CN105884941B - Non-metallocene catalyst, preparation method and application thereof - Google Patents

Abstract

The present invention relates to a non-metallocene catalyst comprising the contact product of a non-metallocene complex and an aluminoxane. The invention also relates to a preparation method of the non-metallocene catalyst and application of the non-metallocene catalyst in olefin polymerization. The non-metallocene catalyst shows an improved polymerization activity as compared to the case where the non-metallocene complex and the aluminoxane are simply used in combination. The non-metallocene catalyst of the present invention is particularly suitable as a catalyst for copolymerizing ethylene and cyclic olefin to produce an ethylene-cyclic olefin copolymer.

Description

Non-metallocene catalyst, preparation method and application thereof

Technical Field

The present invention relates to a non-metallocene catalyst, in particular a non-metallocene catalyst comprising the contact product of a non-metallocene complex and an aluminoxane. The invention also relates to a preparation method of the non-metallocene catalyst and application of the non-metallocene catalyst in olefin polymerization.

Background

With the continuous progress of society, the development of science and technology is changing day by day, and the demand for high-performance materials is also increasing. Ethylene-cycloolefin copolymer is an excellent amorphous thermoplastic polymer material. As one of the high-end products comprehensively utilized by the C5 series, the high-transparency, low-water-absorption, high-heat-resistance and high-refractive index-based optical material has the characteristics of high transparency, low water absorption, high heat resistance, high refractive index and the like, and is expected to replace PC and PMMA to be applied to optical components. In addition, the material may also have a potentially large market in the fields of packaging, electronic components, medical devices, and the like.

Generally, catalysts for manufacturing ethylene-cycloolefin copolymers are metallocene catalysts, and non-metallocene catalysts are relatively rarely reported for manufacturing ethylene-cycloolefin copolymers.

WO03010207 discloses a non-metallocene catalyst and its use in ethylene-cycloolefin copolymerization. However, the non-metallocene catalyst of the prior art still has room for further improvement in polymerization activity.

Accordingly, the current state of the art is that there is still a need for a non-metallocene catalyst which exhibits improved polymerization activity and is particularly suitable as a catalyst for the copolymerization of olefins with cycloolefins to produce olefin-cycloolefin copolymers, particularly ethylene-cycloolefin copolymers.

Disclosure of Invention

The present inventors have assiduously studied on the basis of the prior art and found that the aforementioned problems can be solved if a non-metallocene catalyst comprises a specific reaction product of an aluminoxane and a non-metallocene complex, and thus have completed the present invention.

Specifically, the present invention relates to the following aspects.

1. A non-metallocene catalyst comprising a contact product of an aluminoxane (preferably one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, preferably one or more selected from methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane, most preferably methylaluminoxane and modified methylaluminoxane) with at least one non-metallocene complex selected from the group consisting of the complexes represented by the following formula (I), the following formula (II) and the following formula (I-1) for 60 to 360 minutes (preferably 80 to 300 minutes, more preferably 120 and 250 minutes),

in the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon group, preferably hydrogen; the group Y is O or S, preferably O; the group A is S or O, preferably S; radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched chain alkyl, more preferably methyl; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A linear or branched hydrocarbon group, preferably an isopropyl group or a tert-butyl group, especially a tert-butyl group; radical R₁₀Is hydrogen or C_1-6A linear or branched hydrocarbon group, preferably hydrogen; the group M is selected from metal elements of groups III to XI of the periodic Table of the elements, preferably a metal element of group IVB, more preferably Ti; the group X is halogen, preferably chlorine; symbol- - -represents a coordinate bond.

2. A method for producing a non-metallocene catalyst, comprising the step of contacting an aluminoxane (preferably one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, preferably one or more selected from methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane, most preferably methylaluminoxane and modified methylaluminoxane) with at least one non-metallocene complex selected from the group consisting of the following formula (I), the following formula (II) and the following formula (I-1) for 60 to 360 minutes (preferably 80 to 300 minutes, more preferably 120 to 250 minutes),

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon group, preferably hydrogen; the group Y is O or S, preferably O; the group A is S or O, preferably S; radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched chain alkyl, more preferably methyl; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A linear or branched hydrocarbon group, preferably an isopropyl group or a tert-butyl group, especially a tert-butyl group; radical R₁₀Is hydrogen or C_1-6A linear or branched hydrocarbon group, preferably hydrogen; the group M is selected from metal elements of groups III to XI of the periodic Table of the elements, preferably a metal element of group IVB, more preferably Ti; the group X is halogen, preferably chlorine; symbol- - -represents a coordinate bond.

3. A non-metallocene catalyst kit comprising a first component and a second component, which are present independently of each other, and instructions for the operation, wherein the first component comprises alumoxane (preferably one or more selected from methylalumoxane, modified methylalumoxane, ethylalumoxane, isobutylalumoxane and n-butylaluminoxane, preferably one or more selected from methylalumoxane, modified methylalumoxane and isobutylalumoxane, most preferably methylalumoxane and modified methylalumoxane), preferably the first component consists essentially of said alumoxane, the second component comprises at least one non-metallocene complex selected from the group consisting of the following formulas (I), (II) and (I-1), the second component preferably consists essentially of said at least one non-metallocene complex, wherein the molar ratio of said alumoxane, calculated as Al, to said non-metallocene complex, calculated as metal element M, is from 20 to 2000: 1, preferably 50-1500: 1, more preferably 100-,

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon group, preferably hydrogen; the group Y is O or S, preferably O; the group A is S or O, preferably S; radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched chain alkyl, more preferably methyl; radical R₆And a group R₈may be the same or different and are each independently selected from C_3-6A linear or branched hydrocarbon group, preferably an isopropyl group or a tert-butyl group, especially a tert-butyl group; radical R₁₀Is hydrogen or C_1-6A linear or branched hydrocarbon group, preferably hydrogen; the group M is selected from metal elements of groups III to XI of the periodic Table of the elements, preferably a metal element of group IVB, more preferably Ti; the group X is halogen, preferably chlorine; symbol- - -represents a coordinate bond.

4. A method of using a non-metallocene catalyst, wherein the non-metallocene catalyst is a non-metallocene catalyst described in any preceding aspect, a non-metallocene catalyst manufactured by a manufacturing method described in any preceding aspect, or a non-metallocene catalyst manufactured using a non-metallocene catalyst kit described in any preceding aspect, which is used for olefin polymerization immediately after manufacture.

5. Use of a non-metallocene catalyst as an olefin polymerization catalyst, wherein the non-metallocene catalyst is a non-metallocene catalyst described in any preceding aspect, a non-metallocene catalyst manufactured by a manufacturing method described in any preceding aspect, or a non-metallocene catalyst manufactured using a non-metallocene catalyst kit described in any preceding aspect, which non-metallocene catalyst is used as an olefin polymerization catalyst immediately after manufacture.

6. A method for copolymerizing an alkene with a cyclic olefin, comprising using the non-metallocene catalyst according to any one of the above aspects, the non-metallocene catalyst produced by the production method according to any one of the above aspects, or the non-metallocene catalyst produced using the non-metallocene catalyst kit according to any one of the above aspects as an olefin polymerization catalyst, and polymerizing an alkene (preferably selected from C)_2-6One or more of alkenes, more preferably ethylene) with cycloalkenes.

7. Use of an aluminoxane in combination with a non-metallocene complex as an olefin polymerization catalyst, wherein the aluminoxane, preferably one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, preferably one or more selected from methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane, most preferably methylaluminoxane and modified methylaluminoxane, is contacted with at least one non-metallocene complex selected from the group consisting of the following formula (I), the following formula (II) and the following formula (I-1) for 60 to 360 minutes (preferably 80 to 300 minutes, more preferably 120 and 250 minutes), and then immediately used as an olefin polymerization catalyst for olefin polymerization,

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon group, preferably hydrogen; the group Y is O or S, preferably O; the group A is S or O, preferably S; radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched chain alkyl, more preferably methyl; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A linear or branched hydrocarbon group, preferably an isopropyl group or a tert-butyl group, especially a tert-butyl group; radical R₁₀Is hydrogen or C_1-6A linear or branched hydrocarbon group, preferably hydrogen; the group M is selected from metal elements of groups III to XI of the periodic Table of the elements, preferably a metal element of group IVB, more preferably Ti; the group X is halogen, preferably chlorine; symbol- - -represents a coordinate bond.

8. A method for copolymerizing an alkene with a cycloolefin, comprising the steps of:

Contacting an aluminoxane (preferably one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, preferably one or more selected from methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane, most preferably methylaluminoxane and modified methylaluminoxane) with at least one non-metallocene complex selected from the group consisting of those represented by the following formula (I), formula (II) and formula (I-1) for 60 to 360 minutes (preferably 80 to 300 minutes, more preferably 120 and 250 minutes) to obtain a contact product, and

Immediately using said contact product as an olefin polymerization catalyst, an alkene (preferably selected from C)_2-6One or more of the alkenes, more preferably ethylene) is copolymerized with the cycloalkene,

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon group, preferably hydrogen; the group Y is O or S, preferably O; the group A is S or O, preferably S; radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched chain alkyl, more preferably methyl; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A linear or branched hydrocarbon group, preferably an isopropyl group or a tert-butyl group, especially a tert-butyl group; radical R₁₀Is hydrogen or C_1-6A linear or branched hydrocarbon group, preferably hydrogen; the group M is selected from metal elements of groups III to XI of the periodic Table of the elements, preferably a metal element of group IVB, more preferably Ti; the group X is halogen, preferably chlorine; symbol- - -represents a coordinate bond.

9. The copolymerization process of any preceding aspect, wherein the cyclic olefin is optionally substituted with one or more C_1-10Straight or branched chain hydrocarbon radical (preferably C)_1-10Straight or branched alkyl or C_2-10Straight or branched alkenyl) substituted C_3-20Cycloolefins, preferably selected from the group optionally substituted by one or more C_1-10Straight or branched chain hydrocarbon radical (preferably C)_1-10Straight or branched alkyl or C_2-10Straight or branched alkenyl) optionally substituted with one or more C_1-10Straight or branched chain hydrocarbon radical (preferably C)_1-10Straight or branched alkyl or C_2-10Linear or branched alkenyl) optionally substituted cyclopentadiene, optionally substituted by one or more C_1-10Straight or branched chain hydrocarbon radical (preferably C)_1-10Straight or branched alkyl or C_2-10Linear or branched alkenyl) and a compound represented by the following formula (Y), more preferably selected from norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, 5-methylOne or more of norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene and 8-ethyltetracyclododecene,

In the formula (Y), the groups Ra to Rh may be the same or different and are each independently selected from hydrogen and C_1-10Straight or branched chain hydrocarbon radical (preferably C)_1-10Straight or branched alkyl or C_2-10Straight or branched alkenyl), preferably each independently selected from hydrogen, C_1-3Straight or branched alkyl or C_2-3Straight or branched alkenyl; n is an integer from 0 to 6, preferably 0 or 1; symbolRepresents a single bond or a double bond.

10. The copolymerization process of any preceding aspect, wherein the reaction conditions of the copolymerization reaction include: the reaction temperature is from 0 to 120 deg.C (preferably from 30 to 90 deg.C), the reaction pressure is from 0.1 to 5.0MPa (preferably from 0.1 to 2.0MPa), the molar ratio of cycloolefin/alkene is from 0.1 to 50: 1 (preferably from 0.2 to 40: 1), and hydrogen is either present or not.

Technical effects

The non-metallocene catalyst of the present invention (comprising a specific reaction product of a non-metallocene complex and aluminoxane) shows an improved polymerization activity, as compared to the case where the non-metallocene complex and aluminoxane are simply used in combination. It is known that high polymerization activity can not only reduce the cost but also reduce the ash content of the polymer.

The non-metallocene catalyst of the present invention can be used for catalyzing olefin polymerization, but is particularly suitable as a catalyst for copolymerizing an alkene and a cycloolefin to produce an alkene-cycloolefin copolymer, particularly an ethylene-alkene copolymer.

The non-metallocene catalysts of the present invention are homogeneous. By homogeneous is meant that all components making up the catalyst are in an unsupported state. Olefin polymers (such as copolymers of alkenes and cycloalkenes) produced using the non-metallocene catalysts of the invention as olefin polymerization catalysts have the advantage of low ash content due to the absence of supports, especially inorganic supports (such as porous supports or magnesium halides, etc.).

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.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

In the context of the present invention, the term "linear or branched hydrocarbon group" includes linear or branched alkyl groups, linear or branched alkenyl groups and linear or branched alkynyl groups. As the linear or branched hydrocarbon group, a linear or branched alkyl group is preferable. For example, C_1-4The straight-chain or branched hydrocarbon radicals including C_1-4Straight or branched alkyl, C_2-4Straight or branched alkenyl and C_2-4Straight-chain or branched alkynyl, wherein C is preferred_1-4Straight or branched chain alkyl.

In the context of the present invention, the term "halogen" includes fluorine, chlorine, bromine and iodine, of which chlorine is preferred.

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.

According to the present invention, a non-metallocene catalyst is involved, which comprises the specific reaction product (also referred to as contact product) of an aluminoxane with a non-metallocene complex.

According to the present invention, examples of the aluminoxane include linear aluminoxanes represented by the following formula (B): (R) (R) Al- (Al (R) -O)_n-O-Al (R), and a cyclic aluminoxane represented by the following formula (C): - (Al (R) -O-)_n+2-。

In the aforementioned formulae (B) and (C), the radicals R, which are identical or different from one another, are each independently selected from C₁-C₈Among the alkyl groups, methyl, ethyl, n-butyl and isobutyl are preferred, and methyl is more preferred. n is any integer in the range of 1 to 50, preferably in the range of 10 to 30.

The alumoxanes may further be modified according to the present invention by any means known in the art (also known in the art as modified alumoxanes). Examples of the modified aluminoxane include Modified Methylaluminoxane (MMAO). As the MMAO, a commercially available product may be used as it is, or it may be produced, for example, according to a method disclosed in US 5041584. The modified alumoxanes are also referred to herein simply as alumoxanes.

According to the present invention, as the aluminoxane, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferable, methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane are more preferable, and methylaluminoxane and modified methylaluminoxane are most preferable.

According to the present invention, these aluminoxanes may be used singly or in combination in any ratio.

According to the invention, the non-metallocene complex is selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (I-1). These non-metallocene complexes may be used singly or in combination of two or more in an arbitrary ratio.

According to the invention, in the abovementioned formulae, the radical R₁To the group R₄Group R₇And a group R₉may be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C_1-4Straight or branched alkyl, more preferably each independently selected from hydrogen and methyl, more preferablyAnd (3) hydrogen.

According to the invention, in the aforementioned formulae, the radical Y is O or S, preferably O.

According to the invention, in the abovementioned formulae, the radical A is S or O, preferably S.

According to the invention, in the abovementioned formulae, the radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched alkyl, more preferably C_1-3Straight or branched chain alkyl, most preferably methyl.

According to the invention, in the abovementioned formulae, the radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6Straight or branched chain hydrocarbon radicals such as C_3-6Straight or branched alkyl, preferably each independently selected from C_3-6Branched alkyl, more preferably isopropyl or tert-butyl, especially tert-butyl.

According to the invention, in the abovementioned formulae, the radical R₁₀Is hydrogen or C_1-6Straight or branched hydrocarbon radicals, preferably hydrogen or C_1-4Straight or branched chain alkyl groups, more preferably hydrogen, methyl and ethyl groups, most preferably hydrogen.

According to the invention, in the aforementioned formulae, the group M is selected from metal elements of groups III to XI of the periodic Table of the elements, preferably metal elements of group IVB such as titanium, zirconium and hafnium, more preferably Ti.

According to the invention, in the aforementioned formulae, the radical X is halogen, including fluorine, chlorine, bromine and iodine, with chlorine being preferred.

According to the invention, in each of the aforementioned formulae, the symbol- - -represents a coordinate bond.

according to the invention, as the non-metallocene complex, one of the compounds of the following formula or a mixture thereof in any proportion is more preferred.

According to the present invention, the compound represented by the formula (I) can be produced, for example, by the following production method.

According to the present invention, the production method comprises, for example, a step of obtaining a compound represented by the formula (I) by subjecting a compound represented by the following formula (I-a) to a coordination reaction with a compound represented by the following formula (X) (hereinafter referred to as coordination step a).

MX₄ (X)

According to the invention, in formula (X), the group M is selected from the metal elements of groups III to XI of the periodic Table of the elements, preferably the metal elements of group IVB such as titanium, zirconium and hafnium, of which titanium is more preferred.

According to the invention, in formula (X), the group X is halogen, including fluorine, chlorine, bromine and iodine, with chlorine 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, preferably from 0.9 to 1.3, more preferably from 1 to 1.2.

According to the invention, the complexing step a may be carried out in the presence of a solvent. 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_1-20Alkane, C_6-20Aromatic hydrocarbons and C_4-20Alicyclic hydrocarbons, etc., among which C is preferred_6-12Aromatic 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. As the protective gas, for example, an inert gas such as nitrogen gas and the like can be cited.

According to the present invention, after the completion of the coordination reaction in the coordination step A, the compound represented by the formula (I) can be separated from the mixture obtained in the reaction as a reaction product by a conventional separation means. Examples of the separation method include filtration, 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.

According to the invention, in this formula (I-A), the radical R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C_1-4Straight or branched chain alkyl groups, more preferably each independently selected from hydrogen and methyl, more preferably hydrogen.

According to the invention, in this formula (I-A), the group Y is O or S, preferably O.

According to the invention, in this formula (I-A), the group A is S or O, preferably S.

According to the invention, in this formula (I-A), the radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched alkyl, more preferably C_1-3Straight or branched chain alkyl, most preferably methyl.

According to the invention, in this formula (I-A), the radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6Straight or branched chain hydrocarbon radicals such as C_3-6Straight or branched alkyl, preferably each independently selected from C_3-6Branched alkyl, more preferably isopropyl or tert-butyl, especially tert-butyl.

According to the invention, in this formula (I-A), the radical R₁₀Is hydrogen or C_1-6Straight or branched hydrocarbon radicals, preferably hydrogen or C_1-4Straight or branched chain alkyl groups, more preferably hydrogen, methyl and ethyl groups, most preferably hydrogen.

According to the present invention, as the compound represented by the formula (I-A), a compound represented by the following structural formula is more preferable.

According to the present invention, the compound represented by the formula (I-A) can be produced, for example, by the following production method.

According to the present invention, the manufacturing method may include, for example, the following steps (1) and (2).

Step (1): a compound represented by the following formula (V) is obtained by subjecting a compound represented by the following formula (III) and a compound represented by the following formula (IV) to a condensation reaction.

According to the invention, in this formula (III), the radical R₁To the group R₄May be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C_1-4Straight or branched chain alkyl groups, more preferably each independently selected from hydrogen and methyl, more preferably hydrogen.

According to the invention, in this formula (III), the group A is S or O, preferably S.

According to the invention, in this formula (III), the radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched alkyl, more preferably C_1-3Straight or branched chain alkyl, most preferably methyl.

According to the invention, as the compound represented by the formula (III), 2-aminophenylmethylsulfide is preferred.

According to the invention, in this formula (IV), the radical R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4a linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C_1-4Straight or branched chain alkyl groups, more preferably each independently selected from hydrogen and methyl, more preferably hydrogen.

According to the invention, in this formula (IV), the radical Y is O or S, preferably O.

According to the invention, in this formula (IV), the radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6Straight or branched chain hydrocarbon radicals such as C_3-6Straight or branched alkyl, preferably each independently selected from C_3-6Branched alkyl, more preferably isopropyl or tert-butyl, especially tert-butyl.

According to the invention, in this formula (IV), the radical R₁₀Is hydrogen or C_1-6Straight or branched hydrocarbon radicals, preferably hydrogen or C_1-4Straight or branched chain alkyl groups, more preferably hydrogen, methyl and ethyl groups, most preferably hydrogen.

According to the invention, as the compound represented by the formula (IV), 3, 5-di-tert-butylsalicylaldehyde is preferred.

According to the invention, in this formula (V), the radical R₁To the group R₄Group R₇And a group R₉may be the same or different and are each independently selected from hydrogen and C_1-4A linear or branched hydrocarbon radical, preferably each independently selected from hydrogen and C_1-4Straight or branched chain alkyl groups, more preferably each independently selected from hydrogen and methyl, more preferably hydrogen.

according to the invention, in this formula (V), the radical Y is O or S, preferably O.

According to the invention, in this formula (V), the group A is S or O, preferably S.

According to the invention, in this formula (V), the radical R₅Is C_1-6Straight or branched chain hydrocarbon radicals, preferably C_1-6Straight or branched alkyl, more preferably C_1-3Straight or branched chain alkyl, most preferably methyl.

According to the invention, in this formula (V), the radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6Straight or branched chain hydrocarbon radicals such as C_3-6Straight or branched alkyl, preferably each independently selected from C_3-6Branched alkyl, more preferably isopropyl or tert-butyl, especially tert-butyl.

According to the invention, in this formula (V), the radical R₁₀Is hydrogen or C_1-6Straight or branched hydrocarbon radicals, preferably hydrogen or C_1-4Straight or branched chain alkyl groups, more preferably hydrogen, methyl and ethyl groups, most preferably hydrogen.

According to the present invention, the reaction of the step (1) may be carried out in a solvent (hereinafter referred to as the secondA solvent) is used. The first solvent includes, for example, C_1-15Fatty alcohol, C_6-20Aromatic alcohol, C_4-20Alicyclic alcohol, C_1-20Alkane, C_6-20Aromatic hydrocarbons or C_4-20Alicyclic hydrocarbons, of which C is preferred_1-4Aliphatic alcohols, most preferably methanol or ethanol. These first solvents may be used alone, or two or more of them may be used in combination, or may be used as an aqueous solution, as required.

According to the present invention, the amount of the first solvent is not particularly limited, and any amount may be used as long as it is advantageous for the condensation reaction in the step (1), and for example, the molar ratio of the first solvent to the compound represented by the formula (IV) is 5 to 200: 1, preferably 15 to 50: 1, but not limited thereto.

According to the invention, the molar ratio of the compound of formula (IV) to the compound of formula (III) is generally 0.5-2: 1, preferably 0.8-1.2: 1, when carrying out the condensation reaction of step (1).

According to the present invention, the reaction of step (1) may be carried out in the presence of a catalyst. The catalyst includes, for example, an organic carboxylic acid, and further includes, for example, C_1-10Aliphatic carboxylic acid, C_6-20Aromatic carboxylic acids or C_4-20Alicyclic carboxylic acids, of which C is preferred_1-4Aliphatic carboxylic acids, most preferably acetic acid. These catalysts may be used alone or in combination of two or more. The amount of the catalyst to be used is not particularly limited, and any amount may be used as long as it can promote the reaction in the step (1), and for example, the molar ratio of the catalyst to the compound represented by the formula (IV) is 0.002 to 0.5: 1, preferably 0.01 to 0.1: 1, but not limited thereto.

According to the present invention, the reaction temperature in said step (1) is generally from-20 to 150 ℃, preferably from 20 to 120, more preferably from 50 to 90 ℃.

According to the present invention, the reaction pressure of said step (1) may be any pressure suitable for the reaction to be carried out, but is generally from normal pressure to 0.5MPa for the sake of convenience of implementation.

According to the present invention, the reaction time of said step (1) is generally 0.1 to 20 hours, preferably 1 to 12 hours, more preferably 2 to 6 hours.

According to the present invention, the condensation reaction of step (1) may be carried out under stirring (e.g., stirring at 100-1000rpm) as required to promote the reaction.

According to the invention, after the reaction of step (1) is completed, the compound of formula (V) can be separated from the mixture obtained by the condensation reaction by a conventional separation method. Examples of the separation method include filtration, filtration followed by washing, and optionally further drying. Alternatively, the obtained compound represented by the formula (V) may be purified by a column chromatography method, 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 first solvent, 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.

Step (2): reducing the compound represented by the formula (V), for example, using a reducing agent, to obtain the compound represented by the formula (I-A).

According to the present invention, the reducing agent used in the step (2) is not particularly limited as long as it is a compound having the formula (V) wherein the compound has a-CR at the center of the molecular structure₁₀Reduction of ═ N-to-CHR₁₀Any reducing agent which-NH-does not alter the other molecular structure of the compound, in particular does not lead to the removal of the groups A, especially S, in its molecular structure, can be used. Examples of the reducing agent include a metal hydride or a combination of a metal and an acid. These reducing agents may be used aloneTwo or more of them may be used in combination.

According to the present invention, as the metal hydride, there may be mentioned, for example, any metal hydride conventionally used for this purpose in the field of organic synthesis, specifically, there may be mentioned, for example, an alkali metal hydride (e.g., NaH) or a complex hydride of an alkali metal with Al or B (e.g., LiAlH)₄、NaBH₄Etc.), among them, LiAlH is preferable₄. As the amount of the metal hydride used at this time, the molar ratio of the metal hydride to the compound represented by the formula (V) may be, for example, 0.25 to 4: 1, preferably 0.5 to 2: 1.

According to the present invention, in the combination of the metal and the acid, the metal includes chemically active metals such as Li, Fe, Mg, and Zn, and among them, Fe or Zn is preferable from the viewpoint of low price and easy availability. Examples of the acid include inorganic strong or medium-strong acids such as hydrochloric acid, sulfuric acid and nitric acid, or C_1-10Fatty acid, C_6-20aromatic acid and C_4-20Alicyclic acids and the like. These metals or acids may be used alone or in combination of two or more.

According to the invention, the molar ratio of the metal to the acid in the combination of the metal and the acid may be, for example, 5 to 200: 1, preferably 20 to 100: 1. When used as a reducing agent, the metal and the acid are used in combination in such an amount that the molar ratio of the metal to the compound of the formula (V) is 1 to 30: 1, preferably 2 to 10: 1.

According to the present invention, the reduction reaction of the step (2) may be carried out in the presence of a solvent (hereinafter, referred to as a second solvent). Examples of the second solvent include water, ether (e.g., diethyl ether), and C_1-15Fatty alcohol, C_6-20Aromatic alcohol, C_4-20Alicyclic alcohol, C_1-20Aliphatic hydrocarbons, C_6-20Aromatic hydrocarbons and C_4-20Alicyclic hydrocarbon, among which water, diethyl ether, toluene, methanol, ethanol or propanol is preferable. These second solvents may be used alone or in combination of two or more.

According to the present invention, the amount of the second solvent is not particularly limited, and any amount may be used as long as it is advantageous for the reduction reaction in the step (2), and for example, a molar ratio of the second solvent to the compound represented by the formula (V) is 2 to 500: 1, preferably 5 to 200: 1, but not limited thereto.

According to the present invention, the reaction temperature in said step (2) is generally 10 to 150 ℃, preferably 50 to 110 ℃, more preferably 70 to 100 ℃.

According to the present invention, the reaction pressure of said step (2) may be any pressure suitable for the reaction to be carried out, but is generally from normal pressure to 0.2MPa for the sake of convenience of implementation.

According to the present invention, the reaction time of said step (2) is generally 0.1 to 20 hours, preferably 0.2 to 10 hours, more preferably 0.3 to 5 hours.

According to the present invention, the reduction reaction of step (2) may be performed under stirring (e.g., stirring at a rotation speed of 100-1000rpm) as required to promote the reaction.

according to the present invention, the reduction reaction of the step (2) may be performed under a protective gas atmosphere, if necessary. As the protective gas, for example, an inert gas such as nitrogen gas and the like can be cited.

According to the present invention, after the reaction of the step (2) is completed, the compound represented by the formula (I-A) can be separated from the mixture obtained by the reaction by a conventional separation means. Examples of the separation method that can be used at this time include filtration, concentration of the filtrate under reduced pressure, precipitation by cooling, standing, concentration of the clear solution, and precipitation.

According to the present invention, the compound represented by the formula (I-a) thus obtained may also be purified by a conventionally known purification method such as recrystallization (for example, using methylene chloride, toluene or the like as a solvent for recrystallization) as needed, without particular limitation. Alternatively, the obtained compound represented by the formula (I-A) may be purified by a column chromatography method, preparative chromatography or the like, if necessary.

According to the present invention, the compound represented by the formula (II) can be produced, for example, by the following production method.

According to the present invention, the production method comprises, for example, a step of obtaining the compound represented by the formula (II) by subjecting the compound represented by the formula (V) and the compound represented by the formula (X) to a coordination reaction (hereinafter referred to as coordination step B).

According to the invention, the molar ratio of the compound of formula (X) to the compound of formula (V) when carrying out the complexing step B is generally from 0.7 to 1.5, preferably from 0.9 to 1.3, more preferably from 1 to 1.2.

According to the invention, the complexing step B can be carried out in the presence of a solvent (also referred to as third solvent). The third 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 (V) without interfering with the coordination reaction. Specifically, the third solvent includes, for example, C_1-20Alkane, C_6-20Aromatic hydrocarbons and C_4-20alicyclic hydrocarbons, etc., among which C is preferred_6-12Aromatic hydrocarbons, most preferably toluene, xylene, trimethylbenzene. These third solvents may be used singly or in combination of two or more in any ratio.

According to the present invention, the amount of the third 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 third solvent to the compound represented by the formula (V) is 5 to 200, preferably 10 to 100, but not limited thereto.

According to the invention, the reaction temperature of the complexing step B 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 B 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 B 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 B can be performed under stirring (e.g., stirring at a rotation speed of 100-1000rpm) as required in order to promote the reaction.

According to the present invention, the coordination reaction in the coordination step B may be performed in a protective gas atmosphere, if necessary. As the protective gas, for example, an inert gas such as nitrogen gas and the like can be cited.

According to the invention, after the coordination reaction in the coordination step B is finished, the compound represented by the formula (II) 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, 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 third solvent, 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.

According to the present invention, the compound represented by the formula (I-1) can be produced, for example, by a production method which can include, for example, the following steps (1) and (2).

Step (1): a step of dehydrogenating the compound represented by the formula (I-A) (hereinafter referred to as dehydrogenation step).

According to the present invention, according to this step (1), the group NH and the group YH contained in the compound represented by the aforementioned formula (I-A) are removed, whereby a compound having an anionic structure represented by the formula (I-B) is obtained.

According to the present invention, the method for dehydrogenating the compound represented by the aforementioned formula (I-A) to form the negative ion structure is not particularly limited, and any method conventionally employed in the art for this purpose can be employed. The dehydrogenation can be achieved, for example, by reacting the compound represented by the formula (I-A) with a metal hydride.

According to the present invention, as the hydride, for example, an alkali metal hydride (such as NaH or KH) is mentioned, and among them, KH is preferable. As the amount of the metal hydride used at this time, the molar ratio of the metal hydride to the compound represented by the formula (I-A) may be, for example, 2 to 6: 1, preferably 2 to 4: 1.

According to the invention, the dehydrogenation step may be carried out in the presence of a solvent. The solvent includes, for example, C_6-12Aromatic hydrocarbons, halogenated C_1-10Alkanes and ether solvents, and the like. Specific examples thereof include toluene, xylene, tetrahydrofuran, petroleum ether, diethyl ether, 2, 4-dioxane, methylene chloride, 1, 2-dichloroethane, and carbon tetrachloride, and tetrahydrofuran is most preferable. 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 advantageous for the dehydrogenation reaction, and for example, the molar ratio of the solvent to the compound represented by the formula (I-A) is 100-2000: 1, preferably 200-1000: 1, but not limited thereto.

According to the invention, the reaction temperature of the dehydrogenation step is generally from-80 to 100 ℃, preferably from-50 to 70 ℃, more preferably from-30 to 50 ℃.

According to the invention, the reaction pressure of the dehydrogenation step may be any pressure suitable for the progress of the coordination reaction, but is generally from atmospheric pressure to 0.2MPa for the sake of convenience of implementation.

According to the invention, the reaction time of the dehydrogenation step is generally from 0.1 to 72 hours, preferably from 0.2 to 48 hours, more preferably from 1 to 24 hours.

According to the present invention, the dehydrogenation step may be performed under stirring (e.g., at a stirring rotation speed of 100-1000rpm) in order to promote the reaction, if necessary.

According to the present invention, the dehydrogenation step may be performed under an atmosphere of a protective gas, if necessary. As the protective gas, for example, an inert gas such as nitrogen gas and the like can be cited.

According to the invention, after the end of the dehydrogenation reaction in the dehydrogenation step, by removing any solvent that may be used, a compound of the structure of the anion represented by the formula (I-B), the counter ion of which may be, for example, an alkali metal cation derived from the alkali metal hydride, is obtained as the reaction product of the dehydrogenation step. Examples of the solvent removal method include, but are not limited to, a rotary evaporation solvent removal method, a vacuum solvent removal method, and the like.

Step (2): a step of subjecting the reaction product obtained in the step (1), i.e., the compound represented by the formula (I-B), to a coordination reaction with the compound represented by the formula (X) to obtain the compound represented by the formula (I-1) (hereinafter referred to as coordination step C).

According to the invention, the coordination step C is carried out so that the molar ratio of the compound of formula (X) to the compound of formula (I-B) is generally between 0.7 and 1.5, preferably between 0.9 and 1.3, more preferably between 1 and 1.2.

according to the invention, the complexing step C can be carried out in the presence of a solvent (also referred to as fourth solvent). The fourth 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-B) without interfering with the coordination reaction. Specifically, the fourth solvent includes, for example, C_1-20Alkane, C_6-20Aromatic hydrocarbons and C_4-20Alicyclic hydrocarbons, etc., among which C is preferred_6-12Aromatic hydrocarbons, most preferably toluene, xylene, trimethylbenzene. These fourth solvents may be used alone or in combination of two or more in any ratio.

According to the present invention, the amount of the fourth solvent is not particularly limited, and any amount may be used as long as it is favorable for the coordination reaction, and examples thereof include the fourth solvent and the formula(I_-B) The molar ratio of the compounds shown is, but not limited to, 5 to 200, preferably 10 to 100.

According to the invention, the reaction temperature of the complexation step C is generally from-80 to 100 deg.C, preferably from-50 to 70 deg.C, more preferably from-30 to 50 deg.C.

According to the present invention, the reaction pressure of the coordination step C 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 C 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 C may 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 invention, the coordination reaction of the coordination step C needs to be carried out under an atmosphere of a protective gas. As the protective gas, for example, an inert gas such as nitrogen gas and the like can be cited.

According to the present invention, after the completion of the coordination reaction in the coordination step C, the compound represented by the formula (I-1) can be separated from the mixture obtained in the reaction as a reaction product by a conventional separation means. Examples of the separation method include filtration, 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 fourth solvent, 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.

According to the present invention, the aluminoxane is contacted with the non-metallocene complex for 60 to 360 minutes (hereinafter referred to as a contact reaction), thereby obtaining the contact product. Alternatively, according to the present invention, the non-metallocene catalyst can also be produced by using the contact reaction as an essential step.

According to the present invention, the contact reaction is carried out so that the molar ratio of the aluminoxane as Al to the non-metallocene complex as the metal element M is generally 20 to 2000: 1, preferably 50 to 1500: 1, more preferably 100-1000: 1.

According to the present invention, the contact reaction may be carried out in the presence of a solvent (also referred to as a fifth solvent). The fifth solvent is not particularly limited in the present invention, so long as it can dissolve the aluminoxane and the non-metallocene complex without interfering with the contact reaction. Specifically, the fifth solvent includes, for example, C_1-20alkane, C_6-20Aromatic hydrocarbons and C_4-20Alicyclic hydrocarbons, etc., among which C is preferred_6-12Aromatic hydrocarbons, most preferably toluene, xylene, trimethylbenzene. These fifth solvents may be used singly or in combination of two or more in any ratio.

According to the present invention, the amount of the fifth solvent is not particularly limited, and any amount may be used as long as it is favorable for the contact reaction, and for example, the molar ratio of the fifth solvent to the non-metallocene complex is 1000-.

According to the invention, the reaction temperature of the contact reaction is generally from-30 to 80 ℃, preferably from-20 to 50 ℃, more preferably from-10 to 40 ℃.

According to the present invention, the reaction pressure of the contact reaction may be any pressure suitable for the contact reaction, but is generally from normal pressure to 0.2MPa for the sake of convenience of practice.

According to the present invention, the reaction time of the contact reaction is preferably 80 to 300 minutes, more preferably 120-250 minutes.

The inventors of the present invention have found that when the reaction time of the contact reaction is below the lower limit value defined herein or above the upper limit value defined herein, the polymerization activity of the obtained non-metallocene catalyst tends to be significantly reduced. Therefore, according to the present invention, only the reaction product of the contact reaction for a period of 60 to 360 minutes (preferably 80 to 300 minutes, more preferably 120 to 250 minutes) is taken as the contact product. Other reaction products outside of this time period are not included within the definition of the contact product of the present invention.

According to the present invention, the contact reaction may be carried out under stirring (for example, at a stirring rotation speed of 100-1000rpm) in order to promote the reaction, if necessary.

According to the invention, the contact product (with or without solvent, as the case may be) is obtained by removing any solvent that may be used, or without removing the solvent, after the end of the contact reaction. Although not necessary, examples of the solvent removal method include a rotary evaporation solvent removal method, a vacuum solvent removal method, and the like, but the method is not limited thereto.

According to the present invention, the non-metallocene catalyst comprises the contact product as an essential component; alternatively, according to a most simplified embodiment of the present invention, the contact product is the non-metallocene catalyst. The non-metallocene catalyst may further comprise other components, as required, including but not limited to an inert diluent solvent (such as the aforementioned fifth solvent) and various cocatalysts conventionally used in the field of olefin polymerization (such as various cocatalysts exemplified hereinafter in this specification), and the like. These other components are preferably mixed with the contact product at the end of the manufacture of the contact product and included or introduced as components in the non-metallocene catalyst. The amount of these other components used at this time is not particularly limited depending on the actual use (e.g., dilution requirement or total amount of cocatalyst required for the objective olefin polymerization).

According to the invention, the non-metallocene catalyst is a homogeneous catalyst and thus does not comprise a support. By "support" is meant any component recognized in the art of olefin polymerization as a support or capable of performing a support or similar function, such as a magnesium halide or a porous support such as silica gel. That is, the non-metallocene catalyst is not supported but is in a free or unsupported state. Therefore, the non-metallocene catalyst of the present invention has the characteristic of simple manufacturing method.

It is known to the person skilled in the art that all the process steps described above are preferably carried out under substantially water-and oxygen-free conditions. As used herein, substantially water-free and oxygen-free means that the water content of the system is continuously less than 50ppm and the oxygen content is continuously less than 300 ppm. Moreover, the non-metallocene catalysts of the present invention, if stored after manufacture, typically need to be stored under a tight condition in the presence of a slightly positive pressure inert gas (such as nitrogen, argon, helium, etc.) for future use.

According to the invention, the non-metallocene catalyst is preferably used as an olefin polymerization catalyst immediately after its manufacture, for example for olefin polymerization, in particular for the copolymerization of alkenes with cycloolefins. In the context of the present specification, by "immediately" it is meant that the non-metallocene catalyst is (temporarily) stored only for 300 minutes or less, 200 minutes or less, 150 minutes or less, 100 minutes or less, 60 minutes or less, 40 minutes or less, 20 minutes or less, 10 minutes or less, 5 minutes or less, or 0 minutes (not stored) after completion of production, i.e., is introduced into an olefin polymerization reaction system as an olefin polymerization catalyst to exert its intended function, thereby being able to effectively avoid a decrease in polymerization activity thereof due to storage (corresponding to an extension of the reaction time of the contact reaction). The shelf life of the non-metallocene catalysts of the present invention is very short compared to the prior art non-metallocene catalysts which often take days or even months, and can therefore be considered "immediate".

according to the present invention, the non-metallocene catalyst may be provided in the form of a finished catalyst product, when the contact product has been manufactured. Due to the characteristics of the contact product as described above (shorter shelf life), the non-metallocene catalyst product, after being manufactured or obtained, is generally desired to be used as an olefin polymerization catalyst immediately without further storage, as described above, and thus has a disadvantage of inconvenience in use. In view of this, according to a particular embodiment of the present invention, the non-metallocene catalyst is provided as a catalyst kit, wherein the catalyst kit comprises at least a first component and a second component, and instructions for operation.

According to this embodiment of the invention, said first component comprises, preferably consists essentially of, said aluminoxane. By "consisting essentially of an aluminoxane", it is meant that the first component may further comprise a solvent (such as the aforementioned fifth solvent) used as needed, in addition to the aluminoxane, thereby allowing the aluminoxane to assume a solution state convenient for the user to handle.

According to this embodiment of the invention, the second component comprises, preferably consists essentially of, the non-metallocene complex. By "consisting essentially of a non-metallocene complex", it is meant that the second component may further comprise a solvent (such as the aforementioned fifth solvent) used as needed, in addition to the non-metallocene complex, thereby allowing the non-metallocene complex to assume a solution state convenient for a user to handle.

According to this embodiment of the present invention, the amount ratio of the first component to the second component is such that the molar ratio of the aluminoxane to the non-metallocene complex as the metal element M, calculated as Al, is in the range of from 20 to 2000: 1, preferably from 50 to 1500: 1, more preferably from 100-.

According to this embodiment of the invention, the kit may further comprise other components as desired, which corresponds to the other components which the non-metallocene catalyst may further comprise as desired, as described above, the type and amount of which are specified from the foregoing.

According to this embodiment of the invention, the first component and the second component (and possibly other components) are present independently of each other, e.g. packaged independently of each other, thereby effectively avoiding the possibility of any chemical reaction between these components. Thus, the catalyst kit can be stored for long periods of time (e.g., having a shelf life of several days or even months, as with prior art non-metallocene catalysts) without the risk of deterioration or failure.

According to this embodiment of the invention, the catalyst kit further comprises instructions for operation. According to this operating specification, it is clear that the non-metallocene catalyst is produced by subjecting the first component and the second component to the contact reaction in the manner as described hereinbefore immediately before use (i.e. immediately before use as an olefin polymerisation catalyst, such as for the polymerisation of olefins, in particular the copolymerisation of olefins with cycloolefins), such as simply mixing the first component and the second component in a predetermined ratio for a contact time as defined hereinbefore. Of course, the manner of introduction of the other components can also be carried out as described hereinbefore.

According to this embodiment of the present invention, the non-metallocene catalyst is produced in situ by the user of the catalyst kit after obtaining the catalyst kit, by performing the contact reaction and the like as specified in the operating instructions just before use (i.e., use as an olefin polymerization catalyst, such as for olefin polymerization, especially for copolymerization of an olefin and a cycloolefin). At this time, the non-metallocene catalyst produced has the best performance, such as the polymerization activity is in the peak state, and can be immediately put into a polymerization reaction system to be used as an olefin polymerization catalyst. It is therefore an advantage of this embodiment of the invention that a long shelf life is achieved while ensuring that the performance of the catalyst is at its optimum.

According to another particular embodiment of the present invention, the non-metallocene complex and the aluminoxane may also be provided in combination, for example both from different sources, and not necessarily from the same catalyst kit. In view of this, the present invention also relates to the use of said aluminoxane in combination with said non-metallocene complex as an olefin polymerization catalyst. According to this application, the aluminoxane is brought into contact with the non-metallocene complex as described above and then immediately (as described above) used as an olefin polymerization catalyst, for example for olefin polymerization, especially for copolymerization of an alkene with a cycloolefin.

According to the invention, the non-metallocene catalysts are particularly suitable for use as catalysts for the copolymerization of alkenes and cycloolefins and have an optimum performance, in particular an optimum polymerization activity, compared with the use as other olefin polymerization catalysts. In view of the above, the present invention relates to a method for copolymerizing an alkene and a cycloolefin, comprising the step of copolymerizing the alkene and the cycloolefin using the non-metallocene catalyst as an olefin polymerization catalyst. Alternatively, in view of the aforementioned characteristics (short shelf life) of the non-metallocene catalyst of the present invention, the production method of the non-metallocene catalyst may be combined with the copolymerization method. In view of this, the present invention also relates to a method for copolymerizing an alkene and a cycloolefin, comprising: a step of subjecting said aluminoxane and said non-metallocene complex to said contact reaction as described above to obtain a contact product; and a step of immediately copolymerizing an alkene with a cycloolefin using the contact product as an olefin polymerization catalyst.

In the copolymerization method of the present invention, other than those specifically mentioned below, those conventionally known in the art can be directly applied to the other non-specified matters (for example, a polymerization reactor, a feeding method of a reaction raw material, a catalyst, etc.) without any particular limitation, and the explanation thereof is omitted here.

According to the present invention, the olefin is an olefin having a linear or branched structure, and specifically includes C_2-10Straight or branched olefins, of which C is preferred_2-6Straight or branched olefins or C_2-3Alkenes, more preferably ethylene.

According to the present invention, these olefins may be used alone or in combination of two or more.

According to the invention, the cyclic olefin is an olefin having a double bond on a ring, such asGo out C_3-20A cyclic olefin. As said C_3-20Specific examples of the cycloolefin include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctatetraene and the like, and dicyclopentadiene, norbornene, norbornadiene, and the like,AndAnd spirocyclic, bridged or fused bicyclic or polycyclic cycloalkenes. As said C_3-20Cycloolefins, preferably cyclopentene, cyclopentadiene, dicyclopentadiene, norbornene or tetracyclododecene.

According to the invention, said C_3-20The 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_1-10the linear or branched hydrocarbon group is substituted at a suitable position. As said C_1-10Straight or branched chain hydrocarbon radicals, preferably C_1-10Straight or branched alkyl or C_2-10Straight or branched alkenyl, more preferably C_1-4Straight or branched alkyl or C_2-4Straight or branched alkenyl groups, of which methyl, ethyl, vinyl or ethylidene groups are more preferred.

According to an embodiment of the present invention, as the C_3-20Examples of the cycloolefin further include compounds represented by the following formula (Y).

According to the invention, in formula (Y), the radicals Ra to Rh may be identical or different and are each independently selected from hydrogen and C_1-10A straight or branched chain hydrocarbon group. As said C_1-10Straight or branched chain hydrocarbon radicals, preferably C_1-10Straight or branched alkyl or C_2-10Straight or branched alkenyl.

According to one embodiment of the invention, in formula (Y), the radicals Ra to Rh may be identicalOr may be different and are each independently selected from hydrogen and C_1-4straight or branched alkyl and C_2-4Straight or branched alkenyl radicals such as C_2-3Straight or branched alkenyl groups, of which methyl, ethyl, vinyl or ethylidene groups are more preferred.

According to the invention, in formula (Y), n is an integer from 0 to 6, preferably 0 or 1.

According to the invention, in the formula (Y), the symbolsRepresents a single bond or a double bond.

According to this embodiment of the present invention, as the compound represented by the formula (Y), norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, 5-methylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadiene, pentacyclohexadecene, and 8-ethyltetracyclododecene are preferable.

According to the present invention, the aforementioned cycloolefins may be used alone or in combination of two or more.

According to the invention, the copolymerization is carried out in a ratio (molar ratio) of the cycloolefin to the alkene of generally 0.1 to 50: 1, preferably 0.2 to 40: 1.

According to the present invention, the reaction system 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.

According to the present invention, the copolymerization process may be carried out in the presence of a 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_4-20Alkane, C_6-30Aromatic hydrocarbon, C_3-30Alicyclic hydrocarbon, C_1-20Halogenated alkanes, C_3-20Halogenated alicyclic hydrocarbon and C_6-30Halogenated aromatic hydrocarbons, etc., among which C is preferred_4-12Straight or branched alkanes、C_3-12Cycloalkanes, C_6-12Aromatic hydrocarbon, C_1-12Straight-chain or branched halogenated alkanes, C_3-12Halogenated cycloalkanes and C_6-12Halogenated aromatic hydrocarbons, more preferably C_4-9Straight or branched alkanes, C_4-9Cycloalkanes, C_6-9Aromatic hydrocarbon, C_1-8Straight-chain or branched halogenated alkanes, C_3-8Halogenated cycloalkanes and C_6-9Halogenated aromatic hydrocarbons, most preferably pentane, hexane, cyclohexane or toluene. These copolymerization solvents may be used singly or in combination of two or more at an arbitrary ratio.

According to the present invention, the copolymerization process may further use a cocatalyst, as required. Examples of the cocatalyst include aluminoxane, alkylaluminum hydrolysate, and alkylaluminum halide, among which aluminoxane, alkylaluminum, and alkylaluminum hydrolysate are preferable, and aluminoxane is more preferable.

According to the present invention, examples of the aluminoxane include the aluminoxanes described above for the contact reaction. These aluminoxanes may be used singly or in combination in any ratio.

According to the present invention, examples of the aluminum alkyl include compounds represented by the following formula (D):

Al(R)₃ (D)

In the formula (D), the radicals R, which are identical or different from one another, are each independently selected from C₁-C₈Alkyl groups, of which methyl, ethyl and isobutyl are preferred.

According to the invention, as the aluminum alkyl, trimethylaluminum (Al (CH)₃)₃) Triethylaluminum (Al (CH)₂CH₃)₃) Tri-n-propylaluminum (Al (C)₃H₇)₃) Triisobutylaluminum (Al (i-C)₄H₉)₃) Tri-n-butylaluminum (Al (C)₄H₉)₃) Triisopentylaluminum (Al (i-C)₅H₁₁)₃) Tri-n-pentylaluminum (Al (C)₅H₁₁)₃) Tri-n-hexylaluminum (Al (C)₆H₁₃)₃) Triisohexylaluminum (Al (i-C)₆H₁₃)₃) Diethyl methyl aluminum (Al (CH)₃)(CH₃CH₂)₂) And dimethyl ethyl aluminum (Al (CH)₃CH₂)(CH₃)₂) Etc., more preferred are trimethylaluminum, triethylaluminum, tri-n-propylaluminum and triisobutylaluminum, further preferred are triethylaluminum and triisobutylaluminum, and most preferred is triethylaluminum.

According to the present invention, these alkyl aluminum may be used singly or in combination of plural kinds in an arbitrary ratio.

According to 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.

According to the present invention, these alkyl aluminum hydrolysates may be used singly or in combination of plural kinds in an arbitrary ratio.

According to the present invention, examples of the halogenated alkylaluminum include a compound represented by the following formula (E):

Al(R)_nX_3-n (E)

In this formula (E), the radicals R, equal to or different from each other, are each independently selected from C₁-C₈Alkyl groups, of which methyl, ethyl and isobutyl are preferred, and methyl is most preferred; the group X is halogen, preferably chlorine. n is an integer of 1 or 2.

According to the present invention, as the above-mentioned haloalkylaluminum, for example, dimethylaluminum monochloride (Al (CH)₃)₂Cl), dichloromethylaluminum (Al (CH)₃)Cl₂) Aluminum diethyl monochloride (Al (CH)₃CH₂)₂Cl), ethyl aluminum dichloride (Al (CH)₃CH₂)Cl₂) Aluminum monochlorodipropyl (Al (C)₃H₇)₂Cl), dichloropropylaluminum (Al (C)₃H₇)Cl₂) Aluminum di-n-butyl monochloride (Al (C))₄H₉)₂Cl), n-butylaluminum dichloride (Al (C)₄H₉)Cl₂) Aluminum chlorodiisobutylaluminum (Al (i-C)₄H₉)₂Cl), dichloroisobutyl aluminium (Al (i-C)₄H₉)Cl₂) Monochlorodin-pentylaluminum (Al (C)₅H₁₁)₂Cl), dichloro-n-pentylaluminum (Al (C)₅H₁₁)Cl₂) Aluminum (Al (i-C)) monochlorodiisoamyl₅H₁₁)₂Cl), dichloroisoamyl aluminum (Al (i-C)₅H₁₁)Cl₂) Aluminum di-n-hexyl monochloride (Al (C)₆H₁₃)₂Cl), dichloro-n-hexylaluminum (Al (C)₆H₁₃)Cl₂) Aluminum (Al (i-C)) monochlorodiisohexyl₆H₁₃)₂Cl), dichloroisohexylaluminum (Al (i-C)₆H₁₃)Cl₂) Chloromethyl ethyl aluminum (Al (CH)₃)(CH₃CH₂) Cl), chloromethylpropylaluminum (Al (CH)₃)(C₃H₇) Cl), chloromethyl n-butylaluminum (Al (CH)₃)(C₄H₉) Cl), chloromethyl isobutyl aluminum (Al (CH)₃)(i-C₄H₉) Cl), monochloroethylpropylaluminum (Al (CH)₂CH₃)(C₃H₇) Cl), monochloroethyl n-butylaluminum (AlCH)₂CH₃)(C₄H₉) Cl) and chloromethyl isobutyl aluminum (AlCH)₂CH₃)(i-C₄H₉) 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.

According to the present invention, these alkyl aluminum halides may be used singly or in combination in any ratio.

According to the present invention, the cocatalyst may be used singly or in combination of two or more kinds in an arbitrary ratio as required, and is not particularly limited.

According to the invention, as the amount of the cocatalyst, for example, a molar ratio of the cocatalyst in terms of Al to the non-metallocene catalyst in terms of the metal element M of 30 to 1000: 1, preferably 50 to 500: 1, is used, but it is sometimes not limited thereto.

According to the present invention, the non-metallocene catalyst of the present invention (manufactured using the same type and amount of non-metallocene complex and aluminoxane) shows improved polymerization activity under the same polymerization reaction conditions, as compared to the case where the non-metallocene complex and aluminoxane are simply used in combination. The polymerization activity is generally improved by about 30% and can be up to more than 50%. By "simply used in combination", it is meant that the same type and amount of non-metallocene complex and aluminoxane are added directly to the polymerization system without prior contact reaction as defined in the present invention.

According to the present invention, the reaction pressure (total pressure) of the copolymerization method is generally 0.1 to 5.0MPa, preferably 0.1 to 2.5MPa, more preferably 0.1 to 2.0MPa, but is not limited thereto in some cases.

According to the present invention, the reaction temperature of the copolymerization method is generally 0 to 120 ℃, preferably 0 to 100 ℃, more preferably 30 to 90 ℃, but is not limited thereto in some cases.

According to the invention, the copolymerization process can be carried out in the presence or 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.

According to the present invention, the copolymerization process may be carried out in the presence or 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 of two or more in any ratio as required.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

The respective performance parameters referred to in examples and comparative examples were measured as follows.

(1) Polymerization Activity

The polymerization activity of the catalyst (in units of g (P) · (mol (M) · h)^-1Where P denotes a copolymer and M denotes a metal element M such as Ti) is calculated according to the following formula.

Polymerization Activity ═ m₁×4×Mw/m₂

Wherein the content of the first and second substances,

m₁Amount of copolymer obtained for a polymerization time of 15 minutes (g);

Mw is the molecular weight of the catalyst;

m₂Is the amount of catalyst added (g).

(2) Molecular weight M.eta.of the copolymer

The viscosity average molecular weight M.eta.of the copolymer was calculated in the following manner.

The intrinsic viscosity η of the copolymer was measured by a high temperature dilution Ubbelohde viscometer method (capillary inner diameter 0.44 to 0.60mm, constant temperature bath medium 300 silicone oil, solvent for dilution decahydronaphthalene, measurement temperature 135 ℃) in accordance with ASTM D4020-00, and the viscosity average molecular weight M η of the copolymer was calculated in accordance with the following formula.

Mη＝5.37×10⁴×［η］^1.37

Wherein η is the intrinsic viscosity.

(3)Tg

The Tg of the copolymer was measured by DSC. Specifically, 9mg of the copolymer to be tested was weighed as a sample. The sample is first heated from 30 ℃ to 200 ℃ at a rate of 10 ℃/min, then held for 3min, then cooled to 30 ℃ at a rate of 10 ℃/min, held for 3min, and then raised to 200 ℃ at a rate of 10 ℃/min. Analysis was performed using the second temperature rise curve.

Production example 1

Sequentially adding 2-aminobenzothioide (0.2mol), absolute ethyl alcohol (160ml), 3, 5-di-tert-butyl salicylaldehyde (0.2mol) and acetic acid (0.3ml) into a dry 500ml three-neck flask, heating to reflux temperature, reacting for 2hr, cooling to room temperature, filtering, washing with absolute ethyl alcohol for three times, and vacuum drying to obtain 2-aminobenzothioyl49.7g of 3, 5-di-tert-butyl salicylaldehyde ether, called ligand L1. Elemental analysis: c74.57% (theoretical 74.32%); h8.35% (theoretical 8.22%); n4.07% (theoretical 3.94%).¹H nuclear magnetism δ 13.4(OH), 8.6(CHN), 7.5-7.1(Ar-H), 3.25 (SCH)₃)，1.45(C(CH₃)₃)，1.35(C(CH₃)₃)

Production example 2

2-aminobenzene thioether (0.2mol), absolute ethyl alcohol (160ml), 3, 5-di-tert-butyl salicylaldehyde (0.2mol) and acetic acid (0.3ml) are sequentially added into a dry 500ml three-neck flask, the temperature is raised to the reflux temperature, the reaction lasts for 2 hours, the temperature is reduced to room temperature, the filtration is carried out, the reaction product is washed for three times by the absolute ethyl alcohol, and the vacuum drying is carried out, so that 49.7g of 2-aminobenzene thioether condensed 3, 5-di-tert-butyl salicylaldehyde is obtained.

To a toluene solution of 3, 5-di-tert-butylsalicylaldehyde (0.1mol) condensed with 2-aminobenzothioate was slowly added an ether solution of lithium aluminum hydride (0.2mol), and after completion of the addition, the reaction was continued with stirring for 30 minutes, and the reaction was terminated by adding ice water to the reaction solution. Column chromatography purification gave the compound of the formula designated ligand L2. Elemental analysis: c73.67% (theoretical value 73.90%); h8.71% (theoretical 8.74%); n4.08% (theoretical 3.92%).¹H nuclear magnetism δ 13.3(OH), 8.6(CHN), 7.5-7.1(Ar-H), 5.0(NH), 3.3 (SCH)₃)，1.45(C(CH₃)₃)，1.3(C(CH₃)₃)

Production example 3

A solution of 54ml of toluene containing 0.025mol of ligand L1 was added dropwise to a solution containing 0.031mol of TiCl in a 250ml three-necked flask at 20 ℃₄Adding into 6ml of toluene, continuously stirring and reacting at room temperature for 12 hours after the dropwise addition is finished, filtering, vacuumizing and drying the filtrate to obtain a crude product, and recrystallizing by using dichloromethane/hexaneTo give a compound of the formula, referred to as non-metallocene complex Cl. Elemental analysis: c52.11% (theoretical 51.84%); h5.63% (theoretical 5.54%); n2.98% (theoretical 2.75%).¹H nuclear magnetism δ ═ 8.79(CHN), 7.83 to 7.40(Ar-H), 3.08 (SCH)₃)，1.57(C(CH₃)₃)，1.35(C(CH₃)₃)

Production example 4

A solution of 54ml of toluene containing 0.025mol of ligand L2 was added dropwise to a solution containing 0.031mol of TiCl in a 250ml three-necked flask at 20 ℃₄And then continuously stirring and reacting at room temperature for 12 hours after the dropwise addition, filtering, vacuumizing and drying the filtrate to obtain a crude product, and recrystallizing with dichloromethane/hexane to obtain a compound shown as the following formula, namely the non-metallocene complex C2. Elemental analysis: c52.02% (theoretical value 51.63%); h8.71% (theoretical 8.59%); n2.68% (theoretical 2.74%).¹H nuclear magnetism δ 8.85 (CH)₂N)，7.82-7.40(Ar-H)，4.95(NH)，3.09(SCH₃)，1.55(C(CH₃)₃)，1.30(C(CH₃)₃)

Production example 5

Adding 150ml THF solution containing 0.01mol ligand L2 into a mixture of 0.02mmol KH and 30ml THF dropwise at-20 deg.C in a 250ml three-neck flask, stirring to room temperature, stirring for 2hr, removing solvent under vacuum, adding 40ml toluene, and adding dropwise the liquid to a solution containing 0.011mol TiCl₄And 40ml of toluene, continuously stirring and reacting at room temperature for 12 hours after the dropwise addition is finished, filtering, vacuumizing and drying the filtrate to obtain a crude product, and recrystallizing with dichloromethane/hexane to obtain a compound shown in the following formula, namely the non-metallocene complex C3. Elemental analysis: c55.58% (theoretical value 55.59%); h6.31% (theoretical 6.15%)) (ii) a N2.87% (theoretical 2.95%).¹h nuclear magnetism δ 8.93 (CH)₂N)，7.82-7.40(Ar-H)，3.13(SCH₃)，1.50(C(CH₃)₃)，1.30(C(CH₃)₃)

In all the following application examples, the overall Al/Ti molar ratio is 1500. By "overall Al/Ti molar ratio", it is meant the ratio of the sum of the moles of aluminoxane (if used, which is specifically used to carry out the contact reaction) and of cocatalyst, calculated as Al, to the moles of non-metallocene complex, calculated as metal element M.

Application example 1

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of toluene solution of dehydrated refined toluene, MAO (3mmol) and norbornene (0.056mol) is sequentially added into a pumped 250ml flask, finally, toluene solution containing 2 mu mol of non-metallocene complex Cl is added, a certain stirring speed is kept, after reaction for 15 minutes, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after the polymer is filtered and washed, the polymer is dried in vacuum at 50 ℃ to constant weight, thus obtaining the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 2

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition was complete the mixture was left for the specified contact time (min).

under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 45min is added, a certain stirring speed is kept, after 15 min of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 3

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition was complete the mixture was left for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 140min is added, a certain stirring speed is kept, after 15 min of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 4

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition was complete the mixture was left for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 210min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 5

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition was complete the mixture was left for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 360min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 6

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition was complete the mixture was left for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally, the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 1440min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 7

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 0.8mmol of MAO was slowly added at room temperature with stirring, and after the addition was complete, the mixture was left to stand for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (2.6mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 210min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 8

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 1.2mmol of MAO was slowly added at room temperature with stirring, and after the addition was complete, the mixture was left to stand for the specified contact time (min).

under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (2.4mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 210min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 9

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (3mmol) and norbornene (0.112mol) toluene solution are sequentially added into a pumped 250ml flask, a toluene solution containing 2 mu mol non-metallocene complex Cl is finally added, a certain stirring speed is kept, after reaction for 15 minutes, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after the polymer is filtered and washed, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 10

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition was complete the mixture was left for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.112mol) toluene solution are sequentially added into a pumped 250ml flask, and finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 210min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after the polymer is filtered and washed, the polymer is dried in vacuum at 50 ℃ to constant weight, thus obtaining the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 11

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (3mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally toluene solution containing 2 mu mol non-metallocene complex C2 is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after the polymer is filtered and washed, the polymer is dried in vacuum at 50 ℃ to constant weight, thus obtaining the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 12

Mu. mol of non-metallocene complex C2 were taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition, the mixture was left to stand for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex C2 which is placed for 210min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 13

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (3mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally toluene solution containing 2 mu mol non-metallocene complex C3 is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after the polymer is filtered and washed, the polymer is dried in vacuum at 50 ℃ to constant weight, thus obtaining the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 14

Mu. mol of non-metallocene complex C3 were taken and dissolved in 2ml of toluene, 3mmol of MAO were slowly added at room temperature with stirring, and after the addition, the mixture was left to stand for the specified contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex C3 which is placed for 210min is added, a certain stirring speed is kept, after 15 minutes of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 15

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, a hexane solution containing 3mmol of triethylaluminum was slowly added at room temperature with stirring, and after the addition was completed, the mixture was left for a prescribed contact time (min).

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 45min is added, a certain stirring speed is kept, after 15 min of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 16

Mu. mol of non-metallocene complex Cl was taken and dissolved in 2ml of toluene, a hexane solution containing 3mmol of triisobutylaluminum was slowly added at room temperature with stirring, and the mixture was left for a prescribed contact time (min) after the addition was completed.

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 140min is added, a certain stirring speed is kept, after 15 min of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 17

Mu. mol of non-metallocene complex C2 was taken and dissolved in 2ml of toluene, a hexane solution containing 3mmol of triisobutylaluminum was slowly added at room temperature with stirring, and the mixture was left for a prescribed contact time (min) after the addition was completed.

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 140min is added, a certain stirring speed is kept, after 15 min of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

Application example 18

Mu. mol of non-metallocene complex C3 was taken and dissolved in 2ml of toluene, a hexane solution containing 3mmol of triisobutylaluminum was slowly added at room temperature with stirring, and the mixture was left for a prescribed contact time (min) after the addition was completed.

Under the ethylene atmosphere of 0.1MPa, in an oil bath at 70 ℃, a certain amount of dehydrated refined toluene, MAO (1.5mmol) and norbornene (0.056mol) toluene solution are sequentially added into a pumped 250ml flask, finally the toluene solution containing 2 mu mol non-metallocene complex Cl and placed for 140min is added, a certain stirring speed is kept, after 15 min of reaction, the reaction is stopped by ethanol containing 5% hydrochloric acid, and after filtering and washing, the polymer is dried in vacuum at 50 ℃ to constant weight to obtain the ethylene-norbornene copolymer. The results are shown in Table 1.

TABLE 1

Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.

Claims (59)

1. A non-metallocene catalyst comprising a contact product of aluminoxane and at least one non-metallocene complex selected from the group consisting of those represented by the following formula (I), the following formula (II) and the following formula (I-1) for 60 to 360 minutes, wherein the molar ratio of the aluminoxane to the non-metallocene complex in terms of Al is 300-2000: 1,

In the above formulae, the group R₁to the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A straight or branched chain hydrocarbon group; the group Y is O or S; the group A is S or O; radical R₅Is C_1-6A linear or branched alkyl group; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A straight or branched chain hydrocarbon group; radical R₁₀Is hydrogen or C_1-6A straight or branched chain hydrocarbon group; the group M is selected from the group consisting of the elements of group IVB of the periodic Table of the elements; the group X is halogen; symbol- - -represents a coordinate bond.

2. The non-metallocene catalyst of claim 1, wherein the aluminoxane is one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and n-butylaluminoxane.

3. The non-metallocene catalyst of claim 1 or 2, wherein the contact time is 80-300 minutes.

4. The non-metallocene catalyst of claim 1 or 2, wherein the contact time is 120-250 minutes.

5. The non-metallocene catalyst of claim 1 or 2, wherein the group R₅Is methyl.

6. The non-metallocene catalyst of claim 1 or 2, wherein the group R₆And a group R₈Which may be the same or different, are each independently isopropyl or tert-butyl.

7. The non-metallocene catalyst of claim 1 or 2, wherein the group M is Ti.

8. The non-metallocene catalyst of claim 1 or 2, wherein X is chlorine.

9. A method for producing a non-metallocene catalyst, comprising a step of contacting an aluminoxane with at least one non-metallocene complex selected from the group consisting of those represented by the following formula (I), the following formula (II) and the following formula (I-1) for 60 to 360 minutes, wherein the molar ratio of the aluminoxane to the non-metallocene complex in terms of Al is 300-2000: 1,

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A straight or branched chain hydrocarbon group; the group Y is O or S; the group A is S or O; radical R₅is C_1-6A linear or branched alkyl group; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A straight or branched chain hydrocarbon group; radical R₁₀Is hydrogen or C_1-6A straight or branched chain hydrocarbon group; the group M is selected fromA metal element of group IVB of the periodic Table of elements; the group X is halogen; symbol- - -represents a coordinate bond.

10. The process according to claim 9, wherein the aluminoxane is one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane.

11. The production process according to claim 9 or 10, wherein the contact time is 80 to 300 minutes.

12. The method of claim 9 or 10, wherein the contact time is 120-250 minutes.

13. The production process according to claim 9 or 10, wherein the group R₅Is methyl.

14. The production process according to claim 9 or 10, wherein the group R₆And a group R₈Which may be the same or different, are each independently isopropyl or tert-butyl.

15. The production process according to claim 9 or 10, wherein the group M is Ti.

16. The production process according to claim 9 or 10, wherein X is chlorine.

17. A non-metallocene catalyst kit comprising a first component and a second component which are present independently of each other, and an instruction manual, wherein the first component comprises aluminoxane, the second component comprises at least one non-metallocene complex represented by the following formula (I), the following formula (II) and the following formula (I-1), wherein the molar ratio of the aluminoxane as Al to the non-metallocene complex as the metal element M is 300-2000: 1, and the first component and the second component are contacted for 60-360 minutes immediately before use according to the instruction manual, thereby producing a non-metallocene catalyst,

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A straight or branched chain hydrocarbon group; the group Y is O or S; the group A is S or O; radical R₅Is C_1-6A linear or branched alkyl group; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A straight or branched chain hydrocarbon group; radical R₁₀Is hydrogen or C_1-6A straight or branched chain hydrocarbon group; the group M is selected from the group consisting of the elements of group IVB of the periodic Table of the elements; the group X is halogen; symbol- - -represents a coordinate bond.

18. The non-metallocene catalyst kit of claim 17, wherein the first component consists essentially of the aluminoxane.

19. The non-metallocene catalyst kit of claim 17 or 18, wherein the second component consists essentially of the at least one non-metallocene complex.

20. The non-metallocene catalyst kit of claim 17 or 18, wherein the molar ratio of the aluminoxane to the non-metallocene complex as metal element M is 300-1000: 1.

21. The non-metallocene catalyst kit of claim 17 or 18, wherein the aluminoxane is one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane.

22. The non-metallocene catalyst kit of claim 17 or 18, wherein the contact time is 80-300 minutes.

23. The non-metallocene catalyst kit of claim 17 or 18, wherein the contact time is 120-250 minutes.

24. The non-metallocene catalyst kit of claim 17 or 18, wherein group R₅Is methyl.

25. The non-metallocene catalyst kit of claim 17 or 18, wherein group R₆And a group R₈Which may be the same or different, are each independently isopropyl or tert-butyl.

26. The non-metallocene catalyst kit of claim 17 or 18, wherein the group M is Ti.

27. The non-metallocene catalyst kit of claim 17 or 18, wherein X is chlorine.

28. A method of using a non-metallocene catalyst, wherein the non-metallocene catalyst is the non-metallocene catalyst of any one of claims 1 to 8, a non-metallocene catalyst manufactured by the manufacturing method of any one of claims 9 to 16, or a non-metallocene catalyst manufactured using the non-metallocene catalyst kit of any one of claims 17 to 27, the non-metallocene catalyst being used for olefin polymerization immediately after manufacture.

29. Use of a non-metallocene catalyst as an olefin polymerization catalyst, wherein the non-metallocene catalyst is a non-metallocene catalyst according to any one of claims 1 to 8, a non-metallocene catalyst manufactured by the manufacturing method according to any one of claims 9 to 16, or a non-metallocene catalyst manufactured using the non-metallocene catalyst kit according to any one of claims 17 to 27, the non-metallocene catalyst being used as an olefin polymerization catalyst immediately after manufacture.

30. A method for copolymerizing an olefin and a cycloolefin, comprising the step of copolymerizing an olefin and a cycloolefin by using the non-metallocene catalyst according to any one of claims 1 to 8, the non-metallocene catalyst produced by the production method according to any one of claims 9 to 16, or the non-metallocene catalyst produced by using the non-metallocene catalyst kit according to any one of claims 17 to 27 as an olefin polymerization catalyst.

31. The method of copolymerizing olefin and cycloolefin according to claim 30, wherein the olefin is selected from C_2-6One or more alkenes.

32. The method of copolymerizing an alkene and a cycloolefin according to claim 30, wherein the alkene is ethylene.

33. Use of an aluminoxane in combination with a non-metallocene complex as an olefin polymerization catalyst, wherein the aluminoxane is contacted with at least one non-metallocene complex selected from the group consisting of the following formula (I), the following formula (II), and the following formula (I-1) for 60 to 360 minutes and then immediately used as an olefin polymerization catalyst for olefin polymerization, wherein the molar ratio of the aluminoxane to the non-metallocene complex, calculated as the metal element M, is 300-2000: 1,

In the above formulae, the group R₁To the group R₄Group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C_1-4A straight or branched chain hydrocarbon group; the group Y is O or S; the group A is S or O; radical R₅Is C_1-6A linear or branched alkyl group; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A straight or branched chain hydrocarbon group; radical R₁₀Is hydrogen or C_1-6A straight or branched chain hydrocarbon group; the group M is selected from the group consisting of the elements of group IVB of the periodic Table of the elements;The group X is halogen; symbol- - -represents a coordinate bond.

34. The use as claimed in claim 33, wherein the aluminoxane is one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane.

35. Use according to claim 33 or 34, wherein the contact time is 80-300 minutes.

36. The use of claim 33 or 34, wherein the contact time is 120-250 minutes.

37. Use according to claim 33 or 34, wherein the group R₅Is methyl.

38. Use according to claim 33 or 34, wherein the group R₆And a group R₈Which may be the same or different, are each independently isopropyl or tert-butyl.

39. Use according to claim 33 or 34, wherein the group M is Ti.

40. Use according to claim 33 or 34, wherein X is chloro.

41. A method for copolymerizing an alkene with a cycloolefin, comprising the steps of:

Contacting an aluminoxane with at least one non-metallocene complex selected from the group consisting of those represented by the following formula (I), the following formula (II) and the following formula (I-1) for 60 to 360 minutes to obtain a contact product, wherein the molar ratio of the aluminoxane to the non-metallocene complex in terms of Al is 300-2000: 1, and

Immediately using the contact product as an olefin polymerization catalyst to carry out copolymerization reaction of alkene and cycloolefin,

in the above formulae, the group R₁To the group R₄group R₇And a group R₉May be the same or different and are each independently selected from hydrogen and C₁-₄A straight or branched chain hydrocarbon group; the group Y is O or S; the group A is S or O; radical R₅Is C_1-6A linear or branched alkyl group; radical R₆And a group R₈May be the same or different and are each independently selected from C_3-6A straight or branched chain hydrocarbon group; radical R₁₀Is hydrogen or C_1-6A straight or branched chain hydrocarbon group; the group M is selected from the group consisting of the elements of group IVB of the periodic Table of the elements; the group X is halogen; symbol- - -represents a coordinate bond.

42. The copolymerization process according to claim 41, wherein the aluminoxane is one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane.

43. The copolymerization process of claim 41 or 42, wherein the contact time is from 80 to 300 minutes.

44. The copolymerization process of claim 41 or 42, wherein the contact time is 120-250 minutes.

45. The copolymerization process of claim 41 or 42, wherein the alkene is selected from C_2-6One or more alkenes.

46. The copolymerization process of claim 41 or 42, wherein the alkene is ethylene.

47. The copolymerization process according to claim 41 or 42, wherein,Radical R₅Is methyl.

48. The copolymerization process of claim 41 or 42, wherein the group R₆And a group R₈Which may be the same or different, are each independently isopropyl or tert-butyl.

49. The copolymerization process of claim 41 or 42, wherein the group M is Ti.

50. The copolymerization process of claim 41 or 42, wherein X is chlorine.

51. The copolymerization process of claim 30 or 41, wherein the cyclic olefin is optionally substituted with one or more C_1-10Straight or branched alkyl or C_2-10Straight or branched alkenyl substituted C_3-20A cyclic olefin.

52. The copolymerization process of claim 51, wherein the cyclic olefin is selected from the group consisting of optionally substituted with one or more C_1-10Straight or branched alkyl or C_2-10cyclopentene substituted with linear or branched alkenyl groups, optionally with one or more C_1-10Straight or branched alkyl or C_2-10Cyclopentadiene substituted by a linear or branched alkenyl group, optionally substituted by one or more C_1-10Straight or branched alkyl or C_2-10One or more of linear or branched alkenyl-substituted dicyclopentadiene and a compound represented by the following formula (Y),

In the formula (Y), the groups Ra to Rh may be the same or different and are each independently selected from hydrogen and C_1-10Straight or branched alkyl and C_2-10Straight or branched alkenyl; n is an integer of 0 to 6; symbolRepresents a single bondOr a double bond.

53. The copolymerization process according to claim 51, wherein the groups Ra to Rh, which may be the same or different, are each independently selected from hydrogen and C_1-3Straight or branched alkyl or C_2-3Straight or branched alkenyl.

54. The copolymerization process of claim 51, wherein n is 0 or 1.

55. The copolymerization process of claim 51, wherein the cyclic olefin is one or more selected from the group consisting of norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, 5-methylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, and 8-ethyltetracyclododecene.

56. The copolymerization process of claim 30 or 41, wherein the reaction conditions of the copolymerization reaction include: the reaction temperature is 0-120 ℃, the reaction pressure is 0.1-5.0MPa, the molar ratio of cycloolefin/alkene is 0.1-50: 1, and hydrogen is present or not.

57. The copolymerization process of claim 56, wherein the reaction temperature is from 30 to 90 ℃.

58. The copolymerization process according to claim 56, wherein the reaction pressure is from 0.1 to 2.0 MPa.

59. The copolymerization process of claim 56, wherein the molar ratio of cycloolefin/alkene is from 0.2 to 40: 1.