CN114716599A - Olefin copolymer and preparation method and application thereof - Google Patents

Olefin copolymer and preparation method and application thereof Download PDF

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CN114716599A
CN114716599A CN202110006794.2A CN202110006794A CN114716599A CN 114716599 A CN114716599 A CN 114716599A CN 202110006794 A CN202110006794 A CN 202110006794A CN 114716599 A CN114716599 A CN 114716599A
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cyclopentadienyl
indenyl
diphenylmethylene
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CN114716599B (en
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王伟
侯莉萍
张韬毅
张龙贵
盛建昉
唐毓婧
贾雪飞
任敏巧
郑刚
范国强
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C—CHEMISTRY; METALLURGY
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
    • C08J2343/04—Homopolymers or copolymers of monomers containing silicon

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Abstract

The invention discloses an olefin copolymer, a preparation method and an application thereof, wherein the olefin copolymer comprises structural units shown as a formula (I) and a formula (II):
Figure DDA0002883410530000011
in formula (I), m ≧ 0, and R is selected from the group consisting of1And R2Each independently selected from H, C1～C10When m is 0, R is1Is selected from C1～C10When m is alkyl of>1, repeated R2The same or different; in formula (II), p ≧ 0, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C10Wherein when p is>1, repeated-C (R)2)(R3) -identical or different. The olefin copolymer can be used for film materials. The introduction of silicon-containing monomers into the copolymer can effectively improve copolymerization properties such as lubricity, surface properties and the like.

Description

Olefin copolymer and preparation method and application thereof
Technical Field
The invention belongs to the field of polyolefin, and particularly relates to an olefin copolymer, and a preparation method and application thereof.
Background
Polyolefins are used extensively in daily life, with annual production rates reaching the billions of dollars. The application of a polymer is determined by its physical and mechanical properties, which depend mainly on the composition and structure of the polymer.
Some higher olefins, such as 4-methyl-1-pentene, 3-methyl-1-butene, etc., typically have relatively high melting points for their polymers. These monomers have the common feature that they are branched at the end, and that polymers of normally linear alpha-olefins do not have very high or even undetectable melting points. For example, the melting point of isotactic poly (1-butene) is much lower than that of isotactic polypropylene, and the temperature is only about 140 ℃. However, if the terminal has a branch, such as 3-methyl-1-butene, the melting point of the isotactic polymer may exceed 300 deg.C (Modem, 2014,34(10), 103-105). Some monomers, such as allylcyclopentane, allylcyclohexane, etc., have relatively high melting points after polymerization (ChemCatchem,2016,8, 3218-3223).
Through copolymerization, the processing performance of the high-melting-point polymer can be improved, the toughness of the polymer is improved, and meanwhile, other functional groups are introduced through copolymerization, so that the polymer can be endowed with richer performance.
The organic silicon polymer is the first element organic polymer to be applied industrially, and is also the fastest developing field of the element organic polymers, and a plurality of performances of the organic silicon polymer are unique and precious, and the organic silicon polymer cannot be compared with and substituted by other organic polymers, and becomes an essential novel polymer material in national economy. However, not many silicon-containing monomers are used in polyolefin materials.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides an olefin copolymer, and a preparation method and application thereof. The olefin copolymer comprises two structural units, wherein one structural unit is a monomer containing a silicon element, the copolymer has stereoregularity and a higher melting point, the silicon element endows the copolymer with properties different from those of a hydrocarbon monomer polymer, such as lubricity and surface performance, and the copolymerization can also improve the flexibility of the polymer.
An object of the present invention is to provide an olefin copolymer comprising structural units represented by the formulae (I) and (II):
Figure BDA0002883410510000021
in formula (I), m ≧ 0, and R is selected from the group consisting of1And R2Each independently selected from H, C1～C10Wherein, when m is 0, R is1Is selected from C1～C10Alkyl (i.e., m ═ 0 and R)1Selected from the group consisting of H not being present at the same time) when m is>1, repeated R2The same or different; in formula (II), p ≧ 0, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C10Wherein when p is>1, repeated-C (R)2)(R3) -identical or different.
In a preferred embodiment, in formula (I), R1And R2Each independently selected from H or C1～C 60 ≦ m ≦ 30, wherein, when m ≦ 0, R is1Is selected from C1～C6Alkyl (i.e., m ═ 0 and R)1Selected from H not being present at the same time) when 1<Repeated R when m ≦ 302The same or different; in formula (II), 0 ≦ p ≦ 20, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C6Wherein, when 1 is<repeated-C (R) when p ≦ 202)(R3) -identical or different.
In a further preferred embodiment, in formula (I), 0 ≦ m ≦ 20, and R is not ≠ 01And R2Each independently selected from H, methyl, ethyl, propyl or isopropyl, and when m is 0, R is1Is selected from C1～C5Alkyl (e.g. methyl, ethyl, propyl or isopropyl, i.e. m ═ 0 and R)1Selected from H not being present at the same time) when 1<Repeated R when m ≦ 202The same or different; in formula (II), 0 ≦ p ≦ 10, R1、R2、R3、R4、R5、R6Each independently selected from H, methyl, ethyl, propyl or isopropyl, wherein, when 1<repeated-C (R) when p ≦ 102)(R3) -identical or different.
In a preferred embodiment, the structural unit of formula (I) is polymerized from at least one of the following monomers: 2-methylpropene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-nonene, 2-methyl-1-decene, 2-methyl-1-undecene, 2-methyl-1-dodecene, 2-methyl-1-tridecene, 2-methyl-1-tetradecene, 2-methyl-1-pentadecene, 2-methyl-1-hexadecene, 2-methyl-1-heptadecene, 2-methyl-1-octadecene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3-methyl-1-nonene, 3-methyl-1-decene, 3-methyl-1-undecene, 3-methyl-1-dodecene, 3-methyl-1-tridecene, 3-methyl-1-tetradecene, 3-methyl-1-pentadecene, 3-methyl-1-hexadecene, 3-methyl-1-heptadecene, 3-methyl-1-octadecene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4-methyl-1-heptene, 4-methyl-1-octene, 4-methyl-1-nonene, 4-methyl-1-decene, 4-methyl-1-undecene, 4-methyl-1-dodecene, 4-methyl-1-tridecene, 4-methyl-1-tetradecene, 4-methyl-1-pentadecene, 4-methyl-1-hexadecene, 4-methyl-1-heptadecene, 4-methyl-1-octadecene, 5-methyl-1-hexene, 5-methyl-1-heptene, 5-methyl-1-octene, 5-methyl-1-nonene, 5-methyl-1-decene, 5-methyl-1-undecene, 5-methyl-1-dodecene, 5-methyl-1-tridecene, 5-methyl-1-tetradecene, 5-methyl-1-pentadecene, 5-methyl-1-hexadecene, 5-methyl-1-heptadecene, 5-methyl-1-octadecene, 6-methyl-1-heptene, 6-methyl-1-octene, 6-methyl-1-nonene, 6-methyl-1-decene, 6-methyl-1-undecene, 6-methyl-1-dodecene, 6-methyl-1-tridecene, 6-methyl-1-tetradecene, 6-methyl-1-pentadecene, 6-methyl-1-hexadecene, 6-methyl-1-heptadecene, 6-methyl-1-octadecene, 7-methyl-1-octene, 7-methyl-1-nonene, 7-methyl-1-decene, 7-methyl-1-undecene, 7-methyl-1-dodecene, 7-methyl-1-tridecene, 7-methyl-1-tetradecene, 7-methyl-1-pentadecene, 7-methyl-1-hexadecene, 7-methyl-1-heptadecene, 7-methyl-1-octadecene, 8-methyl-1-nonene, 8-methyl-1-decene, 8-methyl-1-undecene, 8-methyl-1-dodecene, 8-methyl-1-tridecene, 8-methyl-1-tetradecene, 8-methyl-1-pentadecene, 8-methyl-1-hexadecene, 8-methyl-1-heptadecene, 8-methyl-1-octadecene, 9-methyl-1-decene, 9-methyl-1-undecene, 9-methyl-1-dodecene, 9-methyl-1-tridecene, 9-methyl-1-tetradecene, 9-methyl-1-pentadecene, 9-methyl-1-hexadecene, 9-methyl-1-heptadecene, 9-methyl-1-octadecene, 10-methyl-1-undecene, 10-methyl-1-dodecene, 10-methyl-1-tridecene, 10-methyl-1-tetradecene, 10-methyl-1-pentadecene, 10-methyl-1-hexadecene, 10-methyl-1-heptadecene, 10-methyl-1-octadecene, 11-methyl-1-dodecene, 11-methyl-1-tridecene, 11-methyl-1-tetradecene, 11-methyl-1-pentadecene, 11-methyl-1-hexadecene, 11-methyl-1-heptadecene, 11-methyl-1-octadecene, 12-methyl-1-tridecene, 12-methyl-1-tetradecene, 12-methyl-1-pentadecene, 12-methyl-1-hexadecene, 12-methyl-1-heptadecene, 12-methyl-1-octadecene, 13-methyl-1-tetradecene, 13-methyl-1-pentadecene, 13-methyl-1-hexadecene, 13-methyl-1-heptadecene, 13-methyl-1-octadecene, 14-methyl-1-pentadecene, 14-methyl-1-hexadecene, 14-methyl-1-heptadecene, 14-methyl-1-octadecene, 15-methyl-1-hexadecene, 15-methyl-1-heptadecene, 15-methyl-1-octadecene, 16-methyl-1-heptadecene, 16-methyl-1-octadecene, 17-methyl-1-octadecene.
In a preferred embodiment, the structural unit of formula (II) is polymerized from at least one of the following monomers: allyltrimethylsilane, allyltriethylsilane, allyldimethylethylsilane, allylmethyldiethylsilane, allyltriisopropylsilane, 1-butenyltrimethylsilane, 1-pentenyltrimethylsilane, preferably allyltrimethylsilane.
In a preferred embodiment, the molar ratio of the structural unit represented by the formula (I) is 0.1 to 99.9%, and the molar ratio of the structural unit represented by the formula (II) is 99.9 to 0.1%, based on 100% of the total molar amount of the olefin copolymer.
For example, the molar ratios of the structural unit represented by formula (I) and the structural unit represented by formula (II) are 1% and 99%, 5% and 95%, 10% and 90%, 20% and 80%, 30% and 70%, 40% and 60%, 50% and 50%, 60% and 40%, 70% and 30%, 80% and 20%, 90% and 10%, 99% and 1%, respectively.
In a preferred embodiment, the number average molecular weight of the olefin copolymer is 1000 to 1000000, preferably 1000 to 300000, more preferably 1500 to 100000.
In a preferred embodiment, the olefin copolymer has a molecular weight distribution of 1.2 to 3.5, preferably 1.5 to 2.5.
Wherein the molecular weight distribution refers to the ratio of weight average molecular weight to number average molecular weight.
In a preferred embodiment, the olefin copolymer has a melting point of 150 to 280 ℃.
Another object of the present invention is to provide a process for producing an olefin copolymer, which comprises: taking monomers shown in a formula (III) and a formula (IV) as mixed monomers, and reacting in the presence of a metallocene catalyst system to obtain the olefin copolymer:
Figure BDA0002883410510000051
in formula (III), m ≧ 0, and R is selected from the group consisting of1And R2Each independently selected from H, C1～C10When m is 0, R is1Is selected from C1～C10Alkyl (i.e., m ═ 0 and R)1Selected from the group consisting of H not being present at the same time) when m is>1, repeated R2The same or different; in formula (IV), p ≧ 0, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C10Wherein when p is>1, repeated-C (R)2)(R3) -identical or different.
In a preferred embodiment, in formula (III), 0 ≦ m ≦ 30, and R is not equal to 01And R2Each independently selected from H or C1～C6When m is 0, R1Is selected from C1～C6Alkyl (i.e., m ═ 0 and R)1Selected from H not being present at the same time) when 1<Repeated R when m ≦ 302The same or different; in formula (IV), 0 ≦ p ≦ 20, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C6Wherein, when 1 is<repeated-C (R) when p ≦ 202)(R3) -identical or different.
In a further preferred embodiment, in formula (III), 0 ≦ m ≦ 20, and R is not ≠ 01And R2Each independently selected from H, methyl, ethyl, propyl or isopropyl, and when m is 0, R is1Is selected from C1～C5Alkyl (e.g. methyl, ethyl, propyl or isopropyl), i.e. m ═ 0 and R1Selected from H not being present at the same time) when 1<Repeated R when m ≦ 202The same or different; in formula (IV), 0 ≦ p ≦ 10, R1、R2、R3、R4、R5、R6Each independently selected from H, methyl, ethyl, propyl or isopropyl, wherein, when 1<repeated-C (R) when p ≦ 102)(R3) -identical or different.
In a preferred embodiment, the monomer of formula (III) is selected from at least one of the following monomers: 2-methylpropene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-nonene, 2-methyl-1-decene, 2-methyl-1-undecene, 2-methyl-1-dodecene, 2-methyl-1-tridecene, 2-methyl-1-tetradecene, 2-methyl-1-pentadecene, 2-methyl-1-hexadecene, 2-methyl-1-heptadecene, 2-methyl-1-octadecene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3-methyl-1-nonene, 3-methyl-1-decene, 3-methyl-1-undecene, 3-methyl-1-dodecene, 3-methyl-1-tridecene, 3-methyl-1-tetradecene, 3-methyl-1-pentadecene, 3-methyl-1-hexadecene, 3-methyl-1-heptadecene, 3-methyl-1-octadecene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4-methyl-1-heptene, 4-methyl-1-octene, 4-methyl-1-nonene, 4-methyl-1-decene, 4-methyl-1-undecene, 4-methyl-1-dodecene, 4-methyl-1-tridecene, 4-methyl-1-tetradecene, 4-methyl-1-pentadecene, 4-methyl-1-hexadecene, 4-methyl-1-heptadecene, 4-methyl-1-octadecene, 5-methyl-1-hexene, 5-methyl-1-heptene, 5-methyl-1-octene, 5-methyl-1-nonene, 5-methyl-1-decene, 5-methyl-1-undecene, 5-methyl-1-dodecene, 5-methyl-1-tridecene, 5-methyl-1-tetradecene, 5-methyl-1-pentadecene, 5-methyl-1-hexadecene, 5-methyl-1-heptadecene, 5-methyl-1-octadecene, 6-methyl-1-heptene, 6-methyl-1-octene, 6-methyl-1-nonene, 6-methyl-1-decene, 6-methyl-1-undecene, 6-methyl-1-dodecene, 6-methyl-1-tridecene, 6-methyl-1-tetradecene, 6-methyl-1-pentadecene, 6-methyl-1-hexadecene, 6-methyl-1-heptadecene, 6-methyl-1-octadecene, 7-methyl-1-octene, 7-methyl-1-nonene, 7-methyl-1-decene, 7-methyl-1-undecene, 7-methyl-1-dodecene, 7-methyl-1-tridecene, 7-methyl-1-tetradecene, 7-methyl-1-pentadecene, 7-methyl-1-hexadecene, 7-methyl-1-heptadecene, 7-methyl-1-octadecene, 8-methyl-1-nonene, 8-methyl-1-decene, 8-methyl-1-undecene, 8-methyl-1-dodecene, 8-methyl-1-tridecene, 8-methyl-1-tetradecene, 8-methyl-1-pentadecene, 8-methyl-1-hexadecene, 8-methyl-1-heptadecene, 8-methyl-1-octadecene, 9-methyl-1-decene, 9-methyl-1-undecene, 9-methyl-1-dodecene, 9-methyl-1-tridecene, 9-methyl-1-tetradecene, 9-methyl-1-pentadecene, 9-methyl-1-hexadecene, 9-methyl-1-heptadecene, 9-methyl-1-octadecene, 10-methyl-1-undecene, 10-methyl-1-dodecene, 10-methyl-1-tridecene, 10-methyl-1-tetradecene, 10-methyl-1-pentadecene, 10-methyl-1-hexadecene, 10-methyl-1-heptadecene, 10-methyl-1-octadecene, 11-methyl-1-dodecene, 11-methyl-1-tridecene, 11-methyl-1-tetradecene, 11-methyl-1-pentadecene, 11-methyl-1-hexadecene, 11-methyl-1-heptadecene, 11-methyl-1-octadecene, 12-methyl-1-tridecene, 12-methyl-1-tetradecene, 12-methyl-1-pentadecene, 12-methyl-1-hexadecene, 12-methyl-1-heptadecene, 12-methyl-1-octadecene, 13-methyl-1-tetradecene, 13-methyl-1-pentadecene, 13-methyl-1-hexadecene, 13-methyl-1-heptadecene, 13-methyl-1-octadecene, 14-methyl-1-pentadecene, 14-methyl-1-hexadecene, 14-methyl-1-heptadecene, 14-methyl-1-octadecene, 15-methyl-1-hexadecene, 15-methyl-1-heptadecene, 15-methyl-1-octadecene, 16-methyl-1-heptadecene, 16-methyl-1-octadecene, 17-methyl-1-octadecene.
The double bond of the monomer shown in the formula (III) is at one end of the monomer molecule, the monomer molecule is not normal olefin and is required to have a branched chain, and the branched chain can be normal alkyl, alkyl with a branched chain, and a benzene ring or other condensed rings. The number of carbons in the main chain is not limited to 18 carbon atoms, and may be more.
In a preferred embodiment, the monomer of formula (IV) is selected from the group consisting of allyltrimethylsilane, allyltriethylsilane, allyldimethylethylsilane, allylmethyldiethylsilane, allyltriisopropylsilane, 1-butenyltrimethylsilane, and 1-pentenyltrimethylsilane, preferably allyltrimethylsilane.
In a preferred embodiment, the monomer represented by formula (III) is used in a molar amount of 0.1 to 99.9% and the monomer represented by formula (IV) is used in a molar amount of 99.9 to 0.1% based on 100% of the total molar amount of the monomer represented by formula (III) and the monomer represented by formula (IV).
For example, the molar ratio of the monomer represented by the formula (III) is 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99%. The molar ratio of the monomer represented by the formula (IV) is 99%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 1%.
As shown in FIG. 10, as the content of the structural unit represented by the formula (II) in the copolymer increases, the melting point of the copolymer tends to decrease and then increase.
In a preferred embodiment, the metallocene catalyst system comprises a metallocene compound and a cocatalyst.
In a further preferred embodiment, the cocatalyst is selected from boron compounds and/or aluminum compounds.
In a preferred embodiment, the metallocene compound is selected from compounds of formula (V):
Figure BDA0002883410510000081
in formula (V): cp1And Cp2Each independently selected from cyclopentadienyl and C1～C20With a hydrocarbon radical of mono-or polysubstituted cyclopentadienyl, indenyl, C1～C20Alkyl mono-or polysubstituted indenyl, fluorenyl or C1～C20The hydrocarbyl-mono-or polysubstituted fluorenyl; and/or M is selected from titaniumZirconium or hafnium; and/or, X1And X2Each independently selected from a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbyl group; and/or, n ═ 0 or 1; and/or Q is the linkage Cp1And Cp2Is selected from the group consisting of-Si (R)a)(Rb)-、-C(Ra)(Rb)-、-Si(Ra)(Rb)Si(Rc)(Rd)-、-C(Ra)(Rb)C(Rc)(Rd) -, in which Ra、Rb、Rc、RdIndependently selected from H or C1～C20A hydrocarbon group of (1).
Wherein, when n ═ 0, the compound represented by formula (V) is a non-bridged metallocene; when n is 1, the compound of formula (V) is a bridged metallocene, and Cp is1And Cp2Are connected into a ring.
In a further preferred embodiment, in formula (V), M is selected from zirconium; and/or, X1And X2Each independently selected from halogen atoms (e.g., chlorine atoms).
In a still further preferred embodiment, the metallocene compound is selected from diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (4,4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4,4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4,4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4' -methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4,4' -methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4' -methyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4-methyl-4 ' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3,3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (3,3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3,3 '-trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4,4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4,4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4 '-chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4,4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride or (4,4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, rac-vinylbisindenyl zirconium dichloride, rac-dimethylsilyldiindenyl zirconium dichloride, rac-dimethylsilyldi (2-methyl-indenyl) zirconium dichloride, rac-dimethylsilyldi (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyldi (tetramethylcyclopentadienyl) (tert-butylamino) titanium dichloride, and dimethylsilyldi (tetramethylcyclopentadienyl) (cyclohexylamino) titanium dichloride.
Among them, the inventor finds out through a large amount of experiments that: syndiotactic copolymers may be obtained when a substituted methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride is used and isotactic copolymers may be obtained when a racemic ethylene bridged bisindenyl zirconium dichloride is used.
In a preferred embodiment, the concentration of the metallocene compound in the polymerization system is 1X10-2Mol per liter to 1x10-6Mol per liter, preferably 1X10-3Mol per liter to 1x10-5Moles per liter.
In a preferred embodiment, the cocatalyst is selected from alkylaluminoxanes, preferably methylaluminoxane.
In a further preferred embodiment, the molar ratio of the metallocene compound to the alkylalumoxane is from 1:50 to 1:30000, preferably from 1:200 to 1:10000, more preferably from 1:500 to 1:5000, most preferably from 1:1000 to 1: 3000.
In another preferred embodiment, the cocatalyst is selected from the group consisting of boron compounds and aluminum compounds.
In a further preferred embodiment, the boron compound is selected from B (C)6F5)3Or [ B (C)6F5)3]4 -[Ph3C]+Or [ B (C)6F5)3]4 -[PhNHMe2]+(ii) a And/or the general formula of the aluminum compound is AlRxY3-xWherein R is selected from the group consisting of hydrocarbyl, preferably selected from methyl, ethylene, isobutyl, n-hexyl, n-octyl, more preferably ethyl or isobutyl; y is selected from anions, preferably from halogen atoms, alkoxy groups, aryloxy groups, more preferably from chlorine atoms; x is 1 or 2 or 3, preferably 2 or 3.
In a still further preferred embodiment, the molar ratio of the metallocene compound to the boron compound is from 1:1 to 1:3, preferably from 1:1 to 1:2, more preferably from 1:1.1 to 1: 1.5; and/or the molar ratio of boron compound to aluminum compound is from 1:10 to 1:1000, preferably from 1:20 to 1:500, more preferably from 1:50 to 1: 200.
In a preferred embodiment, the reaction is carried out in a solvent or in the bulk of the monomer.
In a further preferred embodiment, the solvent includes, but is not limited to, one or a mixture of two or more of toluene, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, n-octane.
In a preferred embodiment, the temperature of the reaction is from 0 ℃ to 150 ℃, preferably from 25 ℃ to 100 ℃.
In a further preferred embodiment, the reaction time is from 1 minute to 72 hours, preferably from 20 minutes to 24 hours.
The third object of the present invention is to provide the use of the olefin copolymer according to the first object of the present invention or the olefin copolymer obtained by the production method according to the second object of the present invention in a film.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects: the introduction of silicon-containing monomers into the copolymer can effectively improve copolymerization properties such as lubricity and surface properties, and when the silicon-containing monomers are main monomers, the copolymer has a higher melting point (as in example 8).
Drawings
FIG. 1 shows the polymer of comparative example 113A C-NMR spectrum;
FIG. 2 shows the polymer of comparative example 313A C-NMR spectrum;
FIG. 3 shows the polymer of example 313A C-NMR spectrum;
FIG. 4 shows the polymer of example 613A C-NMR spectrum;
FIG. 5 shows the polymer of example 713A C-NMR spectrum;
FIG. 6 shows the GPC curve for the polymer in example 3;
FIG. 7 shows the GPC curve for the polymer in example 6;
FIG. 8 shows the GPC curve for the polymer in example 7;
FIG. 9 shows the DSC curve of the polymer in example 4;
FIG. 10 is a schematic view showing the relationship between the content of the formula (II) in the copolymer and the melting point of the copolymer, wherein in FIG. 10, A represents a homopolymer having a structure represented by the formula (I), B represents a homopolymer having a structure represented by the formula (II), the content of the structural unit represented by the formula (II) increases gradually from the left to the right on the abscissa, and the melting point of the copolymer increases gradually from the bottom to the top on the ordinate.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
Comparative example polymerization of 14-methyl-1-pentene
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 2.5 ml of 4-methyl-1-pentene and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of catalyst solution (containing 5. mu. mol of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.56g polymer with weight average molecular weight Mw of 2.65x104Molecular weight distribution MWD of 1.90; differential scanning calorimetry detection: the melting point was 149.5 ℃ and the enthalpy of fusion was 8.26J/g.
Comparative example polymerization of 24-methyl-1-pentene
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 2.5 ml of 4-methyl-1-pentene and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of catalyst solution (containing 5. mu. mol of racemic ethylenebisindenyl zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminatedPouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, and filtering to obtain the polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 1.62g polymer with weight average molecular weight Mw of 8.5x10 by gel permeation chromatography3Molecular weight distribution MWD ═ 1.94; differential scanning calorimetry detection: the melting point was 208.2 ℃ and the enthalpy of fusion was 45.1J/g.
Comparative example 3 polymerization of allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 3.0 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.77g polymer with weight average molecular weight Mw of 4.63 × 10 by gel permeation chromatography4Molecular weight distribution MWD ═ 1.83; differential scanning calorimetry detection: the melting point was 246.2 ℃ and the enthalpy of fusion was 6.77J/g.
Comparative example 4 polymerization of allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 3.0 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of racemic ethylenebisindenyl zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.69g polymer with weight average molecular weight Mw of 6.1x103Molecular weight distribution MWD ═ 1.75; differential scanning calorimetry detection: the melting point was 281.3 ℃ and the enthalpy of fusion was 19.4J/g.
EXAMPLE 14 copolymerization of methyl-1-pentene and allyltrimethylsilane
Fully driedThe polymerization bottle is vacuumized, flushed with nitrogen and repeated for three times, and finally, nitrogen is filled. 2.0 ml of 4-methyl-1-pentene, 0.6 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.28g polymer with weight average molecular weight Mw of 2.54 × 104Molecular weight distribution MWD ═ 1.85;
this example 1 gives a random copolymer of chemical composition, but it is also syndiotactic in the stereotacticity.
EXAMPLE 24 copolymerization of methyl-1-pentene with allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 1.5 ml of 4-methyl-1-pentene, 1.2 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.30g polymer with weight average molecular weight Mw of 3.73x104The molecular weight distribution MWD was 1.78.
The random copolymer obtained in example 2 was of chemical composition, but was syndiotactic in stereoregularity.
EXAMPLE 34 copolymerization of methyl-1-pentene and allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 1.0 ml of 4-methyl-1-pentene, 1.8 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing methylaluminoxane) were added10 mmol), warmed to 50 deg.c, and started by adding 1 ml of a catalyst solution containing 5 μmol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.41g polymer with weight average molecular weight Mw of 2.88x104Molecular weight distribution, MWD ═ 1.80;13C-NMR shows that the polymer contains 89 mol% of allyl trimethyl silane structural units.
This example 3 gives a random copolymer of chemical composition, but with a syndiotactic stereoregularity in the stereodistribution.
Example 44 copolymerization of methyl-1-pentene and allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 0.5 ml of 4-methyl-1-pentene, 2.4 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.55g polymer with weight average molecular weight Mw of 3.46x10 by gel permeation chromatography4Molecular weight distribution MWD ═ 1.84; differential scanning calorimetry detection: a melting point of 236.0 ℃ and a melting enthalpy of 2.68J/g were detected.
In this example 4, a syndiotactic copolymer having a high degree of regularity was obtained, and a melting point of 236.0 ℃ was detected.
EXAMPLE 54 copolymerization of methyl-1-pentene and allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 2.0 ml of 4-methyl-1-pentene, 0.6 ml of allyltrimethylsilane, and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added theretoThe temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of rac-ethylenebisindenyl zirconium dichloride) was added to start the timer. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 1.56g polymer with weight average molecular weight Mw of 4.7x10 by gel permeation chromatography3Molecular weight distribution MWD ═ 1.69; differential scanning calorimetry detection: a melting point of 158.7 ℃ and a melting enthalpy of 25.2J/g were detected.
The copolymer obtained in this example 5 had an isotactic structure, had a high degree of regularity, and the melting point was detected to be 158.7 ℃.
EXAMPLE 64 copolymerization of methyl-1-pentene with allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 1.5 ml of 4-methyl-1-pentene, 1.2 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of racemic ethylene bridged bisindenyl zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.96g polymer with weight average molecular weight Mw of 5.0x103Molecular weight distribution MWD of 1.71;13C-NMR shows that the polymer contains 66 mol% of allyl trimethylsilane structural unit.
The random copolymer of chemical composition obtained in example 6 was isotactic in stereoregularity.
Example 74 copolymerization of methyl-1-pentene and allyltrimethylsilane
The polymerization bottle after being fully dried is vacuumized, flushed by nitrogen for three times, and finally filled with nitrogen. 1.0 ml of 4-methyl-1-pentene, 1.8 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added thereto, the temperature was raised to 50 ℃ and 1 ml of catalyst solution (containing 5. mu. mol of methylaluminoxane) was added theretoRacemic ethylene bridged bisindenyl zirconium dichloride) was started. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain polymer 1.15g, and gel permeation chromatography to obtain polymer with weight average molecular weight Mw of 6.2x103Molecular weight distribution MWD ═ 1.85;13C-NMR detects that the polymer contains 89 mol% of allyl trimethyl silane structural unit; differential scanning calorimetry detection: a melting point of 251.5 ℃ was detected, with a melting enthalpy of 1.72J/g.
The copolymer obtained in this example 7 had an isotactic structure and a high degree of regularity, and the melting point was detected to be 251.5 ℃.
EXAMPLE 84 copolymerization of methyl-1-pentene and allyltrimethylsilane
The polymerization bottle fully dried is vacuumized, flushed with nitrogen and repeated for three times, and finally filled with nitrogen. 0.5 ml of 4-methyl-1-pentene, 2.4 ml of allyltrimethylsilane and 6 ml of methylaluminoxane solution (containing 10 mmol of methylaluminoxane) were added, the temperature was raised to 50 ℃ and 1 ml of a catalyst solution (containing 5. mu. mol of racemic ethylene bridged bisindenyl zirconium dichloride) was added to start timekeeping. After 60 minutes, the reaction was terminated, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. Vacuum drying at 60 deg.C for 24 hr to obtain 0.71g polymer with weight average molecular weight Mw of 7.5x103Molecular weight distribution MWD ═ 1.69; differential scanning calorimetry detection: a melting point of 273.2 ℃ was detected with a melting enthalpy of 16.5 J.g.
The copolymer obtained in this example 8 has an isotactic structure, has a high degree of regularity, and has a melting point detected as 273.2 ℃.
Comparative example 5
The procedure of example 4 was repeated except that an equal amount of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride was used in place of the diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride).
0.19g of a polymer was obtained, and the weight-average molecular weight Mw of the polymer was 1.37X10 according to gel permeation chromatography4Molecular weight distribution MWD ═1.76; the melting point and glass transition temperature could not be detected by differential scanning calorimetry.
Comparative example 6
The procedure of example 7 was repeated except that an equal amount of pentamethylcyclopentadienyl-2, 6-diisopropylphenoxytitanium dichloride was used in place of the racemic ethylenebridodiindenyl zirconium dichloride.
0.53g of a polymer was obtained, and the weight-average molecular weight Mw of the polymer was 1.92X10 according to gel permeation chromatography4Molecular weight distribution MWD of 1.81; the melting point and glass transition temperature could not be detected by differential scanning calorimetry.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (15)

1. An olefin copolymer comprising structural units represented by formula (I) and formula (II):
Figure FDA0002883410500000011
in formula (I), m ≧ 0, and R is selected from the group consisting of1And R2Each independently selected from H, C1～C10When m is 0, R is1Is selected from C1～C10When m is alkyl of>1, repeated R2The same or different; in formula (II), p ≧ 0, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C10Wherein when p is>1, repeated-C (R)2)(R3) -identical or different.
2. The olefin copolymer according to claim 1, wherein in the formula (I), 0 ≦ m ≦ 30, and R is not less than 01And R2Each independently selected from H or C1～C6When m is 0, R1Is selected from C1～C6Alkyl of (2) when 1<Repeated R when m ≦ 302The same or different; in formula (II), 0 ≦ p ≦ 20, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C6Wherein, when 1 is<repeated-C (R) when p ≦ 202)(R3) -identical or different.
3. The olefin copolymer according to claim 1, wherein in the formula (I), 0 ≦ m ≦ 20, and R is not less than 01And R2Each independently selected from H, methyl, ethyl, propyl or isopropyl, wherein, when m ═ 0, R1Is selected from C1～C5Alkyl of (2) when 1<Repeated R when m ≦ 202The same or different; in formula (II), 0 ≦ p ≦ 10, R1、R2、R3、R4、R5、R6Each independently selected from H, methyl, ethyl, propyl or isopropyl, wherein, when 1<repeated-C (R) when p ≦ 102)(R3) -identical or different.
4. The olefin copolymer according to any one of claims 1 to 3, wherein the molar ratio of the structural unit represented by the formula (I) is 0.1 to 99.9%, and the molar ratio of the structural unit represented by the formula (II) is 99.9 to 0.1%, based on 100% of the total molar amount of the olefin copolymer.
5. The olefin copolymer according to claim 4,
the number average molecular weight of the olefin copolymer is 1000-1000000, preferably 1000-300000; and/or
The molecular weight distribution of the olefin copolymer is 1.2-3.5, preferably 1.5-2.5.
6. A process for producing an olefin copolymer as claimed in any one of claims 1 to 5, which comprises: taking monomers shown in a formula (III) and a formula (IV) as mixed monomers, and reacting in the presence of a metallocene catalyst system to obtain the olefin copolymer:
Figure FDA0002883410500000021
in formula (III), m ≧ 0, and R is not equal to 01And R2Each independently selected from H, C1～C10When m is 0, R is1Is selected from C1～C10When m is alkyl of>1, repeated R2The same or different; in formula (IV), p ≧ 0, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C10Wherein when p is>1, repeated-C (R)2)(R3) -identical or different.
7. The method according to claim 6, wherein in formula (III), 0 ≦ m ≦ 30, and R is not less than 01And R2Each independently selected from H or C1～C6When m is 0, R1Is selected from C1～C6Alkyl of (2) when 1<Repeated R when m ≦ 302The same or different; in formula (IV), 0 ≦ p ≦ 20, R1、R2、R3、R4、R5、R6Each independently selected from H or C1～C6Wherein, when 1 is<repeated-C (R) when p ≦ 202)(R3) -the same or different;
preferably, in formula (III), 0 ≦ m ≦ 20, R when m ≠ 01And R2Each independently selected from H, methyl, ethyl, propyl or isopropyl, and when m is 0, R is1Is selected from C1～C5Alkyl of (2)When 1 is<Repeated R when m ≦ 202The same or different; in formula (IV), 0 ≦ p ≦ 10, R1、R2、R3、R4、R5、R6Each independently selected from H, methyl, ethyl, propyl or isopropyl, wherein, when 1<repeated-C (R) when p ≦ 102)(R3) -identical or different.
8. The method according to claim 6, wherein the monomer of formula (III) is used in a molar amount of 0.1 to 99.9% and the monomer of formula (IV) is used in a molar amount of 99.9 to 0.1% based on 100% of the total molar amount of the monomer of formula (III) and the monomer of formula (IV).
9. The preparation method according to claim 6, wherein the metallocene catalyst system comprises a metallocene compound and a cocatalyst, wherein the cocatalyst is selected from a boron compound and/or an aluminum compound, preferably the concentration of the metallocene compound in the polymerization system is 1x10-2Mol per liter to 1x10-6Mol per liter, preferably 1X10-3Mol per liter to 1x10-5Moles per liter.
10. The process according to claim 9, wherein the metallocene compound is selected from compounds of formula (V):
Figure FDA0002883410500000031
in formula (V): cp1And Cp2Each independently selected from cyclopentadienyl and C1～C20With hydrocarbon radicals being monosubstituted or polysubstituted cyclopentadienyl, indenyl, C1～C20Alkyl mono-or polysubstituted indenyl, fluorenyl or C1～C20The hydrocarbyl-mono-or polysubstituted fluorenyl; and/or, M is selected from titanium, zirconium or hafnium; and/or, X1And X2Each independently selected from the group consisting of pro-halogensA nitrile group, an alkoxy group, an aryloxy group, or a hydrocarbon group; and/or, n ═ 0 or 1; and/or Q is the linkage Cp1And Cp2Is selected from the group consisting of-Si (R)a)(Rb)-、-C(Ra)(Rb)-、-Si(Ra)(Rb)Si(Rc)(Rd)-、-C(Ra)(Rb)C(Rc)(Rd) -, in which Ra、Rb、Rc、RdIndependently selected from H or C1～C20A hydrocarbon group of (2).
11. The process according to claim 10, wherein the metallocene compound is selected from the group consisting of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (4,4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4,4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4,4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, and mixtures thereof, (4,4 '-methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4,4' -methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4 '-methyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4-methyl-4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3,3 '-trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (3,3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride -zirconium dichloride, (3,3 '-trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4,4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4,4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4,4 '-chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4,4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride or (4,4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, rac-vinylbisindenyl zirconium dichloride, rac-dimethylsilyldiindenyl zirconium dichloride, rac-dimethylsilyldi (2-methyl-indenyl) zirconium dichloride, rac-dimethylsilyldi (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyldi (tetramethylcyclopentadienyl) (tert-butylamino) titanium dichloride, and dimethylsilyldi (tetramethylcyclopentadienyl) (cyclohexylamino) titanium dichloride.
12. A method of preparation according to claim 9, wherein the cocatalyst is selected from alkylaluminoxanes, preferably methylaluminoxane; more preferably, the molar ratio of said metallocene compound to said alkylalumoxane is from 1:50 to 1:30000, preferably from 1:200 to 1: 10000.
13. The method of claim 9, wherein the cocatalyst is selected from the group consisting of boron compounds and aluminum compounds, wherein:
the boron compound is selected from B (C)6F5)3Or [ B (C)6F5)3]4 -[Ph3C]+Or [ B (C)6F5)3]4 -[PhNHMe2]+(ii) a And/or the general formula of the aluminum compound is AlRxY3-xWherein R is selected from the group consisting of hydrocarbyl, preferably selected from methyl, ethylene, isobutyl, n-hexyl, n-octyl, more preferably ethyl or isobutyl; y is selected from anions, preferably from halogen atoms, alkoxy groups, aryloxy groups, more preferably from chlorine atoms; x is 1 or 2 or 3, preferably 2 or 3;
preferably, the molar ratio of the metallocene compound to the boron compound is from 1:1 to 1:3, preferably from 1:1 to 1: 2; and/or the molar ratio of boron compound to aluminum compound is from 1:10 to 1:1000, preferably from 1:20 to 1: 500.
14. The method of any one of claims 6 to 13, wherein the reaction is carried out at a temperature of from 0 ℃ to 150 ℃, preferably from 25 ℃ to 100 ℃; and/or the reaction time is from 1 minute to 72 hours, preferably from 20 minutes to 24 hours.
15. Use of the olefin copolymer according to any one of claims 1 to 5 or the olefin copolymer obtained by the production method according to any one of claims 6 to 14 in a film.
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