc, 120 mu mol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 60 mu mol of 3, 5-di-tert-butyl salicyl-2-propylthioanilinium trichloride are added at one time under the conditions of 55 ℃, 1MPa and stirring, ethylene is additionally metered in the polymerization process, and the pressure is controlled to be 1 MPa.
After 0.5h of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 450mL of hydrochloric acid and 3000mL of ethanol) containing 15% (v/v%) of hydrochloric acid, precipitated and filtered, the filter cake was washed with ethanol (1000mL), and dried (60 ℃ C. to constant weight) to obtain 30g of copolymer, the catalyst activity was 1.0X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 3:
A2L tank reactor was used in this example. 30mol of refined vinylnorbornene is dissolved in 1000ml of refined xylene to prepare a solution, the solution is added into a reactor which is replaced by nitrogen in advance, ethylene (1MPa) is punched for a plurality of times to saturate the solution with ethylene, 40ml of a toluene solution with 1mol/L of triisopentylaluminum, 2ml of a toluene solution with 1mol/L of diethyl zinc, 40. mu. mol of 1-butyl-3-methylimidazolium tetrafluoroborate and 40. mu. mol of salicyl 2-methylthioaniline titanium trichloride are added at one time under the conditions of 75 ℃, 1MPa and stirring, ethylene is added by additional metering in the polymerization process, and the pressure is controlled to be 1 MPa.
After 1 hour of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 600mL of hydrochloric acid and 4000mL of ethanol) containing 15% (v/v%) of hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (300mL), and dried (60 ℃ C. to constant weight) to obtain 48g of copolymer, the catalyst activity of which was 1.2X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 4:
A1L tank reactor was used in this example. Dissolving 16mol of refined norbornene in 500ml of refined xylene to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (1MPa) for multiple times to saturate the solution with ethylene, adding 10ml of toluene solution of tri-n-hexylaluminum with the concentration of 1mol/L, 0.4ml of toluene solution of diethyl zinc with the concentration of 1mol/L, 20 mu mol of ferrocenyl tetrafluoroborate and 20 mu mol of salicylidene 2-thiophenyl aniline titanium trichloride at one time under the conditions of 70 ℃, 1MPa and stirring, adding ethylene by additional metering in the polymerization process, and controlling the pressure to be 1 MPa.
After reacting for 15min, the reaction was stopped and allowed to reactThe solution was poured into ethanol (composed of 150mL hydrochloric acid and 1000mL ethanol) containing 15% (v/v%) hydrochloric acid for precipitation, filtered, the filter cake was washed with ethanol (300mL), and dried (60 ℃ C. to constant weight) to give 7g of copolymer, having a catalyst activity of 1.4X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 5:
in a 5L stainless steel kettle type reactor, 90mol of refined vinyl norbornene is dissolved in 2500ml of refined cyclooctane to prepare a solution, the solution is added into a reactor which is replaced by nitrogen in advance, ethylene (2MPa) is punched for a plurality of times to saturate the solution with ethylene, under the conditions of 65 ℃ and 2MPa and stirring, 50ml of toluene solution with the concentration of 1mol/L triisohexylaluminum, 200 mu mol of trityl tetra (pentafluorophenyl) borate, 2ml of toluene solution with the concentration of 1mol/L diethyl zinc and 200 mu mol of salicylidene 2-thiophenyl aniline titanium trichloride are added at one time, ethylene is additionally metered in the polymerization process, and the pressure is controlled to be 2 MPa.
After reacting for 2h, the reaction was stopped, the reaction solution was poured into ethanol (consisting of 750mL hydrochloric acid and 5L ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, filtered, the filter cake was washed with ethanol (2L), and dried (60 ℃ C. to constant weight) to obtain 600 g of copolymer, the catalyst activity of which was 1.5X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 6:
A1L tank reactor was used in this example. Dissolving 21mol of refined ethylidene norbornene in 500ml of a mixed solution of refined toluene and xylene, adding the solution into a reactor which is replaced by nitrogen in advance, pressing ethylene (2MPa) for multiple times to saturate the solution with ethylene, adding 20ml of a toluene solution with the concentration of 1mol/L diethyl methyl aluminum, 60 mu mol of N, N-dimethyl anilinium tetra (pentafluorophenyl) borate, 0.4ml of a toluene solution with the concentration of 1mol/L diethyl zinc and 20 mu mol of 3, 5-di-tert-butyl salicyl-2-propyl thioaniline titanium trichloride at one time under the conditions of 80 ℃, 2MPa and stirring, and adding ethylene in a supplementary metering manner in the polymerization process to control the pressure to be 2 MPa.
After 0.5h of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 150mL of hydrochloric acid and 1000mL of ethanol) containing 15% (v/v%) of hydrochloric acid to precipitate, and the filter cake was filtered with ethanol (30)0ml) was washed and dried (60 ℃ C. to constant weight) to obtain 11g of a copolymer having a catalyst activity of 1.1X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 7:
A0.5L tank reactor was used in this example. Dissolving 9mol of refined ethylidene norbornene in 250ml of refined toluene to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (2MPa) for multiple times to saturate the solution with ethylene, adding 15ml of toluene solution of 1mol/L dimethyl ethyl aluminum, 0.2ml of toluene solution of 1mol/L diethyl zinc, 10 mu mol of 1-butyl-3-methylimidazolium tetrafluoroborate and 10 mu mol of 3-tert-butylsalicylidene-2-propylthio aniline titanium trichloride at one time under the conditions of 50 ℃, 2MPa and stirring, and adding ethylene in a polymerization process by additional metering to control the pressure to be 2 MPa.
After 0.5h of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 150mL hydrochloric acid and 1000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (300mL), and dried (60 ℃ C. to constant weight) to obtain 14g of copolymer, the catalyst activity of which was 2.8X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 8:
A0.5L tank reactor was used in this example. Dissolving 10mol of refined vinyl norbornene in 300ml of refined cyclooctane to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (2MPa) for multiple times to saturate the solution with ethylene, adding 40ml of a 1mol/L tri-n-propylaluminum toluene solution, 1ml of a 1mol/L diethyl zinc toluene solution, 20 mu mol of ferrocene tetrafluoroborate and 10 mu mol of 3, 5-di-tert-butyl salicylidene 2-mercaptoaniline titanium trichloride at one time under the conditions of 40 ℃, 2MPa and stirring, and adding ethylene in a polymerization process by additional metering, wherein the pressure is controlled to be 2 MPa.
After 1.5h of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 150mL hydrochloric acid and 1000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (300mL), and dried (60 ℃ C. to constant weight) to obtain 12g of copolymer, the catalyst activity of which was 0.8X 10 6 g/(molM · h). Copolymerization ofThe physical properties are shown in Table 1.
Example 9:
in a 1L stainless steel tank reactor, 13.5mol of refined norbornene is dissolved in 500ml of refined toluene and cyclohexane to prepare a solution, the solution is charged into a reactor previously replaced with nitrogen, ethylene (1.5MPa) is punched out several times to saturate the solution with ethylene, 5ml of a 1mol/L toluene solution of triisohexylaluminum, 5. mu. mol of trityltetrakis (pentafluorophenyl) borate, 0.2ml of a 1mol/L toluene solution of diethylzinc, and 10. mu. mol of 3-t-butylsalicylidene-2-methylthioanilinium trichloride are charged in one portion under stirring at 55 ℃ and 1.5MPa, ethylene is additionally metered in during the polymerization, and the pressure is controlled to 1.5 MPa.
After reacting for 15min, the reaction was stopped, the reaction solution was poured into ethanol (composed of 150mL hydrochloric acid and 1000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, filtered, the filter cake was washed with ethanol (300mL), dried (60 ℃ C. to constant weight) to obtain 5g of copolymer, catalyst activity 2X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 10:
A1L tank reactor was used in this example. Dissolving 18mol of refined vinylnorbornene in 500ml of refined toluene to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, pressing ethylene (3MPa) for multiple times to saturate the solution with ethylene, adding 20ml of a toluene solution of triisobutylaluminum with a concentration of 1mol/L, 1ml of a toluene solution of diethylzinc with a concentration of 1mol/L, 40. mu. mol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 20. mu. mol of 3, 5-di-tert-butylsalicyl-2-propylthioanilinium titanium trichloride at one time under the conditions of 95 ℃, 3MPa and stirring, and adding ethylene by additional metering in the polymerization process, wherein the pressure is controlled to be 3 MPa.
After reacting for 15min, the reaction was stopped, the reaction solution was poured into ethanol (consisting of 300mL hydrochloric acid and 2000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, filtered, the filter cake was washed with ethanol (300mL), dried (60 ℃ C. to constant weight) to obtain 15g of copolymer, the catalyst activity of which was 3X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 11:
A10L tank reactor was used in this example. 225mol of refined ethylidene norbornene is dissolved in 5L of refined xylene to prepare a solution, the solution is added into a reactor which is replaced by nitrogen in advance, ethylene (3MPa) is punched for a plurality of times to saturate the solution with ethylene, 200ml of toluene solution with 1mol/L of triisobutylaluminum, 10ml of toluene solution with 1mol/L of diethyl zinc, 800 mu mol of 1-butyl-3-methylimidazolium tetrafluoroborate and 200 mu mol of 3, 5-di-tert-butylsalicylidene-2-propylthioaniline titanium trichloride are added at one time under the conditions of 40 ℃ and 3MPa stirring, ethylene is added through additional metering in the polymerization process, and the pressure is controlled to be 3 MPa.
After 1 hour of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 1.5L hydrochloric acid and 10L ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (3L), and dried (60 ℃ C. to constant weight) to obtain 52g of copolymer, catalyst activity 0.26X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Example 12:
A2.5L tank reactor was used in this example. Dissolving 54mol of refined norbornene in 1.5L of refined cyclohexane to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (3MPa) for multiple times to saturate the solution with ethylene, adding 80ml of a toluene solution with 1mol/L of triisopentylaluminum, 0.8ml of a toluene solution with 1mol/L of diethyl zinc, 160 mu mol of ferrocene tetrafluoroborate and 50 mu mol of 3, 5-di-tert-butylsalicylidene-2-mercaptoaniline titanium trichloride at 85 ℃ under the condition of 1MPa and stirring, and adding ethylene by supplementary metering in the polymerization process, wherein the control pressure is 3 MPa.
After 1 hour of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 3000mL of hydrochloric acid and 20L of ethanol) containing 15% (v/v%) of hydrochloric acid to precipitate, and then filtered, the filter cake was washed with 3L of ethanol, and dried (60 ℃ C. to constant weight) to obtain 200g of copolymer, the catalyst activity of which was 4X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Comparative example 1:
A1L tank reactor was used in this example. Dissolving 16mol of refined norbornene in 500ml of refined xylene to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (1MPa) for multiple times to saturate the solution with ethylene, adding 0.4ml of 1mol/L diethyl zinc toluene solution, 20ml of 1.5mol/L modified methylaluminoxane toluene solution and 20 mu mol of salicylidene-2-thiophenylaniline titanium trichloride at one time under the conditions of 70 ℃, 1MPa and stirring, and adding ethylene in a polymerization process by supplementary metering under the condition that the pressure is controlled to be 1 MPa.
After reacting for 15min, the reaction was stopped, the reaction solution was poured into ethanol (composed of 150mL hydrochloric acid and 1000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, filtered, the filter cake was washed with ethanol (300mL), dried (60 ℃ C. to constant weight) to obtain 8g of copolymer, the catalyst activity was 1.6X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Comparative example 2:
in a 5L stainless steel kettle type reactor, 90mol of refined vinyl norbornene is dissolved in 2500ml of refined cyclooctane to prepare a solution, the solution is added into a reactor which is replaced by nitrogen in advance, ethylene (2MPa) is punched for a plurality of times to saturate the solution by the ethylene, 30ml of toluene solution of methylaluminoxane with the concentration of 1.9mol/L, 2ml of diethyl zinc toluene solution with the concentration of 1mol/L and 200 mu mol of salicylidene 2-thiophenyl aniline titanium trichloride are added at one time under the conditions of 65 ℃ and 2MPa and stirring, the ethylene is added by additional measurement in the polymerization process, and the pressure is controlled to be 2 MPa.
After reacting for 2h, the reaction was stopped, the reaction solution was poured into ethanol (consisting of 750mL hydrochloric acid and 5L ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, filtered, the filter cake was washed with ethanol (2L), dried (60 ℃ C. to constant weight) to obtain 675 g of copolymer, which had a catalyst activity of 1.7X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Comparative example 3:
A1L tank reactor was used in this example. Dissolving 21mol of refined ethylidene norbornene in 500ml of a mixed solution of refined toluene and xylene, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (2MPa) for multiple times to saturate the solution with ethylene, adding 20ml of a toluene solution of methylaluminoxane with the concentration of 1.9mol/L, 0.4ml of a toluene solution of diethyl zinc with the concentration of 1mol/L and 20 mu mol of 3, 5-di-tert-butyl salicyl 2-propylthioaniline titanium trichloride at one time under the conditions of 80 ℃ and 2MPa stirring, and adding ethylene in a supplementing and metering manner in the polymerization process to control the pressure to be 2 MPa.
After 0.5h of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 150mL hydrochloric acid and 1000mL ethanol) containing 15% (v/v%) hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (300mL), and dried (60 ℃ C. to constant weight) to obtain 10g of copolymer, the catalyst activity of which was 1.0X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Comparative example 4:
dissolving 15.6mol of refined norbornene in 200ml of refined toluene in a 1L stainless steel kettle type reactor to prepare a solution, adding the solution into a reactor which is replaced by nitrogen in advance, stamping ethylene (1MPa) for multiple times to saturate the solution with ethylene, adding 10ml of 1.9mol/L methylaluminoxane solution and 10 mu mol of 3-tert-butylsalicylidene-2-methylthioaniline titanium trichloride at one time under the conditions of 90 ℃, 1MPa and stirring, and adding ethylene in a polymerization process by additional metering, wherein the pressure is controlled to be 1 MPa.
After reacting for 15min, the reaction solution was poured into ethanol (composed of 300mL hydrochloric acid and 2000mL ethanol) containing 15% (v/v%) hydrochloric acid for precipitation, filtered, the filter cake was washed with ethanol (1000mL), dried (60 ℃ C. to constant weight) to obtain 6 g of copolymer, the catalyst activity was 1.2X 10 6 g/(molM · h). The physical properties of the copolymer are shown in Table 1.
Comparative example 5
In a 250ml glass reactor, 0.013mol of purified norbornene was dissolved in 50ml of purified toluene to prepare a solution, this solution was charged into a reactor previously substituted with nitrogen, ethylene (0.1MPa) was punched out plural times to saturate the solution with ethylene, and 1.03ml of a methylcyclohexane solution of Modified Methylaluminoxane (MMAO) having a concentration of 1.94mol/L and 2. mu. mol of rac-vinylbis (4,5,6, 7-tetrahydro-1-indenyl) zirconium dichloride were sequentially added under stirring at 70 ℃ and 0.1MPa, and the pressure was controlled at 0.1 MPa.
After 0.5h of reaction, the reaction was stopped, the reaction solution was poured into ethanol (composed of 15mL of hydrochloric acid and 100mL of ethanol) containing 15% (v/v%) of hydrochloric acid to precipitate, and then filtered, the filter cake was washed with ethanol (300mL), and dried (dried at 60 ℃ C.)Drying to constant weight) to obtain 5.37 g of copolymer and 5.37X 10 of catalyst activity 6 g/(mol. h). The physical properties of the copolymer are shown in Table 1.
TABLE 1 catalyst Activity and copolymer Properties
Figure 682244DEST_PATH_IMAGE012
It can be confirmed by the examples of the present invention that the α -olefin-cyclic olefin copolymer can be prepared at low cost and with high efficiency by using a non-metallocene catalytic system comprising an alkylaluminum derivative and an organoboron compound as a cocatalyst without using an aluminoxane-based cocatalyst. The activity of the copolymerization reaction is equivalent to or more excellent than that in the case of using an aluminoxane-based cocatalyst, and the physical properties of the resulting copolymer are equivalent to or more excellent. In particular, the non-metallocene catalyst system of the present invention exhibits more excellent activity than the case of using the metallocene catalyst system, and the resulting copolymer has more excellent physical properties.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (14)

1. A method for preparing an α -olefin-cycloolefin copolymer, comprising the steps of: copolymerizing alpha-olefin and cycloolefin in the presence of a non-metallocene complex and a cocatalyst,
the cocatalyst is a mixed system of an organic boron compound and at least one alkyl aluminum derivative selected from alkyl aluminum, alkyl aluminum hydrolysate and halogenated alkyl aluminum.
2. The production method according to claim 1, wherein the α -olefin is represented by the following formula (a),
R-CH=CH 2 　　　　　(a)
in the formula (a), R represents H or C 1-8 Straight or branched alkyl, preferably H or C 1-4 Straight or branched chain alkyl, more preferably H, methyl or ethyl,
the cycloolefin is a compound represented by the following formula (Y),
Figure 882809DEST_PATH_IMAGE001
　　　　　(Y)
in the formula (Y), the groups Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh may be the same or different and are each independently selected from hydrogen or C 1-10 A linear or branched hydrocarbon radical, preferably selected from hydrogen, C 1-10 Straight or branched alkyl or C 2-10 Straight or branched alkenyl, more preferably selected from hydrogen, C 1-4 Straight or branched alkyl or C 2-4 Straight or branched alkenyl; n is an integer from 0 to 6, preferably 0 or 1;
Figure 331108DEST_PATH_IMAGE002
represents a single bond or a double bond,
more preferably, the cycloolefin is at least one selected from the group consisting of norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, 5-methylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene and 8-ethyltetracyclododecene.
3. The production method according to claim 1 or 2, wherein the non-metallocene complex is a compound represented by the following formula (I),
Figure 845266DEST_PATH_IMAGE003
　　　　　(I)
in the formula (I), the radical R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen and C 1-6 A straight or branched hydrocarbon radical, preferably each independently selected from hydrogen and C 1-6 Straight or branched chain alkyl, more preferably each independently selected from hydrogenMethyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl;
R 6 、R 7 、R 8 、R 9 each independently selected from hydrogen and C 1-6 A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C 1-6 Straight or branched chain alkyl, more preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl;
R 5 represents hydrogen or C 1-12 Straight or branched chain hydrocarbon radicals, preferably hydrogen, C 1-6 Straight or branched alkyl or C 6-10 Aryl, more preferably hydrogen, C 1-3 Straight or branched chain alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl or isopropyl;
R 10 represents hydrogen or C 1-6 Straight or branched hydrocarbon radicals, preferably hydrogen or C 1-6 A linear or branched alkyl group, more preferably hydrogen, methyl or ethyl, more preferably hydrogen;
the group Y is O or S, preferably O; the group A is S or O, preferably S; m is selected from group IVB metal elements, preferably from titanium, zirconium and hafnium, more preferably titanium; the group X is selected from fluorine, chlorine, bromine and iodine, preferably chlorine or bromine;
Figure 178158DEST_PATH_IMAGE002
represents a single bond or a double bond, and when the bond is a single bond, H on N is present, and when the bond is a double bond, H on N is absent; represents a coordination bond; n represents the valence of the atom M and is selected from 1,2, 3, 4 or 5.
4. The process according to any one of claims 1 to 3, wherein the non-metallocene complex represented by the formula (I) is a complex selected from the group consisting of 3-t-butylsalicylidene-2-methylthioaniline titanium trichloride, salicylidene-2-phenylthioaniline titanium trichloride, 3, 5-di-t-butylsalicylidene-2-propylthioaniline titanium trichloride, 3, 5-di-t-butylsalicylidene-2-mercaptoaniline titanium trichloride, salicylidene-2-methylthioaniline titanium trichloride, salicylidene-2-propylthioaniline titanium trichloride, 3, 5-di-t-butylsalicylidene-2-methylthioaniline titanium trichloride, titanium trichloride, 3, 5-di-tert-butyl salicyl 2-methylthio aniline titanium trichloride and 3, 5-di-tert-butyl salicyl 2-propylthio aniline titanium trichloride.
5. The production method according to any one of claims 1 to 4, wherein the organoboron compound is at least one selected from the group consisting of an alkylboron, an arylboron and a borate, preferably trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, tris (pentafluorophenyl) boron, tris [3, 5-bis (trifluoromethyl) phenyl ] boron, trimethyl ammonium tetraphenyl borate, triethyl ammonium tetraphenyl borate, tripropyl ammonium tetraphenyl borate, tributyl ammonium tetraphenyl borate, trimethyl ammonium tetra (p-tolyl) borate, tripropyl ammonium tetra (p-tolyl) boron, trimethyl ammonium tetra (o, p-dimethylphenyl) borate, triethyl ammonium tetra (o, p-dimethylphenyl) borate, trimethyl ammonium tetra (p-trifluoromethylphenyl) borate, tributyl ammonium tetra (p-trifluoromethylphenyl) borate, Tributylammonium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetraphenylborate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrapentafluorophenyl borate, diethylammonium tetrapentafluorophenyl borate, trityltetrakis (pentafluorophenyl) borate, 1-butyl-3-methylimidazolium tetrafluoroborate, and ferrocene tetrafluoroborate.
6. The production method according to any one of claims 1 to 5, wherein the aluminum alkyl is a compound represented by the following formula (D); the halogenated alkyl aluminum is a compound shown as the following formula (E);
Al(R 11 ) 3 　　　　　(D)
Al(R 11 ) n X 3-n 　　　　　(E)
in the formulae (D) and (E), the radical R 11 Are the same or different from each other and are each independently selected from C 1-8 Alkyl, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentylAlkyl, hexyl and isohexyl;
in the formula (E), X is halogen, and n is an integer of 1 or 2.
7. The production process according to any one of claims 1 to 6, wherein the molar ratio of the cyclic olefin to the non-metallocene complex in terms of the metal element M in the reaction system is 10 5 ～10 7 1, preferably 5X 10 5 ～5×10 6 1, more preferably 7X 10 5 ～2×10 6 1, preparing a mixture; the molar ratio of the alkyl aluminum derivative calculated by Al to the non-metallocene complex calculated by the metal element M is 50-5000: 1, preferably 100 to 4000: 1, more preferably 500 to 2000: 1; the molar ratio of the organoboron compound calculated by B to the non-metallocene complex calculated by the metal element M is 0.1-20: 1, preferably 0.5 to 10: 1, more preferably 0.8 to 5: 1.
8. the production method according to any one of claims 1 to 7, wherein, at the time of copolymerization, a chain transfer agent is further added; preferably, the chain transfer agent is one or more selected from n-butyl lithium, diethyl zinc, dipropyl zinc, dibutyl zinc, diisobutyl zinc, diethyl magnesium, dibutyl magnesium and n-butyl ethyl magnesium; preferably, the molar ratio of the chain transfer agent calculated by metal elements to the non-metallocene complex calculated by metal elements M is 5-500: 1, preferably 10 to 100: 1, more preferably 10 to 50: 1.
9. the production method according to any one of claims 1 to 8, wherein the concentration of the non-metallocene complex in the reaction solution in terms of the metal element M in the reaction system is 0.1 x 10 -5 mol/L～50×10 -5 mol/L, preferably 0.5X 10 - 5 mol/L～20×10 -5 mol/L, more preferably 1X 10 -5 mol/L～10×10 -5 mol/L; the concentration of the cycloolefin in the reaction solution is 1-100 mol/L, preferably 10-50 mol/L; the organoboron compound in terms of B has a concentration of 1X 10 in the reaction solution -6 mol/L～100×10 -5 mol/L, preferably 5X 10 -6 mol/L～50×10 -5 mol/L; the concentration of the aluminum alkyl derivative in the reaction solution was 1X 10 in terms of Al -3 mol/L～200×10 -3 mol/L, preferably 10X 10 -3 mol/L～150×10 -3 mol/L; the concentration of the chain transfer agent in the reaction is 0-500 x 10 -5 mol/L, preferably 10X 10 -5 mol/L～300×10 -5 mol/L。
10. The production process according to any one of claims 1 to 9, wherein the reaction pressure (total pressure) is from 0.1 to 5.0MPa, preferably from 0.1 to 3.0MPa, more preferably from 0.1 to 2.0 MPa; the reaction temperature is 40 to 100 deg.C, preferably 60 to 100 deg.C, and more preferably 70 to 90 deg.C.
11. The production method according to any one of claims 1 to 10, further comprising a step of precipitating the copolymerization product in acidified ethanol.
12. An α -olefin-cycloolefin copolymer obtained by the production method according to any one of claims 1 to 11.
13. A polymer composition comprising at least the α -olefin-cycloolefin copolymer according to claim 12 and optionally additives.
14. Use of an α -olefin-cyclic olefin copolymer according to claim 12 or a polymer composition according to claim 13 for the manufacture of optical parts, packaging materials, electronic parts, medical devices.
CN202110176242.6A 2021-02-07 2021-02-07 Alpha-olefin-cycloolefin copolymer and preparation method and application thereof Pending CN114907509A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114805654A (en) * 2022-05-16 2022-07-29 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN116217772A (en) * 2023-01-10 2023-06-06 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN116217772B (en) * 2023-01-10 2024-05-28 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114805654A (en) * 2022-05-16 2022-07-29 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN114805654B (en) * 2022-05-16 2023-04-07 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN116217772A (en) * 2023-01-10 2023-06-06 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN116217772B (en) * 2023-01-10 2024-05-28 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof

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