CN105820280A - Ethylene-olefin copolymer and preparation thereof - Google Patents

Ethylene-olefin copolymer and preparation thereof Download PDF

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Publication number
CN105820280A
CN105820280A CN201610022539.6A CN201610022539A CN105820280A CN 105820280 A CN105820280 A CN 105820280A CN 201610022539 A CN201610022539 A CN 201610022539A CN 105820280 A CN105820280 A CN 105820280A
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group
indenyl
double
dimethyl
ethylene
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杨春柄
李泳周
李殷雄
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Hanwha TotalEnergies Petrochemical Co Ltd
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Samsung Total Petrochemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/11—Melt tension or melt strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention provides an ethylene-olefin copolymer. Long-chain branches are introduced into the copolymer, so that the inflection point performance is realized in a dynamic shearing viscosity measuring process, the load in an extrusion processing process is lowered, the melt strength is increased, and the bubble stability is improved in a blown film machining process.

Description

Copolymer based on ethylene and preparation thereof
The related application of cross reference
The application based on require that on January 23rd, 2015 submits to the priority of the korean patent application No.10-2015-0011027 of Korean Intellectual Property Office, the disclosure of which is incorporated by reference herein in its entirety.
Technical field
The present invention relates to a kind of copolymer based on ethylene, it has the extrusion molded processability of excellence, more specifically, relate to such copolymer based on ethylene, it has underload during extrusion, and providing excellent bubble stability, this is owing to being had a long chain branches of predetermined component by introducing and the high fondant-strength during the film course of processing, or relates more specifically to linear polyethylene copolymer and create wide molecular weight distribution.
Background of invention
By using the metallocene-based polyethylene resins prepared by existing metallocene catalyst to provide the mechanical performance of excellence in thin film molding process, this is owing to its molecule performance.But, due to Narrow Molecular Weight Distribution, machining load is high, and the probability producing melt fracture in extrusion process is high.Additionally, melt strength is low, therefore there is many limitations in commercial Application, such speed of production cannot increase, and this is owing to the bubble unstability when processing wide inflation film.Therefore, require the processability of the improvement for metallocene-based polyethylene resins and the melt strength of improvement always.
Generally, in order to reduce machining load, attempting making great efforts to widen molecular weight distribution, but in this case, extrusion load reduces to a certain extent, melt strength is practically without improving, and the bubble stability the most not guaranteed in the course of processing.In korean patent application No.10-2007-7022531, it is proposed that by mixing, there is the method that the polymer of high molecular increases molecular weight distribution and melt strength, but this is unsuitable for thin film application.In addition, have been proposed for a kind of method (korean patent application No.10-2000-7008658) etc. by using heterogeneous catalysis or reaction of high order to increase molecular weight distribution, but the most in this case, described method is also unsuitable for needing the thin film application of the transparency.
Additionally, the method easily using the resin (LDPE etc.) of the blended long chain branches performance with high fondant-strength of part, and in this case, it is not prevented from the deterioration (United States Patent (USP) No.6114457) of the mechanical performance of end product.
As an actual method, it has been proposed that long chain branches to be introduced the method (United States Patent (USP) No.5272236 and korean patent application No.10-1999-7007119) of Metallocenyl linear polyethylene resin.But, the method is carried out with following form, and the macromonomer being in end group double bond state wherein produced in polymerization procedure is embedded in main chain, as comonomer.Therefore, macromonomer based on this reaction mechanism limits to solution methods, is wherein easy close to polymerization catalyst point, and due to the low content of embedded LCB, therefore significantly improves for melt strength and do not have big impact.
In addition, propose the method (korean patent application No.10-2004-0029640) being introduced long chain branches by the additionally arbitrarily large molecule monomer of injection, but the method is following method, it is suitable only for slurry reaction, and may not apply to gas phase polymerization, because the macromonomer of 1-octene or bigger cannot inject in a large number due to the recovery problem of non-product.
The cross-linking reaction proposing the polymer by additionally producing increases the method (United States Patent (USP) No.4714716) of melt strength.But, the method has the such as gelation of following problem, because extrusion cross-linking reaction is extremely difficult, controls the difficulty of melt flow index, and transparency deterioration.
Summary of the invention
An object of the invention is to provide a kind of copolymer resin based on ethylene, it has the advantage that by introducing long chain branches to Metallocenyl linear ethylene copolymer, owing to high fondant-strength has high bubble stability in film manufacturing process and reduces machining load in extrusion process.
In addition, an object of the invention is to provide a kind of copolymer resin based on ethylene, it has the advantage that the degraded in mechanical properties preventing thin film, and be suitable to different processing methods, this owing to existing there is identical melt flow index and the copolymer based on ethylene of density compared with high processability and melt strength.
The invention provides a kind of copolymer based on ethylene with concrete property for realize above-mentioned target, it is different from and uses metallocene polymerization catalyst system by the existing metallocene based polyolefins (co) polymer prepared by gas-phase polymerization.
The copolymer based on ethylene of the present invention has following performance such as 1) melt flow index is 0.1-15.0g/10min (190 DEG C and weight 2.16Kg), 2) density is 0.900-0.929g/mL, 3) molecular weight distribution (weight-average molecular weight/number-average molecular weight) is 2.5-6.0, with 4) in the dependency of complex modulus and phase angle, the correlation curve of phase angle and complex modulus is 103-107Modulus of complex number value between there is flex point, it is measured by Dynamic shear viscosity measurement, and flex point phase angle (critical phase angle δ c) is 20-70.The copolymer based on ethylene of the present invention has performance 1)-4) there is excellent processability the effect such as bubble stability in film manufacturing process and high fondant-strength.
In addition, in the copolymer based on ethylene of the present invention, gross weight based on this copolymer, the content of alpha-olefin (it is comonomer) is preferably 1-20wt% and MFRR value, and (it is melt flow index (MI measured under 190 DEG C and 21.6kg21) and melt flow index (MI measured under 190 DEG C and 2.16kg2) ratio (MI21/MI2)) preferably 15-100.When co-monomer content and melt flow index ratio (MFRR) deviate described scope, it is difficult to show the performance of the copolymer resin based on ethylene being suitable to different processing methods not deteriorating the mechanical performance of the thin film of target of the present invention due to high working property and melt strength, and therefore it is not preferred.
Hereinafter, will be described in present disclosure.
When there are not other definition, technical term used by the present invention has the implication that those skilled in the art are generally understood.
Critical phase angle (δ c) used by the present invention, in rheological method, is compared the polymeric material with different structural behaviours, and described method is particularly well-suited to detect the long chain branches degree of copolymer based on ethylene.The method is referred to as Van-GurpPalmen analysis and (sees RheologyBulletin, 1998,67,5-8,2.CorrelationsbetweentheCharacteristicRheologicalQuantit iesandMolecularStructureofLong-ChainBranchedMetalloceneC atalyzedPolyethylenes, Macromolecules, 2011,44,5401-5413).The polyethylene (PE) with linear structure and the polyethylene with long chain branches (LCB) structure show different behaviors by phase angle displacement (δ) and the figure of complex modulus (G*), it is available from the dynamic frequency scanning measured by ARES device, and in the case of usual linear alpha-alkene copolymer, phase angle is close to 90 °, and it tends to towards the region that wherein complex modulus is little be smooth.But, include in the case of long chain branches (LCB) at resin, general curve changes to form flex point, and this is referred to as critical phase angle (δ c), and along with this value reduces, the content of LCB increases.The reason formed according to analysis flex point is when complex modulus increases, and according to the existence of LCB, compared with linear polymer, quickly shows the elasticity of resin.Detailed analysis method is by described in following exemplary.
Hereinafter, copolymer based on ethylene and the preparation thereof of the present invention will be described.Hereinafter, the preferred embodiment of this preparation method will be described, but the invention is not restricted to this embodiment.
[metallocene catalyst]
The copolymer based on ethylene of the present invention is in Gas-phase reactor, by using metallocene catalyst to be polymerized and prepare, and this metallocene catalyst (it is suitable to prepare copolymer based on ethylene, and it can introduce present invention LCB to be provided and control the rheological property that the present invention is to be provided) can be prepared by the preparation method including below step:
(1) aikyiaiurnirsoxan beta, metallocene compound, titanocenes compound or Binary catalysts are supported on carrier,
(2) catalyst of the load obtained in use organic solvent cleaning step (1)；With
(3) catalyst as catalyst fines cleaned in step (2) after the drying, is collected.
In the preparation method of metallocene catalyst, the carrying method of step (1) can be carried out as got off: adding and stir by by the metallocene compound in aluminoxanes solution, titanocenes compound or Binary catalysts are dissolved in carrier pulp the solution (carrying method (a)) obtained.Selectable, the load-reaction of step (1) can be carried out as got off: by metallocene compound, titanocenes compound or Binary catalysts add and are stirred in the carrier pulp of aikyiaiurnirsoxan beta load, and the carrier pulp of this aikyiaiurnirsoxan beta load is by adding aikyiaiurnirsoxan beta and being stirred in carrier pulp be carried in carrier aikyiaiurnirsoxan beta obtain (carrying method (b)).
Metallocene compound kind used in step (1) is not particularly limited, but as preferred example, this metallocene compound can include dicyclopentadienyl metallocene, crosslinking metallocene or monocyclopentadienyl metallocene.
First, this dicyclopentadienyl metallocene can be as shown in following formula (1).
(CpRn)(CpR’m)MLq(1)
Here Cp is cyclopentadienyl group, indenyl or fluorenyl,
R and R ' represents hydrogen, alkyl, alkyl ether, allyl ether, phosphine or amine independently of one another,
L represents alkyl, pi-allyl, aryl alkyl, amido (amide), alkoxyl or halogen,
M represents periodic chart the 4th or 5 group 4 transition metal,
Integer in the range of n, m and q are the most following: 0≤n < 5,0≤m < 5, and 1≤q≤4.
This crosslinking metallocene can be as shown in following formula (2).
Q(CpRn)(CpR’m)MLq(2)
Here Cp, R, R ', M with L each has the implication identical with formula (1),
Q is the crosslink part between Cp ring, and represents dialkyl group, alkylaryl, diaryl silicon or have the alkyl of 1-20 carbon atom, and
Integer in the range of n, m and q are the most following: 0≤n < 4,0≤m < 4, and 1≤q≤4.
This monocyclopentadienyl metallocene can be as shown in following formula (3).
Here x is 0,1,2,3 or 4, and y is 0 or 1,
R represents the substituent group with 1-20 non-hydrogen atom, selected from hydrogen, has the alkyl of 1-20 carbon atom, silicyl, germyl, cyano group, halogen or its compound group,
(R* represents hydrogen here for Y ' expression-O-,-S-,-NR*-or-PR*-, there is the alkyl of 1-12 carbon atom, there is the oxyl of 1-8 carbon atom, silicyl, there is the haloalkyl of 1-8 carbon atom, there is halogenated aryl or its compound group of 6-20 carbon atom)
Z represents SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2Or GeR*2, R* is identical with definition above,
Each L represents the substituent group with 1-20 non-hydrogen substituent independently, it is selected from halogen, there is the alkyl of 1-20 carbon atom, there is the oxyl of 1-18 carbon atom, there is the hydrocarbylamino of 1-19 carbon atom, there is the alkyl amido (hydrocarbylamide) of 1-18 carbon atom, there is the alkyl phosphorio group of 1-18 carbon atom, there is the alkylthio group of 1-18 carbon atom and be combined group, or two substituent groups L represent neutral conjugation diene or the divalent group with 1-30 carbon atom, and
M represents periodic chart the 4th or 5 group 4 transition metal.
The kind of the dicyclopentadienyl metallocene shown in formula (1) can include bicyclic pentadiene metallocene the most double (cyclopentadienyl group) zirconium dimethyl, double (methyl cyclopentadienyl) zirconium dimethyl, double (n-butyl cyclopentadienyl) zirconium dimethyl, double (indenyl) zirconium dimethyl, double (1, 3-dimethylcyclo-pentadienyl) zirconium dimethyl, (pentamethylcyclopentadiene base) (cyclopentadienyl group) zirconium dimethyl, double (pentamethylcyclopentadiene base) zirconium dimethyl, double (fluorenyl) zirconium dimethyl, double (2-methyl-indenyl) zirconium dimethyl, double (2-phenyl indenyl) zirconium dimethyls and cyclopentadienyl group (2-phenyl indenyl) zirconium dimethyl.
nullCrosslinking metallocene shown in above formula (2) can include double (1-indenyl) zirconium dimethyl of dimetylsilyl，Dimetylsilyl (9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Double (1-cyclopentadienyl group) zirconium dimethyl of dimetylsilyl，Dimetylsilyl (9-fluorenyl) (1-indenyl) zirconium dimethyl，Double (1-indenyl) the dimethyl hafnium of dimetylsilyl，Dimetylsilyl (9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Double (1-cyclopentadienyl group) the dimethyl hafnium of dimetylsilyl，Dimetylsilyl (9-fluorenyl) (1-indenyl) dimethyl hafnium，Ethylenebis (1-cyclopentadienyl group) zirconium dimethyl，Ethylenebis (1-indenyl) zirconium dimethyl，Ethylenebis (4，5，6，7-tetrahydrochysene-1-indenyl) zirconium dimethyl，Ethylenebis (4-methyl isophthalic acid-indenyl) zirconium dimethyl，Ethylenebis (5-methyl isophthalic acid-indenyl) zirconium dimethyl，Ethylenebis (6-methyl isophthalic acid-indenyl) zirconium dimethyl，Ethylenebis (7-methyl isophthalic acid-indenyl) zirconium dimethyl，Ethylenebis (4-phenyl-1-indenyl) zirconium dimethyl，Ethylenebis (5-methoxyl group-1-indenyl) zirconium dimethyl，Ethylenebis (2,3-dimethyl-1-indenyl) zirconium dimethyl，Ethylenebis (4,7-dimethyl-1-indenyl) zirconium dimethyl，Ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dimethyl，Ethylenebis (trimethyl cyclopentadienyl group) zirconium dimethyl，Ethylenebis (5-dimethylamino-1-indenyl) zirconium dimethyl，Ethylenebis (6-dipropylamino-1-indenyl) zirconium dimethyl，Ethylenebis (4，Double (the dimethylamino)-1-indenyl of 7-) zirconium dimethyl，Ethylenebis (5-diphenylphosphine-1-indenyl) zirconium dimethyl，Ethylidene (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Ethylidene (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Ethylidene (9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Ethylenebis (9-fluorenyl) zirconium dimethyl，Ethylenebis (1-cyclopentadienyl group) dimethyl hafnium，Ethylenebis (1-indenyl) dimethyl hafnium，Ethylenebis (4，5，6，7-tetrahydrochysene-1-indenyl) dimethyl hafnium，Ethylenebis (4-methyl isophthalic acid-indenyl) dimethyl hafnium，Ethylenebis (5-methyl isophthalic acid-indenyl) dimethyl hafnium，Ethylenebis (6-methyl isophthalic acid-indenyl) dimethyl hafnium，Ethylenebis (7-methyl isophthalic acid-indenyl) dimethyl hafnium，Ethylenebis (4-phenyl-1-indenyl) dimethyl hafnium，Ethylenebis (5-methoxyl group-1-indenyl) dimethyl hafnium，Ethylenebis (2,3-dimethyl-1-indenyl) dimethyl hafnium，Ethylenebis (4,7-dimethyl-1-indenyl) dimethyl hafnium，Ethylenebis (4,7-dimethoxy-1-indenyl) dimethyl hafnium，Ethylenebis (trimethyl cyclopentadienyl group) dimethyl hafnium，Ethylenebis (5-dimethylamino-1-indenyl) dimethyl hafnium，Ethylenebis (6-dipropylamino-1-indenyl) dimethyl hafnium，Ethylenebis (4,Double (the dimethylamino)-1-indenyl of 7-) dimethyl hafnium，Ethylenebis (5-diphenylphosphine-1-indenyl) dimethyl hafnium，Ethylidene (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Ethylidene (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Ethylidene (9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Ethylenebis (9-fluorenyl) dimethyl hafnium，2,Double (1-cyclopentadienyl group) zirconium dimethyl of 2-propyl group，2,Double (1-indenyl) zirconium dimethyl of 2-propyl group，2,2-propyl group double (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dimethyl，2，Double (4-methyl isophthalic acid-indenyl) zirconium dimethyl of 2-propyl group，2，Double (5-methyl isophthalic acid-indenyl) zirconium dimethyl of 2-propyl group，2,Double (6-methyl isophthalic acid-indenyl) zirconium dimethyl of 2-propyl group，2,Double (7-methyl isophthalic acid-indenyl) zirconium dimethyl of 2-propyl group，2,Double (4-phenyl-1-indenyl) zirconium dimethyl of 2-propyl group，2,Double (5-methoxyl group-1-indenyl) zirconium dimethyl of 2-propyl group，2,2-propyl group double (2,3-dimethyl-1-indenyl) zirconium dimethyl，2,2-propyl group double (4,7-dimethyl-1-indenyl) zirconium dimethyl，2,2-propyl group double (4,7-dimethoxy-1-indenyl) zirconium dimethyl，2,Double (trimethyl cyclopentadienyl group) zirconium dimethyl of 2-propyl group，2,Double (5-dimethylamino-1-indenyl) zirconium dimethyl of 2-propyl group，2,Double (6-dipropylamino-1-indenyl) zirconium dimethyl of 2-propyl group，2,2-propyl group double (4,Double (the dimethylamino)-1-indenyl of 7-) zirconium dimethyl，2,Double (5-diphenylphosphine-1-indenyl) zirconium dimethyl of 2-propyl group，2,2-propyl group (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，2,2-propyl group (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，2,2-propyl group (9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，2,Double (9-fluorenyl) zirconium dimethyl of 2-propyl group，2,Double (1-cyclopentadienyl group) the dimethyl hafnium of 2-propyl group，2,Double (1-indenyl) the dimethyl hafnium of 2-propyl group，2,2-propyl group double (4,5,6,7-tetrahydrochysene-1-indenyl) dimethyl hafnium，2,Double (4-methyl isophthalic acid-indenyl) the dimethyl hafnium of 2-propyl group，2,Double (5-methyl isophthalic acid-indenyl) the dimethyl hafnium of 2-propyl group，2，Double (6-methyl isophthalic acid-indenyl) the dimethyl hafnium of 2-propyl group，2,Double (7-methyl isophthalic acid-indenyl) the dimethyl hafnium of 2-propyl group，2,Double (4-phenyl-1-indenyl) the dimethyl hafnium of 2-propyl group，2，Double (5-methoxyl group-1-indenyl) the dimethyl hafnium of 2-propyl group，2,2-propyl group double (2,3-dimethyl-1-indenyl) dimethyl hafnium，2,2-propyl group double (4,7-dimethyl-1-indenyl) dimethyl hafnium，2,2-propyl group double (4,7-dimethoxy-1-indenyl) dimethyl hafnium，2,Double (trimethyl cyclopentadienyl group) the dimethyl hafnium of 2-propyl group，2,Double (5-dimethylamino-1-indenyl) the dimethyl hafnium of 2-propyl group，2,Double (6-dipropylamino-1-indenyl) the dimethyl hafnium of 2-propyl group，2,2-propyl group double (4,Double (the dimethylamino)-1-indenyl of 7-) dimethyl hafnium，2,Double (5-diphenylphosphine-1-indenyl) the dimethyl hafnium of 2-propyl group，2,2-propyl group (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，2,2-propyl group (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，2,2-propyl group (9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，2，Double (9-fluorenyl) the dimethyl hafnium of 2-propyl group，Double (1-cyclopentadienyl group) zirconium dimethyl of diphenyl methyl，Double (1-indenyl) zirconium dimethyl of diphenyl methyl，Diphenyl methyl double (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dimethyl，Double (4-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenyl methyl，Double (5-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenyl methyl，Double (6-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenyl methyl，Double (7-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenyl methyl，Double (4-phenyl-1-indenyl) zirconium dimethyl of diphenyl methyl，Double (5-methoxyl group-1-indenyl) zirconium dimethyl of diphenyl methyl，Diphenyl methyl double (2,3-dimethyl-1-indenyl) zirconium dimethyl，Diphenyl methyl double (4,7-dimethyl-1-indenyl) zirconium dimethyl，Diphenyl methyl double (4,7-dimethoxy-1-indenyl) zirconium dimethyl，Double (trimethyl cyclopentadienyl group) zirconium dimethyl of diphenyl methyl，Double (5-dimethylamino-1-indenyl) zirconium dimethyl of diphenyl methyl，Double (6-dipropylamino-1-indenyl) zirconium dimethyl of diphenyl methyl，Diphenyl methyl double (4,Double (the dimethylamino)-1-indenyl of 7-) zirconium dimethyl，Double (5-diphenylphosphine-1-indenyl) zirconium dimethyl of diphenyl methyl，Diphenyl methyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Diphenyl methyl (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Diphenyl methyl (9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Double (9-fluorenyl) zirconium dimethyl of diphenyl methyl，Double (1-cyclopentadienyl group) the dimethyl hafnium of diphenyl methyl，Double (1-indenyl) the dimethyl hafnium of diphenyl methyl，Diphenyl methyl double (4,5,6,7-tetrahydrochysene-1-indenyl) dimethyl hafnium，Double (4-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenyl methyl，Double (5-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenyl methyl，Double (6-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenyl methyl，Double (7-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenyl methyl，Double (4-phenyl-1-indenyl) the dimethyl hafnium of diphenyl methyl，Double (5-methoxyl group-1-indenyl) the dimethyl hafnium of diphenyl methyl，Diphenyl methyl double (2,3-dimethyl-1-indenyl) dimethyl hafnium，Diphenyl methyl double (4,7-dimethyl-1-indenyl) dimethyl hafnium，Diphenyl methyl double (4,7-dimethoxy-1-indenyl) dimethyl hafnium，Double (trimethyl cyclopentadienyl group) the dimethyl hafnium of diphenyl methyl，Double (5-dimethylamino-1-indenyl) the dimethyl hafnium of diphenyl methyl，Double (6-dipropylamino-1-indenyl) the dimethyl hafnium of diphenyl methyl，Diphenyl methyl double (4,Double (the dimethylamino)-1-indenyl of 7-) dimethyl hafnium，Double (5-diphenylphosphine-1-indenyl) the dimethyl hafnium of diphenyl methyl，Diphenyl methyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Diphenyl methyl (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Diphenyl methyl (9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Double (9-fluorenyl) the dimethyl hafnium of diphenyl methyl，Double (1-cyclopentadienyl group) zirconium dimethyl of diphenylsilyl group，Double (1-indenyl) zirconium dimethyl of diphenylsilyl group，Diphenylsilyl group double (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dimethyl，Double (4-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenylsilyl group，Double (5-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenylsilyl group，Double (6-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenylsilyl group，Double (7-methyl isophthalic acid-indenyl) zirconium dimethyl of diphenylsilyl group，Double (4-phenyl-1-indenyl) zirconium dimethyl of diphenylsilyl group，Double (5-methoxyl group-1-indenyl) zirconium dimethyl of diphenylsilyl group，Diphenylsilyl group double (2,3-dimethyl-1-indenyl) zirconium dimethyl，Diphenylsilyl group double (4,7-dimethyl-1-indenyl) zirconium dimethyl，Diphenylsilyl group double (4,7-dimethoxy-1-indenyl) zirconium dimethyl，Double (trimethyl cyclopentadienyl group) zirconium dimethyl of diphenylsilyl group，Double (5-dimethylamino-1-indenyl) zirconium dimethyl of diphenylsilyl group，Double (6-dipropylamino-1-indenyl) zirconium dimethyl of diphenylsilyl group，Diphenylsilyl group double (4,Double (the dimethylamino)-1-indenyl of 7-) zirconium dimethyl，Double (5-diphenylphosphine-1-indenyl) zirconium dimethyl of diphenylsilyl group，Diphenylsilyl group (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Diphenylsilyl group (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Diphenylsilyl group (9-fluorenyl) (1-cyclopentadienyl group) zirconium dimethyl，Double (9-fluorenyl) zirconium dimethyl of diphenylsilyl group，Double (1-cyclopentadienyl group) the dimethyl hafnium of diphenylsilyl group，Double (1-indenyl) the dimethyl hafnium of diphenylsilyl group，Diphenylsilyl group double (4,5,6,7-tetrahydrochysene-1-indenyl) dimethyl hafnium，Double (4-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenylsilyl group，Double (5-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenylsilyl group，Double (6-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenylsilyl group，Double (7-methyl isophthalic acid-indenyl) the dimethyl hafnium of diphenylsilyl group，Double (4-phenyl-1-indenyl) the dimethyl hafnium of diphenylsilyl group，Double (5-methoxyl group-1-indenyl) the dimethyl hafnium of diphenylsilyl group，Diphenylsilyl group double (2,3-dimethyl-1-indenyl) dimethyl hafnium，Diphenylsilyl group double (4,7-dimethyl-1-indenyl) dimethyl hafnium，Diphenylsilyl group double (4,7-dimethoxy-1-indenyl) dimethyl hafnium，Double (trimethyl cyclopentadienyl group) the dimethyl hafnium of diphenylsilyl group，Double (5-dimethylamino-1-indenyl) the dimethyl hafnium of diphenylsilyl group，Double (6-dipropylamino-1-indenyl) the dimethyl hafnium of diphenylsilyl group，Diphenylsilyl group double (4,Double (the dimethylamino)-1-indenyl of 7-) dimethyl hafnium，Double (5-diphenylphosphine-1-indenyl) the dimethyl hafnium of diphenylsilyl group，Diphenylsilyl group (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Diphenylsilyl group (4-butyl sulfur-9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium，Diphenylsilyl group (9-fluorenyl) (1-cyclopentadienyl group) dimethyl hafnium and double (9-fluorenyl) the dimethyl hafnium of diphenylsilyl group.
nullMonocyclopentadienyl metallocene shown in above formula (3) can include [(N-tert-butyl group amido) (tetramethyl-η 5-cyclopentadienyl group)-1,2-ethylidene] dimethyl titanium ([(N-t-butylamide) (tetramethyl-η 5-cyclopentadienyl)-1,2-ethandiyl]titaniumdimethyl)，[(N-tert-butyl group amido) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] dimethyl titanium，[(N-methylamino) (tetramethyl-η 5-cyclopentadienyl group)-1,2-ethylidene] dimethyl titanium，[(N-methylamino) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] dimethyl titanium，[(N-phenyl amido) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] dimethyl titanium，[(N-benzylamino) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] dimethyl titanium，(N-methylamino) (η 5-cyclopentadienyl group)-1,2-ethylidene] dimethyl titanium，[(N-methylamino) (η 5-cyclopentadienyl group)-dimethylsilane] dimethyl titanium，[(N-tert-butyl group amido) (η 5-indenyl)-dimethylsilane] dimethyl titanium，[(N-benzylamino) (η 5-indenyl)-dimethylsilane] dimethyl titanium，Dimetylsilyl tetramethyl-ring pentadienyl-tert-butyl group amido zirconium dimethyl (dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconiumdimethyl)，Dimetylsilyl tetramethyl-ring pentadienyl-tert-butyl group amido dimethyl hafnium，Dimetylsilyl t-butyl cyclopentadienyl-tert-butyl group amido zirconium dimethyl，Dimetylsilyl t-butyl cyclopentadienyl-tert-butyl group amido dimethyl hafnium，Dimetylsilyl trimethyl silyl cyclopentadienyl group-tert-butyl group amido zirconium dimethyl，Dimetylsilyl tetramethyl-ring pentadienyl-phenyl amido zirconium dimethyl，Dimetylsilyl tetramethyl-ring pentadienyl-phenyl amido dimethyl hafnium，Aminomethyl phenyl silicyl tetramethyl-ring pentadienyl-phenyl amido zirconium dimethyl，Aminomethyl phenyl silicyl tetramethyl-ring pentadienyl-phenyl amido dimethyl hafnium，Aminomethyl phenyl silicyl t-butyl cyclopentadienyl-tert-butyl group amido zirconium dimethyl，Aminomethyl phenyl silicyl t-butyl cyclopentadienyl-tert-butyl group amido dimethyl hafnium，Dimetylsilyl tetramethyl-ring pentadienyl-align phenyl amido zirconium dimethyl，Dimetylsilyl tetramethyl-ring pentadienyl-align phenyl amido dimethyl hafnium，Dibromo bi triphenyl phosphine nickel，Dichloro bi triphenyl phosphine nickel，Dibromo diacetonitrile nickel，Dibromo two benzonitrile nickel，Dibromo (1,The double diphenyl phosphine oxide of 2-) nickel，Dibromo (1,The double diphenyl phosphine oxide of 3-) nickel，Dibromo (1,The double phosphine ferrocene of 1 '-diphenyl) nickel，The double diphenylphosphine nickel of dimethyl，Dimethyl (1,The double diphenyl phosphine oxide of 2-) nickel，Methyl (1,The double diphenyl phosphine oxide of 2-) nickel Tetrafluoroboric acid ester，(2-diphenylphosphine-1-phenylethylene oxygen) phenylpyridine nickel，Dichloro bi triphenyl phosphine palladium，Dichlorodiethyl nitrile palladium，Dichloro (1,The double diphenyl phosphine oxide of 2-) palladium，The double Tetrafluoroboric acid ester of bi triphenyl phosphine palladium，Double (2,2 '-two pyridines) methyl ferrum Tetrafluoroboric acid ester etherate etc..nullIn addition，The example of monocyclopentadienyl metallocene can include following compound，The most each titanium listed above，" dimethyl " part of zirconium and hafnium compound is that the most following compound of use-case is substituted :-dichloro，-dibromo，-diiodo-，-diethyl，-dibutyl，-dibenzyl，-diphenyl，-bis--2-(N,N-dimethylamino) benzyl，-2-Aden-1,4-diyl，-s-trans-η 4-1,4-diphenyl-1,3-butadiene，-s-trans-η 4-3-methyl isophthalic acid,3-pentadiene，-s-trans-η 4-1,4-dibenzyl-1,3-butadiene，-s-trans-η 4-2,4-hexadiene，-s-trans-η 4-1,3-pentadiene，-s-trans-η 4-1,4-xylyl-1,3-butadiene，-s-trans-η 4-1,Double (trimethyl silyl)-1 of 4-,3-butadiene，-s-cis-η 4-1,4-diphenyl-1,3-butadiene，-s-cis-η 4-3-methyl isophthalic acid,3-pentadiene，-s-cis-η 4-1,4-dibenzyl-1,3-butadiene，-s-cis-η 4-2,4-hexadiene，-s-cis-η 4-1,3-pentadiene，-s-cis-η 4-1,4-xylyl-1,3-butadiene，-s-cis-η 4-1,Double (trimethyl silyl)-1 of 4-,3-butadiene etc..
Employ metallocene catalyst component above for preparing the metallocene catalyst system of the copolymer based on ethylene of the present invention, but at least one or multiple above-mentioned metallocene catalyst component can be included.Additionally, if it is required, this metallocene catalyst system may further include the metallocene catalyst component of other catalytic component, such as non-invention other known to catalytic component.
As the metallocene compound for the present invention, the method having been known that can use open source literature prepare those, or available commercially from those of mCATGmBH (seeing www.mcat.de) or Strem (seeing www.strem.com) or BoulderScientific (seeing www.bouldersci.com).
Titanocenes compound used in step (1) or Binary catalysts can be as shown in following formulas (4).
(CpRn)(CpR’m)TiLq(4)
Here Cp is cyclopentadienyl group, indenyl, tetrahydro indenyl or fluorenyl,
Rn and R ' m represents hydrogen independently of one another, has the alkyl of 1-20 carbon atom, alkyl ether, aIkylsilyl groups, allyl ether, alkoxyalkyl, phosphine or amine,
L represents alkyl, pi-allyl, aryl alkyl, amido (amide), alkoxyl or halogen, and
Integer in the range of n, m and q are the most following: 0≤n < 5,0≤m < 5 and 1≤q≤4.
nullThe kind of the titanocenes or Binary catalysts that meet above formula (4) can include double (cyclopentadienyl group) titanium chloride，Double (methyl cyclopentadienyl) titanium chloride，Double (n-butyl cyclopentadienyl) titanium chloride，Double (1,3-dimethylcyclo-pentadienyl) titanium chloride，Double (pentamethylcyclopentadiene base) titanium chloride，Double (tetramethyl-ring pentadienyl) titanium chloride，Double (trimethyl silyl cyclopentadienyl group) titanium chloride，Double (1,The double trimethyl cyclopentadienyl group of 3-) titanium chloride，Double (indenyl) titanium chloride，Double (4,5,6,7-tetrahydrochysene-1-indenyl) titanium chloride，Double (5-methyl isophthalic acid-indenyl) titanium chloride，Double (6-methyl isophthalic acid-indenyl) titanium chloride，Double (7-methyl isophthalic acid-indenyl) titanium chloride，Double (5-methoxyl group-1-indenyl) titanium chloride，Double (2,3-dimethyl-1-indenyl) titanium chloride，Double (4,7-dimethyl-1-indenyl) titanium chloride，Double (2,3-dimethoxy-1-indenyl) titanium chloride，Double (fluorenyl) titanium chloride etc. and (pentamethylcyclopentadiene base) (cyclopentadienyl group) titanium chloride，(fluorenyl) (cyclopentadienyl group) titanium chloride，(fluorenyl) (pentamethylcyclopentadiene base) titanium chloride，(indenyl) (pentamethylcyclopentadiene base) titanium chloride，(indenyl) (fluorenyl) titanium chloride，(tetrahydro indenyl) (cyclopentadienyl group) titanium chloride，(tetrahydro indenyl) (pentamethylcyclopentadiene base) titanium chloride，(tetrahydro indenyl) (fluorenyl) titanium chloride，(cyclopentadienyl group) (1,The double trimethyl silyl cyclopentadienyl group of 3-) titanium chloride，(pentamethylcyclopentadiene base) (1,The double trimethyl silyl cyclopentadienyl group of 3-) titanium chloride，(indenyl) (1,The double trimethyl silyl cyclopentadienyl group of 3-) titanium chloride，(fluorenyl) (1,The double trimethyl silyl cyclopentadienyl group of 3-) titanium chloride etc..
nullIn addition，This titanocenes or Binary catalysts can include following compound，" dichloride " part of the most each titanium compound listed above is substituted with compound set forth below :-dibromo，-diiodo-，-dimethyl，Diethyl，-dibutyl，-dibenzyl，-diphenyl，-dimethoxy，Methoxyl group chloride，-bis--2-(N,N-dimethylamino) benzyl，-2-Aden-1,4-diyl，-s-trans-η 4-1,4-diphenyl-1,3-butadiene，-s-trans-η 4-3-methyl isophthalic acid,3-pentadiene，-s-trans-η 4-1,4-dibenzyl-1,3-butadiene，S-trans-η 4-2,4-hexadiene，-s-trans-η 4-1,3-pentadiene，-s-trans-η 4-1,4-xylyl-1,3-butadiene，-s-trans-η 4-1,Double (trimethyl silyl)-1 of 4-,3-butadiene，-s-cis-η 4-1,4-diphenyl-1,3-butadiene，-s-cis-η 4-3-methyl isophthalic acid,3-pentadiene，-s-cis-η 4-1,4-dibenzyl-1,3-butadiene，-s-cis-η 4-2,4-hexadiene，-s-cis-η 4-1,3-pentadiene，-s-cis-η 4-1,4-xylyl-1,3-butadiene and-s-cis-η 4-1,Double (trimethyl silyl)-1 of 4-,3-butadiene.
nullThe example of Binary catalysts can include cyclopentadienyl group titanous chloride.，Cyclopentadienyl group titanium trifluoride，Cyclopentadienyl group titanium tribromide，Cyclopentadienyl group titanium triiodide，Cyclopentadienyl group methyl dichloro titanium，Cyclopentadienyl group dimethylammonium chloride titanium，Cyclopentadiene base oxethyl titanium chloride，Cyclopentadienyl group diethoxy titanium chloride，Cyclopentadienyl group benzene oxidatoin titanium chloride，Cyclopentadienyl group hexichol oxidation chlorination titanium，Cyclopentadienyl group trimethyl titanium，Cyclopentadienyl group triethyl group titanium，Cyclopentadienyl group triisopropyl titanium，Cyclopentadienyl group three normal-butyl titanium，Cyclopentadienyl group three sec-butyl titanium，Cyclopentadienyl group front three titanium oxide，Cyclopentadienyl group three ethoxyquin titanium，Cyclopentadienyl group three titanium isopropoxide，Cyclopentadienyl group three fourth titanium oxide，Cyclopentadienyl group triphenyl titanium，Cyclopentadienyl group tribenzyl titanium，Three tolyl titaniums of cyclopentadienyl group，Cyclopentadienyl group three p-methylphenyl titanium，Cyclopentadienyl group three-，P-xylene base titanium，Cyclopentadienyl group three-4-ethylphenyl titanium，Cyclopentadienyl group three-4-hexyl phenyl titanium，Cyclopentadienyl group three-4-methoxyphenyl titanium，Cyclopentadienyl group three-4-ethoxyl phenenyl titanium，Cyclopentadienyl group triphen titanium oxide，Cyclopentadienyl group three-dimethyl amido titanium (cyclopentadienyltitaniumtri-dimethylamide)，Cyclopentadienyl group three-diethyl amido titanium，Cyclopentadienyl group three-diisopropyl amido titanium，Cyclopentadienyl group three-di-sec-butyl amido titanium，Cyclopentadienyl group three-di-t-butyl amido titanium，Cyclopentadienyl group three-two triethylsilyl amido titanium etc..
In addition, this Binary catalysts can include following compound, " cyclopentadienyl group " part of the most each titanium compound listed above is substituted by following compounds: methyl cyclopentadienyl, n-butyl cyclopentadienyl, 1, 3-dimethylcyclo-pentadienyl, pentamethylcyclopentadiene base, tetramethyl pentadienyl, trimethyl silyl cyclopentadienyl group, 1, the double trimethyl silyl cyclopentadienyl group of 3-, indenyl, 4, 5, 6, 7-tetrahydrochysene-1-indenyl, 5-methyl isophthalic acid-indenyl, 6-methyl isophthalic acid-indenyl, 7-methyl isophthalic acid-indenyl, 5-methoxyl group-1-indenyl, 2, 3-dimethyl-1-indenyl, 4, 7-dimethyl-1-indenyl, 4, 7-dimethoxy-1-indenyl and fluorenyl.
It addition, the example of Binary catalysts is set forth below.
null[(N-tert-butyl group amido) (tetramethyl-η 5-cyclopentadienyl group)-1,2-ethylidene] titanium chloride ([(N-t-butylamide) (tetramethyl-η 5-cyclopentadienyl)-1,2-ethandiyl]titaniumdichloride)，[(N-tert-butyl group amido) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] titanium chloride，[(N-methylamino) (tetramethyl-η 5-cyclopentadienyl group)-1,2-ethylidene] titanium chloride，[(N-methylamino) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] titanium chloride，[(N-phenyl amido) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] titanium chloride，[(N-benzylamino) (tetramethyl-η 5-cyclopentadienyl group)-dimethylsilane] titanium chloride，(N-methylamino) (η 5-cyclopentadienyl group)-1,2-ethylidene] titanium chloride，[(N-methylamino) (η 5-cyclopentadienyl group)-dimethylsilane] titanium chloride，[(N-tert-butyl group amido) (η 5-indenyl)-dimethylsilane] titanium chloride，[(N-benzylamino) (η 5-indenyl)-dimethylsilane] titanium chloride etc..
nullIn addition，This Binary catalysts can include following compound，" dichloride " part of the most each Binary catalysts listed above is substituted with compound set forth below :-dibromo，-diiodo-，-dimethyl，Diethyl，-dibutyl，-dibenzyl，-diphenyl，-dimethoxy，Methoxyl group chloride，-bis--2-(N,N-dimethylamino) benzyl，-2-Aden-1,4-diyl，-s-trans-η 4-1,4-diphenyl-1,3-butadiene，-s-trans-η 4-3-methyl isophthalic acid,3-pentadiene，-s-trans-η 4-1,4-dibenzyl-1,3-butadiene，S-trans-η 4-2,4-hexadiene，-s-trans-η 4-1,3-pentadiene，-s-trans-η 4-1,4-xylyl-1,3-butadiene，-s-trans-η 4-1,Double (trimethyl silyl)-1 of 4-,3-butadiene，-s-cis-η 4-1,4-diphenyl-1,3-butadiene，-s-cis-η 4-3-methyl isophthalic acid,3-pentadiene，-s-cis-η 4-1,4-dibenzyl-1,3-butadiene，-s-cis-η 4-2,4-hexadiene，-s-cis-η 4-1,3-pentadiene，-s-cis-η 4-1,4-xylyl-1,3-butadiene and-s-cis-η 4-1,Double (trimethyl silyl)-1 of 4-,3-butadiene.
Titanocenes compound and Binary catalysts can be used alone or in combination.Additionally, titanocenes compound or Binary catalysts can also use after organo-aluminium, organolithium or organic-magnesium reaction.
The organo-aluminium that can react with titanocenes compound or Binary catalysts and be used together can include trialkylaluminium, dialkyl group halogenated aluminum, and alkyl dihalides is for aluminum, more particularly trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three hexyl aluminum, trioctylaluminum, tridecyl aluminum, dimethylaluminum chloride, diethyl aluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide etc..
nullThe organolithium that can react with titanocenes compound or Binary catalysts and be used together can include meeting the lithium of following formula: (wherein R is alkyl to RLi，Selected from the alkyl with 1-10 carbon atom，Alkoxyl，Alkyl amine group (alkylamidegroup)，There is the pi-allyl of 6-12 carbon atom，Allyloxy，Arylamine group，There is the polyoxyethylene base of 7-20 carbon atom，Polyoxyethylene epoxide，Alkylallyl amine base，Alkoxy aryl，Aryl alkyl amido and the thiazolinyl with 2-20 carbon atom，And specifically include lithium methide，Ethyl-lithium，Isopropyl lithium，N-BuLi，S-butyl lithium，Tert-butyl lithium，Methoxyl group lithium，Lithium isopropoxide，Butoxy lithium，Dimethyl amido lithium，Diethyl amido lithium，Lithium diisopropyl amido，Dibutyl amido lithium，Diphenyl amido lithium，Phenyl lithium，Between tolyl lithium，P-methylphenyl lithium，Xylyl lithium，Methoxyphenyl lithium，Phenoxy group lithium，Benzyl lithium etc..
The organic-magnesium that can react with titanocenes compound or Binary catalysts and be used together can include dialkyl magnesium, halogenated alkyl magnesium etc., and specifically includes dimethyl magnesium, magnesium ethide, dibutylmagnesium, diisobutyl magnesium, dihexyl magnesium, dioctyl magnesium, methyl-magnesium-bromide, methyl-magnesium-chloride, ethylmagnesium bromide, ethylmagnesium chloride, butyl magnesium bromide, butylmagnesium chloride, hexyl magnesium bromide, hexyl magnesium chloride, phenyl-magnesium-bromide, phenyl-magnesium-chloride, allylic bromination magnesium, allylmgcl etc..
The amount of titanocenes compound and Binary catalysts for preparing metallocene catalyst is 35:1-2:1, as metallocene compound: titanocenes compound or the mol ratio of Binary catalysts.When the usage rate of titanocenes compound or Binary catalysts is less than 35:1, it is difficult to there is the effect fully increasing molecular weight.Meanwhile, when this usage rate is more than 2:1, polymerization activity significantly deteriorates, and molecular weight adversely becomes excessive.
Aikyiaiurnirsoxan beta used in step (1) is that when this aikyiaiurnirsoxan beta is linear aluminoxanes oligomer, this aikyiaiurnirsoxan beta is expressed as chemical formula R-(Al (R)-O) n-AlR selected from one or more of linear and Cyclic aluminoxane oligomer2；With when this aikyiaiurnirsoxan beta is Cyclic aluminoxane oligomer, this aikyiaiurnirsoxan beta is expressed as chemical formula (-Al (R)-O-)m, wherein R is the alkyl with carbon atom C1-C8, preferably methyl；N is integer 1-40, preferably 10-20；M is 3-40, preferably 3-20.Aikyiaiurnirsoxan beta is the mixture of oligomer, its molecular weight distribution with non-constant width and mean molecule quantity are about 800-1200, preserve usually used as the solution in toluene, and include the MAO etc. of such as 10% or 30%, AlbemarleCorporation manufacture.
When step (1) is to use carrying method (a) to carry out, it is 5-30wt% by metallocene compound being dissolved in alumoxane concentration in the solution obtained in aluminoxanes solution, and the concentration of metallocene catalyst component is preferably 0.001-1.0wt%, calculate based on metallic atom (M).When the concentration of each component exceedes described scope, catalyst activity is the most too low or too high.
Solution can include that aromatic hydrocarbons, aliphatic hydrocarbon or clicyclic hydrocarbon are as solvent.
In the preparation method of the metallocene catalyst of the copolymer based on ethylene for preparing the present invention, in step (1), used carrier is porosu solid microgranule, preferably inorganic material, such as silicon is or/and the oxide of aluminum, most preferably there is the silicon dioxide of spheroidal particle, such as obtained by spray drying process, and there is OH group or other include the particulate form of functional group of active hydrogen atom.
The particle mean size of this carrier is 10-250 μm, preferably 10-150 μm, and the average diameter of its micropore isIt is 0.1-10ml/g and preferred 0.5-5ml/g with volume, and surface area is 5-1000m2/ g and preferred 50-600m2/g。
When silicon dioxide is used as carrier, it should have at least some activity hydroxy [OH], and its concentration is preferably 0.5-2.5mmol/1g silicon dioxide, and more preferably 0.7-1.6mmol/g.When hydroxyl concentration is less than 0.5mmol, the amount of the aikyiaiurnirsoxan beta of load reduces, and the most undesirably, catalyst activity reduces, and when hydroxyl concentration is more than 2.5mmol, catalytic component is adversely inactivated by hydroxyl.
The hydroxyl of silicon dioxide can be detected by IR spectrographic method, and the amount of hydroxyl concentration required on silicon dioxide by silica sample contact with methyl-magnesium-bromide, can be measured the amount (by measurement pressure) of the methane that foams and measure.
The silicon dioxide with [OH] concentration and physical property that are suitable to the present invention can use surface area to be 300m2/ g and pore volume are those of 1.6ml/g, and it is commercially available by DavisonchemicaldivisionofW.R.Graceandcompany under trade (brand) name XPO-2402, XPO-2410, XPO-2411 and XPO-2412.Additionally, at trade (brand) name Davision948,952 and 955 times commercially available wet silicon dioxide can pass through heating means, [OH] concentration is adjusted to desired level and uses.
Carrying method in step (1) is preferably by after loading to aikyiaiurnirsoxan beta on carrier; load to metallocene carry out on carrier; and when silicon dioxide is used as the carrier in step (1); under the anhydrous condition not having oxygen; the hydroxyl of silicon dioxide provides the site for load metallocene by reacting with aikyiaiurnirsoxan beta to be loaded, and protects metallocene (it may lose its activity by the sensitiveest reaction with external catalyst poisonous substance) simultaneously.Therefore, along with the increase of the aikyiaiurnirsoxan beta amount of load, the amount of the metallocene of load increases, and metallocene is not increased by the probability of external catalyst toxic poisoning, and therefore can increase activity.
Carrier pulp used in step (1) is prepared by being suspended in by carrier in hydrocarbon solvent or hydrocarbon solvent mixture.
In step (1), the temperature during carrying method is preferably 40-160 DEG C and more preferably 80-120 DEG C, but when outside temperature is in this scope, catalyst activity reduces, and polymer is the most adversely assembled.Time used by this carrying method is preferably 30 minutes-4 hours, and more preferably 1-2 hour, but when outside the time is in this scope, economy reduces or this underaction is to serve as catalyst, and this is disadvantageous.
In the catalyst solution of the load obtained by completing the carrying method of step (1), there is a small amount of unreacted aikyiaiurnirsoxan beta and the most unsupported metallocene catalyst, and needed to remove this small amount of material before being dried step.Without removing unreacted aikyiaiurnirsoxan beta, then the catalyst of those loads flocks together, and therefore causes poor injection problem when the catalyst of dried forms is injected polymer reactor.The catalyst that injection is assembled causes problem such as sheet and aggregation, and this crosses reaction owing to local in reactor.Additionally, unsupported metallocene is easily detached from the carrier in polymerization process, forms the polymer of the thinnest particulate forms, and therefore cause reaction fouling problem.
In order to remove such unsupported material, the catalyst of load is cleaned in step (2), preferably clean twice with organic solvent such as aromatic solvent and aliphatic hydrocarbon solvent.In the first cleaning step, eliminate unsupported metallocene and aikyiaiurnirsoxan beta, and when the metallocene of load departs from this step, the activity reduction of the catalyst of this load.The most in the present invention, in order to prevent such problem, this first cleaning step is carried out at a lower temperature, so that the fastness of the metallocene of this load and aluminoxane component can strengthen, the metallocenes being therefore prevented from this load departs from the second cleaning step subsequently.This first cleaning temperature preferably-10 to 60 DEG C.
Being dried in step (3) can use common drying means to carry out.
Al content in the metallocene catalyst of load prepared according to the methods of the invention is 10wt% or bigger.
[gas-phase polymerization]
The copolymer based on ethylene of the present invention can be in the presence of the metallocene catalyst of the load of the above-mentioned preparation as major catalyst, and by making gas-phase polymerization composition react prepare, said composition comprises hydrogen, ethylene and comonomer as required.
This comonomer is preferably nonvinylic alpha-olefin, and it is selected from propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-endecatylene, 1-dodecylene, tetradecene, cetene and 1-eicosylene.
The content of comonomer and ethylene is than preferably 0.005-0.02 and more preferably 0.008-0.015, for the mol ratio of copolymer/ethylene.In this case, when the mol ratio of comonomer/ethylene is less than 0.005 or is more than 0.02, the copolymer being in aspiration level can not adversely be obtained.
In the preparation of the copolymer based on ethylene of the present invention, preferably metallocene catalyst is mixed with at least one activator and form olefin polymerization catalyst system.Preferred activator used by this situation includes alkyl aluminum compound (such as diethyl aluminum chloride), aikyiaiurnirsoxan beta, modified alumoxane, neutral or ion ionizes activator, noncoordinating anion, the 13rd noncoordinating race's metal or metalloid anion, borine, borate/salt etc..
As alkyl aluminum compound, it is possible to use chemical formula AlRnX(3-n)(wherein R is the alkyl with 1-16 carbon atom to shown alkyl aluminum compound；X is halogen atom；With 1≤n≤3).The object lesson of this alkyl aluminum compound preferably includes triethyl aluminum, trimethyl aluminium, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, three-2-methyl amyl aluminum etc., more preferably triisobutyl aluminium, triethyl aluminum, tri-n-hexyl aluminum or tri-n-octylaluminium.
Preferably alkyl aluminum compound is with following mol ratio in gas-phase polymerization, and this depends on desired polymer performance.
Alkyl aluminum compound/transition metal≤1000 in 1≤major catalyst
It is further preferred that alkyl aluminum compound/transition metal≤300 in 10≤major catalyst
When in major catalyst, alkyl aluminum compound/transition metal mole ratio is less than 1, it is impossible to obtain enough polymerization activities, and when this mol ratio is more than 1000, polymerization activity adversely reduces.
In the preparation of the copolymer based on ethylene of the present invention, in polyreaction preferably when there is not hydrocarbon solvent, at 60-120 DEG C, more preferably 65-100 DEG C, carry out at a temperature of most preferably 70-80 DEG C and preferably under the pressure of 2-40 atmospheric pressure and more preferably 10-30 atmospheric pressure.
When in reactor, polymerization temperature is less than 60 DEG C, it is impossible to obtain enough polymerization efficiencies, and when polymerization temperature is more than 120 DEG C, may adversely produce polymer aggregation.Additionally, when the operating pressure in reactor is less than 2 atmospheric pressure, ethylene partial pressure is low, enough polymerization efficiencies the most possibly cannot be obtained, and when this operating pressure is more than 40 atmospheric pressure, it is difficult to control described reaction and undesirably add reactor burden.
The metallocene catalyst component of load of the major catalyst being used as in the copolymer based on ethylene of the preparation present invention before as the component of polyreaction, may be used for in the pre-polymerization of ethylene or alpha-olefin.Pre-polymerization can be in the presence of catalytic component and organo-aluminum compound such as triisobutyl aluminium, under the conditions of hydrocarbon solvent such as hexane, carries out at of a sufficiently low temperature and ethylene or alpha-olefin pressure condition.This pre-polymerization helps to improve the shape of polymer after polymerization, because catalyst particle is surrounded by polymer keeps catalyst shape.The weight ratio of pre-polymerization post-consumer polymer/catalyst is typically 0.1:1-200:1.Preferably organo-metallic compound includes trialkylaluminium, and it has C1-C6 alkyl, such as triethyl aluminum, triisobutyl aluminium and mixture thereof.In some cases, it is possible to use there is the organo-aluminum compound of at least one halogen or hydride group, such as ethylaluminum dichloride, diethyl aluminum chloride, ethyl aluminium sesquichloride and diisobutyl aluminium hydride.
According to the present invention, copolymer based on ethylene prepared in gas-phase polymerization includes the long chain branches in main chain, and as result, it is provided that with common Metallocenyl resin-phase ratio, high fondant-strength and low machining load.
Foregoing summary is merely illustrative, is not intended to limit by any way.In addition to illustrative above aspect, embodiment and feature, by with reference to accompanying drawing and detailed description below, other aspect, embodiment and feature will become clear from.
Accompanying drawing explanation
Fig. 1 is showing the figure of the drawing practice of the modulus of complex number spirogram for calculating prepared copolymer resin.
Fig. 2 is showing the figure of the dynamic testing method of phase angle displacement (δ) figure for calculating prepared copolymer resin.
Fig. 3 is showing the figure of the result that wherein complex modulus is drawn together with phase angle displacement.
Fig. 4 is showing the figure of the method calculating critical phase angle value.
Fig. 5 is showing the figure of the rheology tonometer (rheotensionmeter) for measuring melt strength.
Fig. 6 is a figure, it is shown that the complex modulus of the copolymer resin obtained in embodiment and comparative example and the figure of phase angle.
Detailed description of the invention
In the following detailed description, with reference to the accompanying drawing constituting a description part.Illustrative embodiment described in detailed description of the invention, drawings and claims does not indicates that restriction.Other embodiments can be used, and other changes can be carried out, without deviating from purport or the scope of the theme proposed here.
Hereinafter, the present invention will be more fully described by the following examples and comparative example, so that those skilled in the art can readily implement.The following examples are only used for the example of the example present invention, and the scope of the present invention is not limited to this.
[embodiment 1]
Prepare the catalyst of metallocene load
By commercially available under trade (brand) name XPO-2402 for 5g dehydrated silica (particle mean size 50 microns, surface area 300m2/ g, micro pore volume 1.6ml/g, and OH concentration 1mmol/g) weigh in anhydrous conditions, and stir into slurry form together with 20ml toluene.The serosity obtained injection 1L is equipped with in the reactor of agitator and cooling condenser.After the methylaluminoxane solution (10wt%) of 120ml quantifies in quality graduated cylinder, by ethylenebis (indenyl) zirconium dichloride [Et (IND)2ZrCl2] (metallocene/silicon dioxide=120 μm ol/g silicon dioxide) and dicyclic pentylene titanium dichloride [Cp2TiCl2](Cp2TiCl2/ silicon dioxide=18 μm ol/g silicon dioxide) (it is the metallocene catalyst component quantified in advance in 250mlschlenk flask) is in mixed at room temperature and stirs 5 minutes, and by solid metallocene catalyst and Cp2TiCl2Dissolve and react with each other simultaneously.While the temperature of this reactor is maintained at room temperature, add MAO-metallocene solution.Thereafter, under agitation reaction temperature is increased to 100 DEG C.At such a temperature, load-reaction is carried out 120 minutes.After the completion of the reaction, transfer to product, in schlenk flask, then decant its supernatant.After stirring product, when temperature reaches room temperature, this product is placed 10 minutes, decant supernatant, and use the 100ml toluene of-5 DEG C to clean first product.After stirring product, when temperature reaches room temperature, this product is placed, decant supernatant, and use the 100ml toluene of room temperature to carry out secondary cleaning this product.Thereafter, the hexane of the catalyst system purification obtained is cleaned, be then dried under gentle vacuum condition.
Gas-phase polymerization
Polymerization is carried out in continuous gas-phase fluidized-bed reactor.This fluid bed comprises polymer particle.The gas phase feed streams of ethylene and hydrogen and monomer is incorporated in the recycle gas pipeline under reactor beds.1-hexene is used as comonomer.Controlling ethylene, hydrogen and the respective flow of comonomer keep desired constant composition.Control the ethylene partial pressure that ethylene concentration keeps constant.Control hydrogen and uniformly keep the mol ratio of hydrogen/ethylene.The concentration of all gas is measured by online gas chromatography, so that the composition of the air-flow of recirculation is relative constancy.The reaction bed comprising polymer particle keep the fluidisation state as stream continuously, supplement wherein and recirculation gas pass through reaction zone.This reactor is at 19.2Kgf/cm2Gross pressure under run.This reaction is by being caused with constant speed injection by the catalyst of metallocene load prepared above, using tri-n-octylaluminium, (it is the alkyl aluminum compound as activator, for injecting catalyst and cause described reaction simultaneously) dilute with hexane, it is then injected into its 30ppm, based on the concentration in bed.Additionally, for reaction stability, by antistatic additive AS990 oil dilution, and inject, so that the content in bed remains to 25ppm.When polyreaction is carried out, in order to keep constant temperature of reactor, while recirculation gas passes through the velocity variations that heat exchanger controls to be polymerized produced heat, the temperature continuously adjusting recirculation gas increases or reduces.Reclaim a part of described bed by the speed identical with the generation speed of product, fluid bed is maintained at predetermined height.Table 1 below lists the detailed gas phase polymerisation conditions for preparing ethylene copolymer above.
[table 1]
The physical property of prepared copolymer based on ethylene is measured by method below.
The method measuring physical property
(1) melt flow index
Melt flow index is at 230 DEG C and 2.16kg, measures under conditions of ASTMD1238.
(2) density
Density is in density gradient column, is measured by ASTMD1505 method.
(3) melt flow rate (MFR) ratio (MFRR)
MFRR is by 190 DEG C and weight 21.6kg (MI21) and 2.16kg (MI2) the ratio (MI of melt flow index21/MI2) calculate.
(4) molecular weight distribution
Molecular weight distribution is calculated by the ratio (Mw/Mn) of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and number-average molecular weight (Mn).
(5) zero-shear viscosity: dynamically flow-data is by frequency scanning method, at a temperature of 190 DEG C, uses rheology ARES flowing meter to measure and calculate.Interval in parallel-plate structure is 2mm, and this board diameter is 25mm, and strain amplitude is 10%.This frequency is measured in 0.05-300rad/sec scope.Zero-shear viscosity uses Carraeu pattern to calculate.
(6) shear viscosity ratio (SHI): SHI is to be calculated by the ratio of the complex viscosity under the frequency of 0.1rad/sec and the complex viscosity under 100rad/sec frequency, and it is measured by ARES.
(7) critical phase angle (δ c)
First, dynamic flow-data is by frequency scanning method, uses the ARES device of TAInstrumentsCorporation to measure.When being prepared the figure of phase angle displacement (δ) and complex modulus (G*) by measurement data, linear structure PE and LCB structure PE show different behaviors, and the PE with LCB structure has flex point, at this flex point, in the figure of phase angle displacement (δ) and complex modulus (G*), graph gradient changes, and it is referred to as critical phase angle (δ c).Generally, this critical phase angle (δ c) is relevant with the content of LCB, and as result, it is known that along with the increase of LCB content, δ c reduces.The method of the critical phase angle of this calculating (δ c) is to be carried out by the dynamic flow-data of upper planar survey.
1. the calculating of modulus of complex number spirogram
G* is to use equation below 1., by storage modulus G ' and loss modulus G " result calculate, and draw as shown in Figure 1.
G * = ( G &prime; ) 2 + ( G &prime; &prime; ) 2 = T &gamma; ……①
Wherein, G '=(σ 0/ γ 0) cos δ, G "=(σ 0/ γ 0) sin δ
2. the calculating of phase angle displacement (δ) figure
The dynamic testing method using the ARES of strain controlling type is a kind of by vibration strain being added to melt polymers with the SIN function shown in Fig. 2, the method measuring relation between stress and strain, and measure stress at that time, and have resilient homophase performance and have the combination performance viscoelasticity of sticking out-phase performance.Complex modulus G* calculated above is drawn together with phase angle displacement (δ), obtains result shown in Fig. 3.Fig. 3 shows linear structure PE and the mapping result of LCB structure PE, and it can be seen that according to the difference of described structure.
The calculating of the most critical phase angle (δ c)
Flex point, phase angle (δ) becomes critical phase angle (δ c) with the slope of figure in the curve of complex modulus (G*) wherein.These computational methods impart a cycle (G* value becomes straight line from downside wherein) and carry out slope calculations, as shown in Figure 4.Equally, after by flex point, its straight point of change is assigned slope calculations.After the slope calculating two cycles, in the critical phase angle of intersection calculations (δ c).
(8) melt strength
The melt strength of each sample uses rheology tonometer to measure, as shown in Figure 5.The melt resin being passed through hole by constant power is removed by gathering way, and is applied to stress thereon with load cell measurement.Melt tension increases according to the increase of removing speed, but is held in predetermined value, and this value is that the melt tension value as measured resin measures.It is 90 DEG C with chamber temp that the temperature of molten-bath is 150 DEG C.Described bore dia is 2mm, and L/D is 32/2, and resin injection angle is 30 °, and piston speed is 10mm/min.
(9) mist degree (%)
The haze value (%) of mold film is measured by ASTMD-1003-95.
[embodiment 2]
Prepare the catalyst of metallocene load
Catalyst is to prepare by method same as in Example 1, except, in the preparation method of the catalyst loaded at the metallocene of embodiment 1, using ethylenebis (indenyl) zirconium dichloride [Et (IND)2ZrCl2] (metallocene/silicon dioxide=60 μm ol/g silicon dioxide), and ethylenebis (4,5,6,7-tetrahydro indenyl) zirconium dichloride [Et (THI)2ZrCl2] (metallocene/silicon dioxide=35 μm ol/g silicon dioxide), and two (cyclopentadienyl group) titanium chloride [Cp2TiCl2](Cp2TiCl2/ silicon dioxide=18 μm ol/g silicon dioxide) replace ethylenebis (indenyl) zirconium dichloride [Et (IND)2ZrCl2] (metallocene/silicon dioxide=120 μm ol/g silicon dioxide) and dicyclic pentylene titanium dichloride [Cp2TiCl2](Cp2TiCl2/ silicon dioxide=18 μm ol/g silicon dioxide) outside.
Gas-phase polymerization
This ethylene copolymer is to obtain by carrying out gas-phase polymerization same as in Example 1, except in the gas phase polymerization process of embodiment 1, outside the hydrogen/ethylene molar ratio being used for regulating hydrogen phase composition is adjusted to 0.02 and the 1-hexene/ethylene molar ratio being used for regulating comonomer (1-hexene) gas phase composition is adjusted to 0.1.
[embodiment 3]
Synthesis dimethylated methylene silylation (tert-butyl group amido) tetramethyl-ring pentadienyl) dibenzyl Titanium [(Me 2 Si(NtBu)(Cp*)Ti(Bn) 2 ]
Measure the Ti (CH of 5.2mmol2Ph)4With the dimethylated methylene silylation (tert-butyl group amido) (tetramethyl-ring pentadienyl) of 4.0mmol, and it is completely dissolved by injecting the 50mL toluene of regulation in Schlenk line.This reactor covering daylight is warmed up to 60 DEG C and reacts 12 hours.This product is dried in a vacuum.Dry product pentane is extracted again and is again vacuum dried, finally obtain Me2Si(NtBu)(Cp*)Ti(Bn)2.Productivity > 90%.The structure of the finalization compound obtained be as1HNMR is detected.
1HNMR (400MHz, C6D6) 7.16 (Ph, 4H, d), 6.95 (Ph, 4H, t), 6.90 (Ph, 2H, t), 2.58 (CH2Ph, 2H, d), 2.25 (CH2Ph, 2H, d), 1.81 (C5Me4, 6H, s), 1.63 (C5Me4, 6H, s), 1.43 (tNBu, 9H, s), 0.41 (SiMe2, 6H, s)
Prepare the catalyst of metallocene load
This catalyst is to be prepared by method same as in Example 1, except, in the preparation method of the catalyst loaded at the metallocene of embodiment 1, using ethylenebis (indenyl) zirconium dichloride [Et (IND)2ZrCl2] (metallocene/silicon dioxide=35 μm ol/g silicon dioxide), dimethylated methylene silylation (tert-butyl group amido) tetramethyl-ring pentadienyl) dibenzyl titanium [Me2Si(NtBu)(Cp*)Ti(Bn)2] (metallocene/silicon dioxide=120 μm ol/g silicon dioxide) (it is above synthesis) and double-CyclopentadienyltitaDichloride Dichloride [Cp2TiCl2](Cp2TiCl2/ silicon dioxide=18 μm ol/g silicon dioxide) replace ethylenebis (indenyl) zirconium dichloride [Et (IND)2ZrCl2] (metallocene/silicon dioxide=120 μm ol/g silicon dioxide) and dicyclic pentylene titanium dichloride [Cp2TiCl2](Cp2TiCl2/ silicon dioxide=18 μm ol/g silicon dioxide) outside.
Gas-phase polymerization
This ethylene copolymer is to obtain by carrying out gas-phase polymerization same as in Example 1, except in the gas phase polymerization process of embodiment 1, outside the hydrogen/ethylene molar ratio being used for regulating hydrogen phase composition is adjusted to 0.016 and the 1-hexene/ethylene molar ratio being used for regulating comonomer (1-hexene) gas phase composition is adjusted to 0.08.
<comparative example 1>
This ethylene copolymer is to be obtained by gas-phase polymerization same as in Example 1, in addition to using the 1018CA (it is commercially available as metallocene catalyst) of ExxonmobilCorporation.
<comparative example 2>
This ethylene copolymer is to be obtained by gas-phase polymerization same as in Example 1, in addition to using the 7120S (it is commercially available as metallocene catalyst) of SamsungTotalCorporation.
<comparative example 3>
This ethylene copolymer is to be obtained by gas-phase polymerization same as in Example 1, in addition to the 4220S (it is commercially available as metallocene catalyst) and use 1-butylene except using SamsungTotalCorporation replaces 1-hexene as comonomer.
Measuring embodiment and the physical property of copolymer resin that comparative example is obtained, and be summarised in table 2 below, Fig. 6 shows the complex modulus of various resin and the figure of phase angle.
[table 2]
As listed in table 2 with shown in Fig. 6, it is similar to embodiment 1-3, it can be seen that flex point (it is LCB performance) is the critical phase angle to be had according to metallocene catalyst and is formed.Further it can be seen that described metallocene catalyst resin is compared with the ziegler-natta-based resin (it is same molecular amount (MI=1)) of comparative example shows high fondant-strength.
Prepare inflation film
Thin film molding is by following condition, uses the copolymer resin (MI=1) of embodiment 2 in embodiment and the copolymer resin of comparative example 1-3 to carry out, and measures processability and the physical property of prepared thin film.
Thickness be the inflation film of 50 μm be processing temperature 190 DEG C, screw rod rpm is 50rpm and BUR2, uses inflation film moulding press (screw rod 50mm φ, port mould diameter 100mm and mouth die gap 2.5mm) to prepare.
Measurement result, processability and the physical property of prepared thin film are listed in the table below in 3.
[table 3]
As listed by table 3, the resin of embodiment 2 has minimum load during extrusion method, the resin not having the comparative example 1 of flex point at phase angle has the highest machining load and bubble unstability, and in the comparative example 2 with flex point, bubble is stable, and machining load is higher than ziegler-natta-based resin.In comparative example 3 (it is ziegler-natta-based resin), even if there be no LCB performance, owing to wide molecular weight distribution performance, bubble is stable, and machining load is relatively low, but mist degree is the highest and mechanical performance is low.With existing Metallocenyl resin-phase ratio, the performance that embodiment 2 has excellence and the extrusion processing characteristics significantly improved, there is no the rapid degradation of thin film mechanical performance.
From foregoing teachings, it will be appreciated that describe the different embodiments of the present invention for purposes of illustration, and different changes can be carried out, without deviating from the scope and spirit of the present invention.Therefore, different embodiment disclosed herein is not intended to be restrictive, and real scope and spirit are represented by claim below.

Claims (8)

1. a copolymer based on ethylene, it is by using metallocene catalyst copolymerization of ethylene and alpha-olefin to prepare, and has following performance:
1) melt flow index is 0.1-15.0g/10 minute (190 DEG C and 2.16Kg weight),
2) density is 0.900-0.929g/mL,
3) molecular weight distribution (weight-average molecular weight/number-average molecular weight) is 2.5-6.0, and
4) in the dependency of complex modulus and phase angle the correlation curve of phase angle and complex modulus 103-107Modulus of complex number value between there is flex point, it is measured by Dynamic shear viscosity measurement, and critical phase angle (δ c) is 20-70.
2. the copolymer based on ethylene of claim 1, wherein this alpha-olefin is selected from propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-endecatylene, 1-dodecylene, tetradecene, cetene and 1-eicosylene.
3. the copolymer based on ethylene of claim 1, wherein said metallocene catalyst is to be prepared by the preparation method including below step:
(1) aikyiaiurnirsoxan beta, metallocene compound, titanocenes compound or Binary catalysts are supported on carrier, wherein metallocene compound: the use ratio of titanocenes compound or Binary catalysts is 35:1-2:1 mol ratio；
(2) catalyst of load obtained in (1) is cleaned with organic solvent；With
(3) catalyst as catalyst fines of cleaning in (2) after the drying, is collected.
4. the copolymer based on ethylene of claim 3, wherein said metallocene compound is selected from least one of the compound shown in formula (1)-(3):
(CpRn)(CpR’m)MLq‥‥‥(1)
Here Cp is cyclopentadienyl group, indenyl or fluorenyl,
R and R ' represents hydrogen, alkyl, alkyl ether, allyl ether, phosphine or amine independently of one another,
L represents alkyl, pi-allyl, aryl alkyl, amido, alkoxyl or halogen,
M represents the transition metal of the 4th or 5 races in periodic chart,
Integer in the range of n, m and q are the most following: 0≤n < 5,0≤m < 5 and 1≤q≤4,
Q(CpRn)(CpR’m)MLq‥‥‥(2)
Here Cp, R, R ', M with L have the implication identical with formula (1),
Q is the crosslink part between Cp ring, and represents dialkyl group, alkylaryl, diaryl silicon or have the alkyl of 1-20 carbon atom, and
Integer in the range of n, m and q are the most following: 0≤n < 4,0≤m≤4 and 1≤q≤4,
Here x is 0,1,2,3 or 4, and y is 0 or 1,
R represents the substituent group with 1-20 non-hydrogen atom, selected from hydrogen, has the alkyl of 1-20 carbon atom, silicyl, germyl, cyano group, halogen or its compound group,
Y ' represents-O-,-S-,-NR*-or-PR*-(R* represents hydrogen, the alkyl with 1-12 carbon atom, has the oxyl group of 1-8 carbon atom, silicyl, has the haloalkyl of 1-8 carbon atom, the halogenated aryl with 6-20 carbon atom or its compound group here)
Z represents SiR*2、CR*2、SiR*2SiR*2、CR*2CR*2, CR*=CR*, CR*2SiR*2Or GeR*2, R* be defined above identical,
Each L represents the substituent group with 1-20 non-hydrogen substituent independently, its selected from halogen, the alkyl with 1-20 carbon atom, the oxyl group with 1-18 carbon atom, have 1-19 carbon atom hydrocarbylamino, there is the alkyl amido of 1-18 carbon atom, the alkyl phosphorio group with 1-18 carbon atom, the alkylthio with 1-18 carbon atom are rolled into a ball and are combined group, or two substituent groups L represent neutral conjugation diene or the divalent group with 1-30 carbon atom, and
M represents the 4th or 5 group 4 transition metal in periodic chart.
5. the copolymer based on ethylene of claim 3, wherein titanocenes compound or Binary catalysts are selected from the compound shown in following formula (4):
(CpRn)(CpR’m)TiLq‥‥‥(4)
Here Cp is cyclopentadienyl group, indenyl, tetrahydro indenyl or fluorenyl；
Rn and R ' m represents hydrogen independently of one another, has the alkyl of 1-20 carbon atom, alkyl ether, aIkylsilyl groups, allyl ether, alkoxyalkyl, phosphine or amine,
L represents alkyl, pi-allyl, aryl alkyl, amido, alkoxyl or halogen, and
Integer in the range of n, m and q are the most following: 0≤n < 5,0≤m < 5 and 1≤q≤4.
6. the copolymer based on ethylene of claim 1, wherein ethylene copolymer is prepared in gas-phase polymerization reactor.
7. the copolymer based on ethylene of claim 1, wherein measured under 190 DEG C and 21.6kg melt flow index (MI21) and melt flow index (MI measured under 190 DEG C and 2.16kg2) ratio (MI21/MI2) it is 15-100.
8. the copolymer based on ethylene of claim 1, wherein the alpha-olefin content of copolymer is 1-20wt%.
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