CN106674400A

CN106674400A - Ethylene copolymer having excellent processability

Info

Publication number: CN106674400A
Application number: CN201610868139.7A
Authority: CN
Inventors: 杨春柄; 李泳周; 李殷雄
Original assignee: Samsung Total Petrochemicals Co Ltd
Current assignee: Hanwha TotalEnergies Petrochemical Co Ltd
Priority date: 2015-11-11
Filing date: 2016-09-30
Publication date: 2017-05-17
Anticipated expiration: 2036-09-30
Also published as: KR20170055149A; KR101740149B1; CN106674400B

Abstract

The invention relates to an ethylene copolymer having excellent processability, and more particularly, relates to an ethylene copolymer having excellent extrusion processability and being prepared in a gas-phase reactor with a metallocene catalyst. The metallocene catalyst includes (A) a metallocene catalyst component, (B) a non-halogenated mono-ring pentadiene 4-group metal compound, (C) activative cocatalyst, and (D) a carrier component.

Description

The ethylene copolymer of excellent in workability

Technical field

The present invention relates to warm water and steam heating pipe ethylene copolymer, in detail, are related in Metallocene catalysts technique With the existing ethylene copolymer with identical melt index, molecular weight distribution and density compare rigidity, impact resistance etc. this The physical property of sample is maintained, while the more excellent ethylene copolymer of processability.

Background technology

As warm water and heating tank plastic tube raw material, use polyethylene, polrvinyl chloride, polypropylene, polybutene etc. several Plastic raw materialss are planted, in these raw materials, when polyethylene compares with other raw materials, if comparing merits and demerits, strong point is dominant, because This takes advantage in the market.Crosslinking polyethylene and non-cross-linked polyvinyl in polyethylene raw material, crosslinked polyethylene is given birth in material Cross-linking process step must be added during product, thus have that the quality problems such as the homogeneity of additional expense and quality produce is main Reason.In addition, in the feature of crosslinked products itself, recirculation is difficult, and environment amenable main cause has restriction Factor.On the other hand, non-cross-linked polyvinyl itself has in conventional polyvinyl resin pressure, environmental stress resistance characteristic (ESCR) there is weakness on.But, recently due to the polyolefin appearance of new metallocene catalyst, with the past impossible Polyvinyl resin is designed to possibility, and such weakness is constantly occupied in the market as leading temperature by significantly perfect The water and steam heating pipe position of plastic tube raw material.

Metallocene can typically use formula L_nMQ_pRepresent, wherein M is the metal of IIIB races, Group IVB, VB races or group vib；Q It is the alkyl or halogen of the carbon atom with 1~20；P is atomicity -2 of M, and L is the part combined with metal M, and n is 4-p. The metallocene compound is combined by the MAO (MAO) as promoter, organo-aluminium with anionic property lewis acid And be activated, for polyethylene manufacture.The side of polyethylene is manufactured with the catalyst for having used metallocene catalyst and aikyiaiurnirsoxan beta etc. It is various known to method.But, in the case of the polyethylene especially with metallocene catalyst manufacture, due to Narrow Molecular Weight Distribution and Homogeneous comonomer (comonomer) distribution and show excellent mechanical properties, but during extrusion molding engine load and Resin pressure exceedingly rises, and produces the problem of poor in processability.As the example, disclose in Japanese Unexamined Patent Publication 10-193468 The crosslinking pipe of the polyethylene manufactured with metallocene catalyst is used.But, in the case of the polyethylene, due to narrow molecular-weight point Cloth, generates extrusion plus the above-mentioned problem in man-hour and melt fracture (melt occurs on the surface of the pipe processed Fracture problem) coarse, that thus pipe physical property is reduced.

As for improve polyethylene extrusion processability method, it is known make molecular weight distribution broaden, introduce long-chain divide The method propped up.The molecular weight distribution for making polyethylene broadens and also to processability produce main impact sometimes, but, make molecular weight point The method that cloth exceedingly broadens can make product mechanical properties and the transparency reduction, occur low-molecular weight increases cause glue Even with the problem of surface migration, it is not suitable as improving the scheme of extrusion processability.

In Korean Patent 10-0263803, melt index ratio (MI is described₁₀/MI₂) >=5.63, meet molecular weight distribution (Mw/M)≤(MI₁₀/MI₂) -4.63, the main chain along polymer there is having per 1000 0.01~3 long chain branches of carbon The substantially polymer of linear olefin of elasticity, adopts the polymer for manufacturing in manner just described, it is characterised in that all melt fractures The critical shearing stress of the starting point of (Gloss Melt fracture) is than 4 × 10⁶dyne/cm²Greatly.But, in above-mentioned patent The specific data with regard to processability are not mentioned.

Melt index ratio (MI has been recorded in Korean Patent 10-0529425₂₁/MI₂) be 35~80 the poly- second of linear, low density The easy processing method of the improvement of alkene.But, for long chain branches effect is not specifically referred in above-mentioned patent, it is considered to by When the molecular weight distribution that embodiment is referred to is more than 5, it is difficult to be considered as the effect of long chain branches introducing.

Molecular weight distribution has been recorded in Korean Patent 2010-0094931 for more than 3.5, DRI (Dow Rheology Index) it is the improved olefin polymer of processability that more than 0.3, flow-activation energy is 40~80kJ/mol.Although point Son amount distribution is wide to 3.5~8.2 or so, and activation energy shows 44~81kJ/mol, but DRI (Dow Rheology Index) is aobvious 0.3~0.82 or so low value is shown, it is difficult to obtain the effect of processability improvement.In addition, in above-mentioned patent, for processability Specific data are not referred to.

Melt flow index has been recorded in Korean Patent 10-0646249 for 0.3~1.0g/10 point, density be 0.930~ 0.945g/mL, molecular weight distribution are the effective polyethylene of feed pipe of 5~30 excellent in workability.Molecule shown in embodiment Amount is distributed as 17.3~18.2, shows that outlet pipe molecular weight distribution wide when processing makes the improved feature of processability.

The metallocene catalyst by using mono-cyclopentadienyl based structures has been recorded in EP Published Patent EP1935909A1 Long chain branches are introduced so as to show the linear low density polyethylene (LLDPE) of the extrusion molding of raising.As expression long chain branches degree Index, using DRI (Dow Rheology Index), is referred to 0 ＜ DRI/MI₂＜ 0.002G'-0.745 (elastic modulus G ' be Value under loss moduluses (loss modulus) G'=500Pa), but MI₂DRI under=1 level is too low, and as little as 0.2~0.3 is left It is right, it is difficult to expect the effect for greatly improving of extrusion processability.

The a small amount of organic peroxy of addition is proposed in the A1 of the US publication US 005962598 and A1 of US 0035545 Compound and improve the technology of the foaming stability of polyethylene, but adopt the film that manufactures in such a way and produce impact strength, tear The problem that the mechanical properties such as intensity decline to a great extent.

For above-mentioned metallocene catalyst, in order to used in mobile phase reactor or slurry-phase reactor, it is necessary to load On appropriate support, in addition, each catalyst particle for having loaded metallocene only shows sufficiently activity, just will not produce Problem caused by raw catalyst support residue.

Now one of manufacture method of representational metallocene supported catalyst of application is to make metallocene catalysis Agent be carried on together with MAO silicon dioxide method (with reference to U.S. Patent No. 4,808,561, U.S. Patent No. 4, 897, No. 455, U.S. Patent No. 5,240,894).The method is the hydroxyl of silicon dioxide reacted, made with MAO MAO is carried on silica surface, makes the method that metallocene catalyst is carried on the MAO for having loaded.Just For metallocene catalyst component, simultaneously load with MAO, or by adding after MAO load is made Reaction load it.The activity of the catalyst for being loaded is proportional to the amount of the metallocene composition for being loaded, in addition also with have The load capacity for helping the MAO of the load of metallocene catalyst component is proportional.MAO not only facilitates luxuriant gold The load of metal catalyst, and performance protects metallocene catalyst component from the effect of the impact of catalyst toxin.Therefore, first The load capacity of base aikyiaiurnirsoxan beta directly produces impact to the activity of catalyst.

The content of the invention

The invention problem to be solved

Here, the present inventor is in order to solve above-mentioned problem of the prior art, have studied does not make molecular weight distribution excessively become Suitably be adjusted in the case of width, to manufacture and design physical property and voltage endurance is excellent and warm water of excellent in workability and Steam heating pipe non-crosslinking ethylene copolymer, is as a result designed so that alpha-olefin comonomer concentrates on height in molecular weight distribution Molecular weight fractions and be distributed, suitably Molecular regulator amount distribution, while introduce long chain branches in polymer, manufactured with excellent Different processability, pressure and environmental stress resistance characteristic ethylene copolymer.

Therefore, it is an object of the invention to provide keep the excellent pipe physical property characteristic such as pressure and environmental stress resistance characteristic, Simultaneously pipe adds man-hour to improve the ethylene of the processing problems such as the rising of machining load, rubbery (メヤニ) (Die build-up) Copolymer resin.

The solution of problem

The present invention is in order to realize above-mentioned purpose, there is provided ethylene copolymer, it is characterised in that (1) melt flow index is 0.2~2.0g/10 minutes (190 DEG C, 2.16Kg load), (2) density is 0.930~0.955g/mL, and (3) molecular weight distribution is (heavy Average molecular weight/number-average molecular weight) it is 2.5~4.0, (4) BOCD indexes (BOCDI, Broad Orthogonal Comonomer Distribution Index) ＞ 0.5, (5) critical phase angle (Critical phase angles, δ_C) ＜ 70.0.Meet above-mentioned The ethylene copolymer of condition ((1)~(5)) meet the physical property of the ethylene copolymer resin for want resulting improvement in the present invention with Processability, beyond the above-mentioned condition ((1)~(5)) in the case of do not obtain in terms of physical property characteristic, processability and meet what is required As a result.

Present disclosure is explained below.

In technical terms used in the present invention, in the case of without other definition, with the technical field of the invention In there is the implication that is generally understood that of personnel of common knowledge.

BOCD indexes (BOCDI, Broad Orthogonal Comonomer Distribution used in the present invention Index：Generalized orthogonal comonomer distribution index) it is the distribution that alpha-olefin comonomer is numerically represented in olefin copolymer Concept.That is, in GPC, for comonomer analysis, using being provided with FTIR (Fourier Transform Infrared Spectroscopy：Fourier transform infrared spectrometer) GPC-IR be analyzed and calculate.In GPC-IR analysis results with SCB (SCB, Short on the basis of weight average molecular weight (Mw), to determining upper 80% site (high molecular site) of molecular weight Chain Branch (short chain branch), mean comonomer) content (#/1000C) and the next 20% site (low-molecular-weight position Point) SCB contents be measured, calculate BOCD indexes with following mathematical expressions.

From above-mentioned formula, for BOCD indexes, in macromolecule both sides, SCB contents are higher, and the value of BOCD indexes more rises Height, by such structure BOCD structures are referred to as.Therefore, it is not BOCD structures if BOCD exponential quantities are less than 0, if super 0 is crossed, then can be described as the olefin copolymer of BOCD structures, be worth bigger, it may be said that the characteristic is more excellent.Claim in the present invention The BOCD values of ethylene copolymer be minimum more than 0.5, more hour can not improve the physical property such as pressure and environmental stress resistance characteristic.

Critical phase angle (Critical phase angle, δ used in the present invention_C) it is for comparing with each other The rheol method of the polymer substance of different architectural characteristics, especially for the long chain branches for confirming ethylene copolymer (Long Chain Branch, LCB) degree is useful method.

The method is otherwise referred to as Van-Gurp Palmen analysis (list of references, 1.Rheology Bulletin,1998,67,5-8、2.Correlations between the Characteristic Rheological Quantities and Molecular Structure of Long-Chain Branched Metallocene Catalyzed Polyethylenes,Macromolecules,2011,44,5401-5413)。

By the phase place obtained by dynamic frequency scanning (Dynamic frequency sweep) with ARES measuring apparatus Angular displacement (shift) (δ) makes linear structure polyethylene (PE) and LCB structure polyethylene with the figure (plot) of complex modulus (G*) Different behaviors are shown, LCB is bigger under certain G* values, then more show low phase angle.Phase angle (δ) with it is multiple The flex point that the slope of coordinate diagram changes is produced in elastic modelling quantity (G*) curve, critical phase angle (δ is referred to as_C), with LCB's There is dependency relation in degree, LCB is bigger, then δ_CIt is lower.The critical phase angle of the ethylene copolymer claimed in the present invention (Critical phase angles, δ_C) ＜ 70.0, processing problems can not be improved when bigger.Detailed analytic process is said below It is bright.

The manufacture method of the ethylene copolymer of the present invention is illustrated below.Being exemplified below the example of manufacture method is carried out Illustrate, but be not limited to the example.

The ethylene copolymer of the present invention for example can using catalyst as following, adopt gas-phase polymerization reactor (Gas-phase Recator) is manufactured.The ethylene copolymer of manufacture is characterised by：(1) melt flow index be 0.3~ 2.0g/10 minutes (190 DEG C, 2.16Kg load), (2) density is 0.930~0.955g/mL, and (3) molecular weight distribution (is divided equally again Sub- amount/number-average molecular weight) it is 2.5~4.0, (4) BOCD indexes (BOCDI, Broad Orthogonal Comonomer Distribution Index) ＞ 0.5, (5) critical phase angle (δ_C) ＜ 70.0, for as the poly- second of warm water and steam heating pipe Alkene materials application is useful.

Catalyst

Catalyst used in the manufacture of the ethylene copolymer of the present invention preferably comprises (A) metallocene compound, (B) non-halogen Change the race's metallic compound of monocyclopentadienyl 4, (C) active cocatalyst (Activating cocatalysts) composition and (D) The metallocene catalyst of carrier components.

For (A) metallocene compound in above-mentioned catalyst constituent, to its species, there is no particular restriction, used as excellent Example is selected, the dicyclopentadienyl metallocene of following formulas (1) or the bridging bonding metallocene of following formulas (2) can be included.

First, dicyclopentadienyl metallocene can be represented by following formula (1).

(CpR_n)(CpR'_m)ML_q (1)

Wherein, Cp be cyclopentadienyl group, indenyl or fluorenyl,

R and R' represent independently of one another hydrogen, alkyl, alkyl ether (alkylether), aryl ether (allylether), phosphine (phosphine) or amine (amine),

L represents alkyl, pi-allyl, aryl alkyl, amide (amide), alkoxy or halogen (halogen),

M represents the transition metal (Transition metal) of 4 races of periodic chart or 5 races,

N is the positive number of 0≤n of satisfaction ＜ 5, and m is the positive number of 0≤m of satisfaction ＜ 5, and q is the positive number of satisfaction 1≤q≤4.

Above-mentioned bridging bonding metallocene can be represented by following formula (2).

Q(CpR_n)(CpR'_m)ML_q (2)

Wherein, Cp, R, R', M, L have and above-mentioned formula (1) identical implication, and Q is the bridging key of C interannulars, represents dioxane The alkyl of base (Dialkyl), alkylaryl (Alkylaryl), diaryl silicon (Diaryl silicon) or carbon number 1~20, n To meet the positive number of 0≤n ＜ 4, m is the positive number of 0≤m of satisfaction ＜ 4, and q is the positive number of satisfaction 1≤q≤4.

For the species of the dicyclopentadienyl metallocene compound of the structure for meeting above-mentioned formula (1), however it is not limited to this, Double (cyclopentadienyl group) zirconium dimethyl, double (methyl cyclopentadienyl) zirconium dimethyls, double (n-butyl cyclopentadiene can be included Base) zirconium dimethyl, double (indenyl) zirconium dimethyls, double (1,3- dimethylcyclo-pentadienyl) zirconium dimethyls, (pentamethylcyclopentadiene Base) (cyclopentadienyl group) zirconium dimethyl, double (pentamethylcyclopentadiene base) zirconium dimethyls, double (fluorenyl) zirconium dimethyls, double (2- first Base indenyl) zirconium dimethyl, double (2- phenyl indenyls) zirconium dimethyls, cyclopentadienyl group (2- phenyl indenyls) zirconium dimethyl etc. bicyclic penta Dialkylene metallocene.

As the bridging bonding metallocene represented by above-mentioned formula (2), however it is not limited to this, dimethyl silane can be included Base double (1- indenyls) zirconium dimethyl, dimetylsilyl (9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, dimethyl methyl silicon Alkyl double (1- cyclopentadienyl groups) zirconium dimethyl, dimetylsilyl (9- fluorenyls) (1- indenyls) zirconium dimethyl, dimethyl methyls Silylation double (1- indenyls) hafnium dimethyl, dimetylsilyl (9- fluorenyls) (1- cyclopentadienyl groups) hafnium dimethyl, dimethyl Double (1- cyclopentadienyl groups) the hafnium dimethyl of silicyl, dimetylsilyl (9- fluorenyls) (1- indenyls) hafnium dimethyl, sub- second Base double (1- cyclopentadienyl groups) zirconium dimethyl, ethylenebis (1- indenyls) zirconium dimethyl, ethylenebis (4,5,6,7- tetrahydrochysene -1- Indenyl) zirconium dimethyl, ethylenebis (4- methyl isophthalic acids-indenyl) zirconium dimethyl, ethylenebis (5- methyl isophthalic acids-indenyl) zirconium diformazan Base, ethylenebis (6- methyl isophthalic acids-indenyl) zirconium dimethyl, ethylenebis (7- methyl isophthalic acids-indenyl) zirconium dimethyl, ethylenebis (4- phenyl -1- indenyls) zirconium dimethyl, ethylenebis (5- methoxyl group -1- indenyls) zirconium dimethyl, ethylenebis (2,3- diformazans Base -1- indenyls) zirconium dimethyl, ethylenebis (4,7- dimethyl -1- indenyls) zirconium dimethyl, ethylenebis (4,7- dimethoxys - 1- indenyls) zirconium dimethyl, ethylenebis (front three cyclopentadienyl group) zirconium dimethyl, ethylenebis (5- dimethylamino -1- indenes Base) zirconium dimethyl, ethylenebis (6- dipropylamino -1- indenyls) zirconium dimethyl, ethylenebis (4,7- double (dimethylaminos Base) -1- indenyls) zirconium dimethyl, ethylenebis (5- diphenylphosphino -1- indenyls) zirconium dimethyl, ethylidene (1- dimethylaminos Base -9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, ethylene (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, Ethylidene (9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, ethylenebis (9- fluorenyls) zirconium dimethyl, ethylenebis (1- rings penta Dialkylene) hafnium dimethyl, ethylenebis (1- indenyls) hafnium dimethyl, ethylenebis (4,5,6,7- tetrahydrochysene -1- indenyls) hafnium diformazan Base, ethylenebis (4- methyl isophthalic acids-indenyl) hafnium dimethyl, ethylenebis (5- methyl isophthalic acids-indenyl) hafnium dimethyl, ethylenebis (6- methyl isophthalic acids-indenyl) hafnium dimethyl, ethylenebis (7- methyl isophthalic acids-indenyl) hafnium dimethyl, ethylenebis (4- phenyl -1- indenes Base) hafnium dimethyl, ethylenebis (5- methoxyl group -1- indenyls) hafnium dimethyl, ethylenebis (2,3- dimethyl -1- indenyls) hafnium two Methyl, ethylenebis (4,7- dimethyl -1- indenyls) hafnium dimethyl, ethylenebis (4,7- dimethoxy -1- indenyls) hafnium diformazan Base, ethylenebis (front three cyclopentadienyl group) hafnium dimethyl, ethylenebis (5- dimethylamino -1- indenyls) hafnium dimethyl, Ethylenebis (6- dipropylamino -1- indenyls) hafnium dimethyl, ethylenebis (4,7- double (dimethylamino) -1- indenyls) hafnium two Methyl, ethylenebis (5- diphenylphosphino -1- indenyls) hafnium dimethyl, ethylidene (1- dimethylamino -9- fluorenyls) (1- rings penta Dialkylene) hafnium dimethyl, ethylidene (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) hafnium dimethyl, ethylidene (9- fluorenyls) Double (1- cyclopentadienyl groups) zirconiums two of (1- cyclopentadienyl groups) hafnium dimethyl, ethylenebis (9- fluorenyls) hafnium dimethyl, 2,2- propyl group Double (4,5,6, the 7- tetrahydrochysene -1- indenyls) zirconium dimethyls of double (1- indenyls) zirconium dimethyl of methyl, 2,2- propyl group, 2,2- propyl group, 2,2- Double (4- methyl isophthalic acids-indenyl) zirconium dimethyls of propyl group, double (5- methyl isophthalic acids-indenyl) zirconium dimethyls of 2,2- propyl group, the double (6- of 2,2- propyl group Methyl isophthalic acid-indenyl) zirconium dimethyl, double (7- methyl isophthalic acids-indenyl) zirconium dimethyl of 2,2- propyl group, the double (4- phenyl -1- indenes of 2,2- propyl group Base) zirconium dimethyl, double (5- methoxyl group -1- indenyls) zirconium dimethyl of 2,2- propyl group, 2,2- propyl group be double (2,3- dimethyl -1- indenyls) Double (4, the 7- dimethyl -1- indenyls) zirconium dimethyls of zirconium dimethyl, 2,2- propyl group, double (4, the 7- dimethoxy -1- indenes of 2,2- propyl group Base) zirconium dimethyl, double (front three cyclopentadienyl group) zirconium dimethyl of 2,2- propyl group, the double (5- dimethylamino -1- indenes of 2,2- propyl group Base) zirconium dimethyl, double (6- dipropylamino -1- indenyls) zirconium dimethyl of 2,2- propyl group, double (4, the 7- double (dimethyl of 2,2- propyl group Amino) -1- indenyls) zirconium dimethyl, 2,2- propyl group double (5- diphenylphosphino -1- indenyls) zirconium dimethyl, 2,2- propyl group (1- diformazans Base amino -9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, 2,2- propyl group (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) Double (9- fluorenyls) zirconium dimethyl of zirconium dimethyl, 2,2- propyl group (9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, 2,2- propyl group, 2, Double (1- cyclopentadienyl groups) the hafnium dimethyl of 2- propyl group, double (1- indenyls) the hafnium dimethyl of 2,2- propyl group, 2,2- propyl group double (4,5,6,7- Tetrahydrochysene -1- indenyls) hafnium dimethyl, double (4- methyl isophthalic acids-indenyl) the hafnium dimethyl of 2,2- propyl group, double (the 5- methyl isophthalic acids-indenes of 2,2- propyl group Base) hafnium dimethyl, double (7- methyl isophthalic acids-indenyl) the hafnium dimethyl of 2,2- propyl group, double (4- phenyl -1- indenyls) the hafnium diformazans of 2,2- propyl group Double (2,3- dimethyl -1- indenyls) the hafnium dimethyl of base, 2,2- propyl group pair (5- methoxyl group -1- indenyls) hafnium dimethyl, 2,2- propyl group, Double (4,7- dimethyl -1- indenyls) the hafnium dimethyl of 2,2- propyl group, double (4,7- dimethoxy -1- indenyls) the hafnium diformazans of 2,2- propyl group Double (front three cyclopentadienyl group) the hafnium dimethyl of base, 2,2- propyl group, double (5- dimethylamino -1- indenyls) the hafnium diformazans of 2,2- propyl group Double (4,7- double (the dimethylamino) -1- indenes of double (6- dipropylamino -1- indenyls) the hafnium dimethyl of base, 2,2- propyl group, 2,2- propyl group Base) hafnium dimethyl, 2,2- propyl group double (5- diphenylphosphino -1- indenyls) hafnium dimethyl, 2,2- propyl group (1- dimethylamino -9- Fluorenyl) (1- cyclopentadienyl groups) hafnium dimethyl, 2,2- propyl group (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) hafnium dimethyl, 2,2- propyl group (9- fluorenyls) (1- cyclopentadienyl groups) hafnium dimethyl, 2,2- propyl group double (9- fluorenyls) hafnium dimethyl, diphenyl methyls Double (1- indenyls) zirconium dimethyls of double (1- cyclopentadienyl groups) zirconium dimethyls, diphenyl methyl, diphenyl methyl double (4,5,6,7- tetra- Qing ー 1- indenyls) zirconium dimethyl, double (4- methyl isophthalic acids-indenyl) zirconium dimethyl of diphenyl methyl, diphenyl methyl it is double (5- methyl- 1- indenyls) zirconium dimethyl, double (6- methyl isophthalic acids-indenyl) zirconium dimethyl of diphenyl methyl, double (the 7- methyl isophthalic acids-indenes of diphenyl methyl Base) zirconium dimethyl, double (4- phenyl -1- indenyls) zirconium dimethyl of diphenyl methyl, diphenyl methyl be double (5- methoxyl group -1- indenyls) Double (2, the 3- dimethyl -1- indenyls) zirconium dimethyls of zirconium dimethyl, diphenyl methyl, double (4, the 7- dimethyl -1- indenes of diphenyl methyl Base) zirconium dimethyl, double (4, the 7- dimethoxy -1- indenyls) zirconium dimethyl of diphenyl methyl, double (the front three basic rings penta of diphenyl methyl Dialkylene) zirconium dimethyl, double (5- dimethylamino -1- indenyls) zirconium dimethyl of diphenyl methyl, double (the 6- dipropyls of diphenyl methyl Base amino -1- indenyls) zirconium dimethyl, double (4,7- double (the dimethylamino) -1- indenyls) zirconium dimethyl of diphenyl methyl, diphenyl Methyl double (5- diphenylphosphino -1- indenyls) zirconium dimethyl, diphenyl methyl (1- dimethylamino -9- fluorenyls) (1- rings penta 2 Thiazolinyl) zirconium dimethyl, diphenyl methyl (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, diphenyl methyl (9- Fluorenyl) (1- cyclopentadienyl groups) zirconium dimethyl, double (9- fluorenyls) zirconium dimethyl of diphenyl methyl, double (the 1- rings penta of diphenyl methyl Dialkylene) hafnium dimethyl, double (1- indenyls) the hafnium dimethyl of diphenyl methyl, double (4,5,6, the 7- tetrahydrochysene -1- indenes of diphenyl methyl Base) hafnium dimethyl, double (4- methyl isophthalic acids-indenyl) the hafnium dimethyl of diphenyl methyl, double (5- methyl isophthalic acids-indenyl) hafniums of diphenyl methyl Double (6- methyl isophthalic acids-indenyl) the hafnium dimethyl of dimethyl, diphenyl methyl, double (7- methyl isophthalic acids-indenyl) the hafnium diformazans of diphenyl methyl Double (5- methoxyl group -1- indenyls) the hafnium dimethyl of base, diphenyl methyl pair (4- phenyl -1- indenyls) hafnium dimethyl, diphenyl methyl, Double (2,3- dimethyl -1- indenyls) the hafnium dimethyl of diphenyl methyl, double (4,7- dimethyl -1- indenyls) the hafnium diformazans of diphenyl methyl Double (4,7- dimethoxy -1- indenyls) the hafnium dimethyl of base, diphenyl methyl, double (front three cyclopentadienyl group) hafniums of diphenyl methyl Double (5- dimethylamino -1- indenyls) the hafnium dimethyl of dimethyl, diphenyl methyl, the double (6- dipropylamino -1- of diphenyl methyl Indenyl) hafnium dimethyl, double (4,7- double (dimethylamino) -1- indenyls) the hafnium dimethyl of diphenyl methyl, the double (5- of diphenyl methyl Diphenylphosphino -1- indenyls) hafnium dimethyl, diphenyl methyl (1- dimethylamino -9- fluorenyls) (1- cyclopentadienyl groups) hafnium two Methyl, diphenyl methyl (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) hafnium dimethyl, diphenyl methyl (9- fluorenyls) (1- Cyclopentadienyl group) hafnium dimethyl, double (9- fluorenyls) the hafnium dimethyl of diphenyl methyl, double (the 1- cyclopentadiene of diphenylsilyl group Base) zirconium dimethyl, double (1- indenyls) zirconium dimethyl of diphenylsilyl group, double (4,5,6, the 7- tetrahydrochysene -1- of diphenylsilyl group Indenyl) zirconium dimethyl, double (4- methyl isophthalic acids-indenyl) zirconium dimethyl of diphenylsilyl group, double (the 5- first of diphenylsilyl group Base -1- indenyls) zirconium dimethyl, double (6- methyl isophthalic acids-indenyl) zirconium dimethyl of diphenylsilyl group, diphenylsilyl group be double (7- methyl isophthalic acids-indenyl) zirconium dimethyl, diphenylsilyl group double (4- phenyl -1- indenyls) zirconium dimethyl, diphenyl silicons Double (2, the 3- dimethyl -1- indenyls) zirconium dimethyls of double (5- methoxyl group -1- indenyls) zirconium dimethyl of base, diphenylsilyl group, two Double (4, the 7- dimethyl -1- indenyls) zirconium dimethyls of phenyl silyl groups, double (4, the 7- dimethoxy -1- indenes of diphenylsilyl group Base) zirconium dimethyl, double (front three cyclopentadienyl group) zirconium dimethyl of diphenylsilyl group, the double (5- bis- of diphenylsilyl group Methylamino -1- indenyls) zirconium dimethyl, diphenylsilyl group double (6- dipropylamino -1- indenyls) zirconium dimethyl, diphenyl Double (4,7- double (the dimethylamino) -1- indenyls) zirconium dimethyl of silicyl, diphenylsilyl group it is double (5- diphenylphosphinos - 1- indenyls) zirconium dimethyl, diphenylsilyl group (1- dimethylamino -9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, two Phenyl silyl groups (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) zirconium dimethyl, diphenylsilyl group (9- fluorenyls) (1- Cyclopentadienyl group) zirconium dimethyl, double (9- fluorenyls) zirconium dimethyl of diphenylsilyl group, double (the 1- rings penta of diphenylsilyl group Dialkylene) hafnium dimethyl, double (1- indenyls) the hafnium dimethyl of diphenylsilyl group, diphenylsilyl group double (4,5,6,7- tetra- Hydrogen -1- indenyls) hafnium dimethyl, double (4- methyl isophthalic acids-indenyl) the hafnium dimethyl of diphenylsilyl group, diphenylsilyl group be double (5- methyl isophthalic acids-indenyl) hafnium dimethyl, diphenylsilyl group double (6- methyl isophthalic acids-indenyl) hafnium dimethyl, diphenyl silicons Double (7- methyl isophthalic acids-indenyl) the hafnium dimethyl of base, diphenylsilyl group double (4- phenyl -1- indenyls) hafnium dimethyl, diphenylmethyls Double (5- methoxyl group -1- indenyls) the hafnium dimethyl of silylation, double (2,3- dimethyl -1- indenyls) the hafnium diformazans of diphenylsilyl group Double (4,7- dimethyl -1- indenyls) the hafnium dimethyl of base, diphenylsilyl group, diphenylsilyl group it is double (4,7- dimethoxys - 1- indenyls) hafnium dimethyl, double (front three cyclopentadienyl group) the hafnium dimethyl of diphenylsilyl group, diphenylsilyl group be double Double (6- dipropylamino -1- indenyls) the hafnium dimethyl of (5- dimethylamino -1- indenyls) hafnium dimethyl, diphenylsilyl group, Double (4,7-bis- (dimethylamino)-1- indenyls) the hafnium dimethyl of diphenylsilyl group, double (the 5- hexichol of diphenylsilyl group Base phosphino- -1- indenyls) hafnium dimethyl, diphenylsilyl group (1- dimethylamino -9- fluorenyls) (1- cyclopentadienyl groups) hafnium two Methyl, diphenylsilyl group (4- butylthio -9- fluorenyls) (1- cyclopentadienyl groups) hafnium dimethyl, diphenylsilyl group (9- Fluorenyl) (1- cyclopentadienyl groups) hafnium dimethyl, double (9- fluorenyls) the hafnium dimethyl of diphenylsilyl group etc..

In addition, as the example of metallocene compound, also can include above-mentioned each titanium, zirconium and the hafnium compound enumerated " dimethyl " partial replacement is-dichloro,-dibromo,-diiodo-,-diethyl,-dibutyl,-dibenzyl,-diphenyl,-bis- -2- (N, N- dimethylaminos) benzyl, -2-butylene-Isosorbide-5-Nitrae-diyl, the trans-η 4-1 of-s-, 4- diphenyl -1,3-butadiene, the trans-η of-s- 4-3- methyl isophthalic acids, the trans-η 4-1 of 3- pentadienes,-s-, the trans-η 4-2 of 4- dibenzyl -1,3-butadiene,-s-, 4- hexadienes, - Trans-η the 4-1 of s-, the trans-η 4-1 of 3- pentadienes,-s-, the trans-η 4-1 of 4- bis- (tolyl) -1,3-butadiene,-s-, 4- are double Cis-η the 4-1 of (trimethyl silyl) -1,3-butadiene,-s-, the cis-η 4-3- first of 4- diphenyl -1,3-butadiene,-s- Cis-η the 4-1 of base -1,3-pentadiene,-s-, the cis-η 4-2 of 4- dibenzyl -1,3-butadiene,-s-, 4- hexadienes,-s- be cis - Double (the trimethyl first of the cis-η 4-1 of η 4-1,3- pentadiene,-s-, the cis-η 4-1 of 4- bis- (tolyl) -1,3-butadiene,-s-, 4- Silylation) -1,3-butadiene etc. compound etc..

In above-mentioned catalyst constituent, above-mentioned (B) non-halogenated race's metallic compound of monocyclopentadienyl 4 can be by following Formula (3) represent.

Wherein, x is 0,1,2,3 or 4, y are 0 or 1, R are hydrogen, the alkyl of carbon number 1~20, silicyl, germyl, cyanogen Base, halogen or their composite base, represent there is the substituent group of 1~20 non-hydrogen atoms, Y' represent-O- ,-S- ,-NR*-, Or-PR*- (wherein, R* be hydrogen, the alkyl of carbon number 1~12, the oxyl of carbon number 1~8, silicyl, the halo of carbon number 1~8 Alkyl, the halogenated aryl of carbon number 6~20 or their composite base), Z represents SiR*₂、Si(OR*)R*、Si(OR*)₂、Si(NR*) R*、Si(NR*)₂、CR*₂、SiR*₂SiR*₂、CR*₂CR*₂, CR*=CR*, CR*₂SiR*₂Or GeR*₂, R* is as defined above, L represents independently of one another the alkyl of carbon number 1~30, and M represents Ti or Zr.

As the example of above-mentioned (B) the non-halogenated race's metallic compound of monocyclopentadienyl 4, [(N- tert-butyls can be included Amido) (tetramethyl-η 5- cyclopentadienyl groups) -1,2- ethane diyls] titanium dimethyl, [(N- tert-butyl amidos) (tetramethyl-η 5- Cyclopentadienyl group)-dimethylsilane] titanium dimethyl, [(N- methylaminos) (tetramethyl-η 5- cyclopentadienyl groups) -1,2- ethane Diyl] titanium dimethyl, [(N- methylaminos) (tetramethyl-η 5- cyclopentadienyl groups)-dimethylsilane] titanium dimethyl, [(N- benzene Base amido) (tetramethyl-η 5- cyclopentadienyl groups)-dimethylsilane] titanium dimethyl, [(N- benzylaminos) (tetramethyl-η 5- rings Pentadienyl)-dimethylsilane] titanium dimethyl, [(N- methylaminos) (η 5- cyclopentadienyl groups) -1,2- ethane diyls] titanium two Methyl, [(N- methylaminos) (η 5- cyclopentadienyl groups)-dimethylsilane] titanium dimethyl, [(N- tert-butyl amidos) (η 5- indenes Base)-dimethylsilane] titanium dimethyl, [(N- benzylaminos) (η 5- indenyls)-dimethylsilane] titanium dimethyl, dimethyl methyl silicon Alkyl tetramethyl-ring pentadienyl-tert-butyl amido zirconium dimethyl, dimetylsilyl tert-butyl cyclopentadienyl group-tert- Butylamino zirconium dimethyl, dimetylsilyl trimethyl silyl cyclopentadienyl group-tert-butyl amido zirconium dimethyl, Dimetylsilyl tetramethyl cyclopentadienyl group ー phenyl amido zirconium dimethyls, aminomethyl phenyl silicyl tetramethyl-ring penta 2 Thiazolinyl-phenyl amido zirconium dimethyl, aminomethyl phenyl silicyl tert-butyl cyclopentadienyl group-tert-butyl amido zirconium dimethyl, Dimetylsilyl tetramethyl-ring pentadienyl-p- N- phenyl amido zirconium dimethyl etc., or by the above-mentioned each titanizing enumerated " dimethyl " partial replacement of compound and zirconium compoundss is-compound of diethyl ,-dibutyl ,-dibenzyl ,-diphenyl etc. Deng more than a kind in these can be used.

The catalyst of the present invention can include more than a kind as described above using above-mentioned such metallocene compound Metallocene compound (A).Furthermore it is possible to include additional catalyst, it is necessary in the case of, such as the metallocene in the present invention is urged Can further comprising other known catalyst components beyond agent composition.

Metallocene compound (A) used in the present invention makes with non-halogenated monocyclopentadienyl 4 race's metallic compound (B) With than (A：B) represented with mol ratio, be 0.01：1 to 100：1.If mol ratio is 0.01：Less than 1, then polymerization activity is significantly Reduce, if 100：More than 1, it is difficult to obtain the increase effect of the polymerization activity to be realized in the present invention.

(C) active cocatalyst (Activating cocatalysts) is into subpackage in the catalyst constituent of the present invention Containing aikyiaiurnirsoxan beta, organo-aluminum compound or Ionizing activators.

Aikyiaiurnirsoxan beta includes straight chain and/or cyclic alkyl aluminoxanes oligomer, is that linear alumoxanes I is oligomeric in above-mentioned aikyiaiurnirsoxan beta In the case of thing, by chemical formula R- (Al (R)-O)_n-AlR₂Represent, in the case of for Cyclic aluminoxane oligomer, by chemical formula (-Al(R)-O-)_mRepresent, wherein R is the alkyl of carbon number 1~8, preferably methyl, n is 1~40, and preferably 10~20, m is 3 ~40, preferably 3~20.Above-mentioned aikyiaiurnirsoxan beta for the non-constant width of molecular weight distribution oligomer mixture, usual mean molecule quantity For about 800~1200.Above-mentioned aluminoxanes solution can be excellent comprising aromatic hydrocarbon, aliphatic hydrocarbon or alicyclic hydrocarbon as solvent Choosing is used mainly as the solution in toluene, as its concrete example, there is 10% or 30% methyl manufactured by Albemarle companies Aikyiaiurnirsoxan beta etc..

As above-mentioned organo-aluminum compound, can use by formula AlR_nX_(3―n)(wherein, R for carbon number 1~16 alkyl, X For halogens, the alkyl aluminum compound of 1≤n≤3) represent.As the specific example of abovementioned alkyl aluminium compound, preferably make With triethyl aluminum, trimethyl aluminium, tri-n-n-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, three (2- methyl amyls) aluminum etc., particularly preferably using triisobutyl aluminium, triethyl aluminum, tri-n-hexyl aluminum or tri-n-octylaluminium.

In order to neutral metallocene compound ionizing is needed into above-mentioned Ionizing activators, can from following formula (4), (5) select in the compound or shown in (6).

B(R^a)₃‥‥‥(4)

[R^b]⁺[BR^a]^-‥‥‥(5)

[R^c-H]⁺[BR^a]^-‥‥‥(6)

In above-mentioned formula (4), (5) and (6), B is boron atom, R³For phenyl or phenoxy group, the phenyl or phenoxy group can quilts Selected from fluorine atom, can be replaced by fluorine atoms or unsubstituted C1~C20 alkyl or and then can be replaced by fluorine atoms or unsubstituted Carbon number 1~20 alkoxyl in 3~5 substituent groups replace, R^bFor the group of naphthene base of carbon number 5~7, (C1~C20) alkane Base (C6~C20) aromatic yl group or (C6~C30) aryl (C1~C20) alkyl group, [R^c-H]⁺It is by 1~3 (C1~C20) Alkyl-substituted An Huo Phosphonium ions.

As the specific example of the boron compound equivalent to above-mentioned formula (4), (5) and (6), trimethyl ammonium four can be included (phenyl) borine, triethyl ammonium four (phenyl) borine, tripropyl ammonium four (phenyl) borine, tributyl ammonium four (phenyl) borine, three Ammonium methyl four (p- tolyl) borine, trimethyl ammonium four (adjacent, p- 3,5-dimethylphenyl) borine, (the p- fluoroform of trimethyl ammonium four Base phenyl) borine, tributyl ammonium four (pentafluorophenyl group) borine, DMA (アミリジウ system) four (phenyl) borines, N, N- diethylaniline four (phenyl) borine, DMA four (pentafluorophenyl group) borine, N, N- diethylanilines four (five Fluorophenyl) borine, (phenyl) borine of San Jia Ji Phosphonium four, triphenyl phosphonium four (phenyl) borine, (pentafluorophenyl group) boron of San Jia Ji Phosphonium four Alkane, triphenyl phosphonium four (pentafluorophenyl group) borine, triphenylcarbenium four (p- trifluoromethyl) borine, triphenylcarbenium four (five Fluorophenyl) borine, trityl four (five trifluorophenyls) borine etc..

(D) carrier is the porous of solid particulate, preferably inorganic substances, example in the catalyst constituent of the present invention Such as silicon and/or aluminum oxide, most preferably deposited with the form of spheroidal particle, the particle obtained for example with spray drying process In the silicon dioxide of other effect groups most preferably with OH bases or containing active hydrogen atom.For above-mentioned carrier, averagely Granularity is 10~250 μm, it is preferable that particle mean size is 10~150 μm, is with average diameter Fine gas Hole, fine pores volume is 0.1~10ml/g, preferably 0.5~5ml/g, and the surface area of above-mentioned carrier is 5~1000m²/ g, Preferably 50~600m²/g。

Using silicon dioxide as above-mentioned carrier in the case of, it is necessary to have at least one of activity hydroxy (OH), hydroxyl Base concentration is preferably per 1g above-mentioned 0.5~more than 2.5mmole of silicon dioxide, more preferably 0.7~1.6mmole/g, if not To 0.5mmole, the load capacity of MAO is reduced, activity reduce and not preferably, if it exceeds 2.5mmole, due to OH, urges Agent composition disactivation and it is not preferred.

The hydroxyl of above-mentioned silicon dioxide can detect that the quantitative of the hydroxyl concentration on silicon dioxide is led to by IR spectrum analysis Crossing makes silica sample contact with methyl-magnesium-bromide, determines (adopting piezometry) methane gas release and carries out.

As the silicon dioxide with [OH] concentration and physical characteristics for being adapted to the present invention, surface area 300m can be used²/ The business that can be bought by the Davison Chemicals Divisions of W.R. グレースア Application De カ Application パニー of g, pore volume 1.6ml/g The name of an article XPO-2402, XPO-2410, XPO-2411 and XPO-2412 etc., in addition, also commercially available trade name Davision 948, Silicon dioxide before the dehydrations such as 952 and 955, is adjusted to desired [OH] concentration and uses through heating process.

Above-mentioned catalyst used in the manufacture of the ethylene copolymer of the present invention is by making above-mentioned (A), (B) and (C) composition It is carried on and is manufactured as the carrier of (D) composition, its loading process is preferably carried on aikyiaiurnirsoxan beta after carrier, bears metallocene Carry, using silicon dioxide as above-mentioned carrier in the case of, the hydroxyl of silicon dioxide under the anhydrous condition that there is no oxygen with aluminum Oxygen alkane reacts, and loads aikyiaiurnirsoxan beta, there is provided to treat the position (site) of load metallocene, while playing protection to outside catalyst poison Element very sensitively reacts and the easily effect of deactivated metallocene.Therefore, the load capacity of aikyiaiurnirsoxan beta is higher, metallocene Load capacity is more raised, and the probability do not poisoned by external catalyst toxin is more raised, and activity can be improved.

The manufacture of ethylene copolymer

The ethylene copolymer of the present invention is non-comprising above-mentioned (A) metallocene catalyst component as major catalyst, (B) The race's metallic compound of halogenation monocyclopentadienyl 4, (C) active cocatalyst (Activating cocatalysts) composition and (D) combine in the presence of the metallocene supported catalyst of carrier components the gas-phase polymerization comprising hydrogen, ethylene and comonomer Thing gas phase reaction and manufacture.

Used as concrete example, the ethylene copolymer of the present invention can be by using above-mentioned metallocene catalyst, as reaction The hydrocarbon of solvent, is selected from making in the presence of the hydrocarbon in propane, iso-butane, hexane, heptane etc. comprising hydrogen, ethylene and comonomer Gas-phase polymerization carry out gas-phase polymerization with compositionss and manufacture.

In the manufacture of the ethylene copolymer of the present invention, contained above-mentioned hydrogen is used to adjust in above-mentioned gas-phase polymerization compositionss The molecular weight of the polymer of thing as a result, above-mentioned hydrogen is that hydrogen/ethylene is represented with mol ratio with the content ratio of above-mentioned ethylene, is 0.0005~0.005, preferably 0.0008~0.0015.If the mol ratio of above-mentioned hydrogen/ethylene is less than 0.0005, or exceedes 0.005, the molecular weight of polymer is too low or too high, and the application as product becomes difficult.

It is contained above-mentioned in above-mentioned gas-phase polymerization compositionss in addition, in the manufacture method of the ethylene copolymer of the present invention Alpha-olefin beyond ethylene as the preferred propylene of comonomer, 1-butylene, 1- hexenes, 4-methyl-1-pentene etc., above-mentioned copolymerization Monomer is that comonomer/ethylene is represented with mol ratio with the content ratio of above-mentioned ethylene, is 0.005~0.05, preferably 0.008~ 0.025.If the mol ratio of the comonomer/ethylene is less than 0.005, or more than 0.025, then cannot get being total to for target level Polymers.This is because, if the content of comonomer contained in gas-phase polymerization compositionss is too low, plus man-hour is in copolymer Intercrystalline sized fraction ground becomes big, and the transparency reduces, if on the contrary, the too high levels of comonomer, the softening of copolymer Point (softening temperature) is reduced, and the reaction stability in gas-phase polymerization reactor is poor.

In the manufacture method of the ethylene copolymer of the present invention, metallocene supported catalyst is except using when catalyst is manufactured Beyond active cocatalyst composition, the activator preferably with more than a kind coordinates, forms ethylene rolymerization catalyst system.Preferably There are alkyl aluminum compound (such as diethyl aluminum chloride), aikyiaiurnirsoxan beta, modified alumoxane, neutral or ionic ionizing in activator Activator, non-coordinating anion, noncoordinating 13 race metal or metalliod anions, borine, borate etc..

As the alkyl aluminum compound that can be used as above-mentioned activator, it is possible to use by formula AlRnX_(3―n)(wherein, R is carbon The alkyl of number 1~16, X is halogens, the alkyl aluminum compound of 1≤n≤3) represent.As the tool of abovementioned alkyl aluminium compound The example of body, preferably uses triethyl aluminum, trimethyl aluminium, tri-n-n-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, three n-hexyls Aluminum, tri-n-octylaluminium, three (2- methyl amyls) aluminum etc., particularly preferably using triisobutyl aluminium, triethyl aluminum, tri-n-hexyl aluminum or Tri-n-octylaluminium.

Abovementioned alkyl aluminium compound preferably according to desired polymer characteristicses, with

Transition metal≤1000 in 100≤alkyl aluminum compound/major catalyst

Mol ratio use in gas-phase polymerization, more preferably with

Transition metal≤500 in 300≤alkyl aluminum compound/major catalyst

Mol ratio use in gas-phase polymerization.

If the mol ratio of the transition metal in abovementioned alkyl aluminium compound/major catalyst is less than 100, it is impossible to obtain abundant Polymerization activity, if it exceeds 1000, on the contrary reduce polymerization activity.

Or, abovementioned alkyl aluminium compound, according to desired polymer characteristicses, preferably with

10≤Al/ Gas-phase reactor beds (BED) amounts≤200

, more preferably

30≤Al/ Gas-phase reactor beds amount≤50

Content (ppm) use.

If above-mentioned Al/ Gas-phase reactor bed amount can not obtain sufficient polymerization activity less than 10ppm, in addition cannot Guarantee the uniformity reacted, produce reaction temperature fluctuation (hunting), play a role as the reason for causing unstability, such as Fruit then shows on the contrary the effect run counter to desire of polymerization activity reduction more than 200ppm.

As above-mentioned activator, the use of aikyiaiurnirsoxan beta or deformation aikyiaiurnirsoxan beta and/or using by neutral metallocene compound from The neutral or ionic Ionizing activators of sonization, (pentafluorophenyl group) borine of such as three (normal-butyl) ammonium four or three perfluorophenyl boron Alkane metalloid precursor is also within the scope of the invention.There are triphenylborane, three second in other compounds that can be used as activator Base borine, three-normal-butyl ammonium tetraethyl borate, triarylborane etc..Aluminate is also the activator compound that can be used.

The present invention ethylene copolymer manufacture in, polyreaction is in the presence of hydrocarbon solvent, preferably 60~120 DEG C, More preferably 65~100 DEG C, further preferably 70~80 DEG C of temperature and preferably 2~40 atmospheric pressure, more preferably 10 Carried out by gas-phase polymerization under the pressure of~30 atmospheric pressure.

If the above-mentioned polymerization temperature in gas phase fluidized bed reactor is less than 60 DEG C, it is impossible to obtain sufficient polymerization efficiency, If it exceeds 120 DEG C, there is a problem of easily generating polymer blocks.In addition, if the above-mentioned fortune in gas phase fluidized bed reactor Turn pressure less than 2 atmospheric pressure, then the thermal capacity of per unit volume is too low, it is impossible to obtain sufficient polymerization efficiency, if it exceeds 40 atmospheric pressure, the then control reacted becomes difficult, and out of the question requirement is given to reactor.

In the manufacture of the ethylene copolymer of the present invention, preferably further inject into for preventing beyond above-mentioned catalyst component The formation of the sheet material (sheet) that only electrostatic causes and the antistatic additive for stable reaction.

Antistatic additive suppress fouling and cohesion (agglomeration) phenomenon, but if being excessively used, on the contrary by with cyclopentadienyl The reaction of metallic catalyst and make catalyst activity reduction, generate low-molecular weight polymer, hinder alpha-olefin insertion.Cause This, preferably properly adjusting can make electrostatic generation and content in the bed of the activator of the minimal activity reduction of catalyst and resist Content ratio in the bed of electrostatic agent.Antistatic additive is the thing that the phenomenon relevant with electrostatic can be limited by intrinsic functional group Matter, the coacervation being prevented between polyolefin particles, be prevented from around reactor wall and dispersion plate, recyclegas it is defeated Send road, the fouling of internal heat exchanger wall.As such antistatic additive, have by alcoxyl base system amine, alcoxyl base system amide Class, preferably, long-chain (long chain) diethanolamine constitute non-volatile liquid.Further, it is possible to use carbon number 8~30 Fatty acid as organic carboxyl acid the slaine of at least more than one, molecular weight for 150~1,200 scope, above-mentioned gold Category includes alkali metal, alkaline-earth metal.As commercially available antistatic additive, there is the trade (brand) name of AKZONOBEL companies ATMER163, AS990 of ARMOSTAT400, ARMOSTAT1800 or CIBAGEIGY company etc..As preferred antistatic additive, Can include with R-N (C₂H₄OH)₂Double (2- hydroxyethyls) amine of the N of the structure of (wherein, R is the alkyl of carbon number 12~16), N- Class.

Above-mentioned antistatic additive is preferably used with following content (ppm) based on fluidized bed bed benchmark in polymerization.

10≤antistatic additive compound/Gas-phase reactor bed amount≤200

It is highly preferred that

30≤antistatic additive compound/Gas-phase reactor bed amount≤80.

If above-mentioned antistatic additive compound/bed amount removes low effort less than 10ppm, electrostatic, it is impossible to guarantee reaction Stability, if it exceeds 200ppm, then cause on the contrary the deformation of catalyst, shows the effect of polymerization activity reduction.It is such Because of the species and content of the activator used in polymerization reaction system, strange land manifests the effect of antistatic additive.

The above-mentioned metallocene supported catalyst composition used as major catalyst during the manufacture of the ethylene copolymer of the present invention Pre-polymerization is carried out before can using as composition in the polymerization with ethylene or alpha-olefin and use.Pre-polymerization can be at oneself In above-mentioned catalyst component at sufficiently low temperature and ethylene or alpha-olefin pressure condition in the presence of hydrocarbon solvent as alkane Carry out with the presence of organo-aluminum compound as triisobutyl aluminium.Pre-polymerization contributes to surrounding catalyst pellets with polymer Son, the shape for maintaining catalyst shape, improving polymer after polymerisation.The weight of the polymer/catalyst after pre-polymerization is than big General is 0.1：1 to 200：1.Used as preferred organo-metallic compound, triethyl aluminum, triisobutyl aluminium are such to have carbon number 1 The trialkylaluminium and their mixture of the individual~alkyl of 6 is beneficial.Sometimes ethylaluminum dichloride, diethyl chlorine can be used Change the such organo-aluminium chemical combination with the halogen of more than 1 or hydrogen-based of aluminum, ethyl aluminium sesqui chloride, diisobutyl aluminium hydride Thing.

The effect of invention

The ethylene copolymer manufactured using the method for the present invention is shown low resin pressure in tube extrusion molding and is started Machine load and excellent process velocity, processability is very excellent.

Description of the drawings

Fig. 1 is the skeleton diagram of the circulation gas phase fluidized bed reaction unit in embodiments of the invention used in polymerization.

Fig. 2 a are to represent the figure of the measured value of storage moduluss (G') and loss moduluses at 190 DEG C (G ").

Fig. 2 b are to show complex elasticity mould by the result of the measured value of storage moduluss (G') at 190 DEG C and loss moduluses (G ") The figure of amount (G*).

Fig. 3 is the figure for representing the example that the phase angle displacement (δ) at 190 DEG C based on complex modulus is drawn.

Fig. 4 calculates phase angle (δ at 190 DEG C for expression to complex modulus_C) example figure.

Fig. 5 represents the complex modulus (G*) of embodiment 1~3 and comparative example 1,2 for phase angle (δ) curve.It is critical Phase angle is the COV of such two slopes as the above description.

Fig. 6 is the figure of the GPC-IR curves and BOCD indexes (BOCDI) for representing embodiment 2.

Fig. 7 is the figure of the GPC-IR curves and BOCD indexes (BOCDI) for representing comparative example 2.

The explanation of reference

1. reactor top enlarged portion

2. fluidized bed

3. heat exchanger

4. compressor

Specific embodiment

The present invention is illustrated in greater detail by the following examples.But, these embodiments be for illustrative purposes, The present invention is not limited by these embodiments.

Production Example

The race's metallic compound of non-halogenated monocyclopentadienyl 4 (dimethylated methylene silylation (tert-butyl group amido)-(tetramethyl Cyclopentadienyl group)-titanium dibenzyl：Me₂Si(NtBu)(Cp*)Ti(Bn)₂) synthesis

Measure Ti (CH₂Ph)₄5.2mmol and dimethylated methylene silylation (tert-butyl group amido)-(tetramethyl-ring pentadiene Base) (Dimethylsilylene (t-butylamido) is (tetramethycyclopentadienyl)) 4.0mmol, injection use The refined toluene 50mL of uncommon Rec technology (Schlenk Line), is completely dissolved.By the temperature of the reactor of blocking daylight Bring up to 60 DEG C so as to react 12 hours.

Reactant is dried in a vacuum.The reactant of drying is used again pentane extraction, by it again in a vacuum It is dried, has finally given Me₂Si(NtBu)(Cp*)Ti(Bn)₂.Yield is more than 90%.The structure of compound passes through¹H NMR are true Recognize.

¹H NMR(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)

Embodiment 1

[manufacture of metallocene supported catalyst]

For trade name XPO-2402 (Grace companies (U.S.), particle mean size~50 μm, surface area 300m²It is/g, fine Pore volume 1.6ml/g, OH concentration 1mmol/g) dehydrated silica, in anhydrous conditions quantitative 500g, is stirred using toluene Mix as slurry form.In being injected into the 10L reactors with agitator and condenser.With graduated cylinder to methylaluminoxane solution After (10 weight %) (MAO/g silicon dioxide=15mmol/g silicon dioxide) is quantitative, in injecting reactor.Then side Implement stirring side and temperature of reactor is warmed up to into 110 DEG C.Load-reaction is set to carry out 90 minutes at such a temperature.After reaction terminates, Placing response thing, makes top solution decantation (decantation).Injection toluene solution 500mL, after cleaning to reactant, Placing response thing, makes top solution decantation.The operation is repeated into 2 times.

Using quantitative ethylenebis (4,5,6, the 7- tetrahydro indenyl) zirconium dichloride (Et as metallocene catalyst component (THI)₂ZrCl₂) [metallocene (Et (THI)₂ZrCl₂)/silicon dioxide=100 μm ol/g silicon dioxide] and above-mentioned Production Example in Race metallic compound (the Me of non-halogenated monocyclopentadienyl 4 of synthesis₂Si(NtBu)(Cp*)Ti(Bn)₂)[Me₂Si(NtBu) (Cp*)Ti(Bn)₂/ silicon dioxide=150 μm ol/g silicon dioxide] dilution in toluene 200mL at normal temperatures respectively, manufacture molten Liquid.

In being injected into above-mentioned reactor, temperature is brought up to into 50 DEG C, make load-reaction carry out 6 at such a temperature little When.After reaction terminates, reactant is transferred to after Xi Laike containers, makes top solution decantation (decantation).Add toluene 500mL, after being stirred to reactant, places, and is decanted supernatant.Clean as implementing 3 times.Then, will obtain Catalyst cleaned with refined hexane after, be dried it under gentle vacuum, obtained free flowing powder (Free Flowing Powder) form catalyst.

[polymerization]

Implement polymerization process in continuous gas phase fluidized bed reactor as shown in Figure 1.Fluidized bed is by polymer particle structure Into.The gas phase supply stream and monomer of ethylene and hydrogen are imported into recycle gas pipeline under reactor layer.1- hexenes are used as altogether Polycondensation monomer.Ethylene, hydrogen and the respective flow of comonomer are adjusted so that keeping certain composition of target.Adjust ethylene concentration with Cause to keep certain ethylene partial pressure.Hydrogen is adjusted so that hydrogen and ethylene molar ratio are remained necessarily.Surveyed by online gas chromatogram Determined the concentration of all gas so that the composition of stream of recycled gases to become comparison constant.The reaction that will be made up of polymer particle Layer is maintained at following state：Flowed on a large scale and continuously so as to flow through reaction by supplementing aliment and recirculation gas Change.Reactor is made in 19.2Kgf/cm²Stagnation pressure under operate.By the load manufactured under these conditions with certain speed injection Metallocene catalyst and start reaction, with catalyst inject simultaneously, in order to start reaction and using as the alkyl aluminum of activator Compound is that tri-n-octylaluminium dilutes in hexane, in terms of the interior intensity reference of bed (BED), is filled with 30ppm.In addition, in order to anti- Should stablize, antistatic additive AS990 is diluted in oil, inject in bed so that keeping the content of 50ppm.As polyreaction is entered OK, in order to keep certain temperature of reactor, in the way of it can adjust the exotherm rate produced by polymerization and change, while making to follow again By heat exchanger, side constantly makes the temperature of recirculation gas be raised and lowered and adjust to ring gas.For fluidized bed, pass through A part for layer is reclaimed with the speed same with the formation speed of product, so as to be maintained at certain height.It is poly- with regard to gas phase For conjunction condition, implement under the polymerizing condition of table 1 below, polymerization result is shown in Table 1.

[polymeric properties analysis]

For the polymer obtained by above-mentioned polymerization, following analysis is implemented.

(1)MFRR(Melt flow rate ratio：Melt flow rate (MFR) ratio)：Carried with 190 DEG C, 21.6kg and 2.16kg The ratio of the melt index under lotus is calculated.

(2) molecular weight distribution：With by GPC (Gel Permeation Chromatography：Gel permeation chromatography) determine Weight average molecular weight (Mw) and number-average molecular weight (Mn) ratio (Mw/Mn) calculate.

(3) zero-shear viscosity：Frequency scanning is adopted at a temperature of 190 DEG C using rheometry ARES effusion meters (Frequency Sweep) mode determines dynamic flow characteristics data and calculates.In parallel-plate structure at intervals of 2mm, board diameter For 25mm, strain amplitude is 10%.It is to determine in the range of 0.05~300rad/sec in frequency.Using カロウ models (Carraeu Model) calculates zero-shear viscosity.

(4) shear viscosity ratio (SHI)：By complex viscosity and frequency under frequency 0.1rad/sec determined from ARES The ratio of the complex viscosity under 100rad/sec is calculated.

(5) critical phase angle (δ_C)

First, (Frequency Sweep) mode is frequency scanned using the ARES equipment of TA Instruments companies Determine dynamic flow characteristics data.If being made the figure of phase angle displacement (δ) and complex modulus (G*) by determination data, Linear structure PE shows different behaviors from LCB structures PE, and the PE of LCB structures is in the phase angle (δ) and complex modulus (G*) flex point of the slope variation of coordinate diagram is produced in figure, critical phase angle (δ is referred to as_C).Usually critical phase angle Value (δ_C) there is dependency relation with the content of LCB, it is known that LCB is bigger, then δ_CIt is lower.

Critical phase angle (δ_C) calculation method calculates by the dynamic flow characteristics data for determining as described below.

1. complex modulus (complex modulus) is drawn and is calculated

By storage moduluss G'(storage modulus) and the loss moduluses G " result of (loss modulus), under use State formula (1) and calculate G* (complex modulus), draw as shown in Figure 2.

2. phase angle displacement (δ) is drawn and is calculated

Dynamic test (dynamic test) side of the ARES of Deformation control type (Strain control type) is used Method is polymer melt (polymer melt) to be applied with SIN function (sin function) to vibrate as shown in Figure 3 (oscillation) method for deforming, determining stress (stress) now and determine the dependency relation between stress and deformation, uses Homophase (in phase) characteristic of elastic (elastic) and the combination of viscosity (viscous) anti-phase (out of phase) (combination) representing viscoelasticity.The above-mentioned G* (complex modulus) for trying to achieve is carried out as phase angle displacement (δ) Draw, obtain result as Fig. 3.

Fig. 3 is the result drawn for linear structure PE and LCB structure PE, it is known that the difference that structure is produced.

3. critical phase angle (δ_C) calculate

The flex point that the slope of coordinate diagram changes in above-mentioned complex modulus (G*) is for phase angle (δ) curve becomes Critical phase angle (δ_C).In the same manner as Fig. 4, from G* values, a low side starts to be designated as the interval of straight line the method asked for, Obtain slope.Again in the position that straight line is designated as after flex point, slope is obtained.After obtaining the slope in two intervals, Obtain critical phase angle (δ in cross point_C)。

(6) BOCD indexes (BOCDI, Broad Orthogonal Composition Distribution Index)

Using being mounted with FTIR for comonomer analysis in the GPC used in above-mentioned molecular weight distribution analysis The GPC-IR of (Fourier Transform Infrared Spectroscopy), is analyzed and calculates.In GPC-IR analyses As a result on the basis of weight average molecular weight (Mw) to determine upper 80% site (high molecular site) of molecular weight SCB contents and The SCB contents of the next 20% site (low-molecular-weight site) are measured, and with following mathematical expressions BOCD indexes are calculated.

[pipe molding]

Using the polymer obtained in above-mentioned polymerization experiment, pipe molding is implemented under the following conditions, it is manufactured The characteristic of pipe is shown in Table 3.

Pipe forming machine (Pipe Machine)：IKEGAI 50mm pipe M/C

Pipe processing temperature：180~200 DEG C

Pipe sample size：32~33mm of profile, 2.9~3.1mm of thickness

Embodiment 2

In embodiment 1, not using ethylenebis (4,5,6,7- tetrahydro indenyl) zirconium dichloride (Et (THI)₂ZrCl₂) As metallocene catalyst component, using double (n-butyl cyclopentadienyl group) zirconium dichlorides under conditions of similarly to Example 1 Manufacture catalyst, implements polymerization under conditions of similarly to Example 1.

Embodiment 3

In embodiment 1, not using ethylenebis (4,5,6,7- tetrahydro indenyl) zirconium dichloride (Et (THI)₂ZrCl₂) As metallocene catalyst component, using double (1- ethyl -3- methyl cyclopentadienyls) two under conditions of similarly to Example 1 Zirconium chloride manufactures catalyst, and polymerization and pipe molding are implemented under conditions of similarly to Example 1.

Comparative example 1~3

In order to compare pipe physical property and processability, have selected what is manufactured using Z-N (Z-N) and metallocene catalyst Existing article of commerce line style medium density polyethylene.

Comparative example 1：Commercially available MDPE (medium density polyethylene) in the Korea of MI=0.73 density=0.938

Comparative example 2：Commercially available MDPE (medium density polyethylene) in the Korea of MI=0.56 density=0.936

Comparative example 3：Commercially available MDPE (medium density polyethylene) in the Korea of MI=0.62 density=0.934

【Table 1】

【Table 2】

(note) ND：Do not detect (Not Detected)

【Table 3】

The ethylene copolymer of the present invention shows narrow molecular weight distribution, by critical phase as shown in above-mentioned table 1 Parallactic angle value and flow-activation energy value understand there is long chain branches (LCB).In addition, in the distribution of comonomer, by BOCD indexes Will also realize that, according to molecular weight, be more distributed in the big part of molecular weight.In addition, in the ethylene copolymer structure of the present invention The characteristic of molecule also shows good as shown in above-mentioned table 3, in pipe processability and pipe physical property.I.e., it is known that despite phase To narrow molecular weight distribution, but pipe plus man-hour show low engine load and high process velocity, and the physical property of pipe is also excellent. This excellent physical property that can be described as being expected pipe by narrow molecular weight distribution manifests, and due to the performance of long chain branches (LCB), overcomes The inferior position of Narrow Molecular Weight Distribution and show excellent pipe processability.

Above-mentioned such result also embodies well in the comparison with the comparative example of table 2.Compare with comparative example 1 and 3, it is real The molecular weight distribution of the result despite opposite, narrow of example is applied, but shows excellent processability, compared with comparative example 2, BOCD refers to Numerical value is raised, and shows low engine load and excellent process velocity.

Claims

1. ethylene copolymer, it is characterised in that manufactured ethylene and alpha-olefin copolymer using metallocene catalyst, with following Characteristic：

(1) melt flow index is 0.2~2.0g/10 minutes (190 DEG C, 2.16Kg load),

(2) density is 0.930~0.955g/mL,

(3) molecular weight distribution (weight-average molecular weight/number-average molecular weight) is 2.5~4.0,

(4) BOCD indexes ＞ 0.5, and

(5) critical phase angle (Critical phase angles, δ_C) ＜ 70.0.

2. ethylene copolymer according to claim 1, it is characterised in that above-mentioned metallocene catalyst includes (A) metallocene Catalyst component, (B) non-halogenated race's metallic compound of monocyclopentadienyl 4, (C) active cocatalyst composition and (D) carrier into Point.

3. ethylene copolymer according to claim 2, it is characterised in that (A) above-mentioned in above-mentioned metallocene catalyst cyclopentadienyl gold Metal catalyst composition is the dicyclopentadienyl metallocene of following formulas (1) or the bridging bonding metallocene of following formulas (2)：

(CpR_n)(CpR'_m)ML_q (1)

Wherein, Cp be cyclopentadienyl group, indenyl or fluorenyl,

R and R' represent independently of one another hydrogen, alkyl, alkyl ether, allyl ether, phosphine or amine,

L represents alkyl, pi-allyl, aryl alkyl, amide, alkoxy or halogen,

M represents 4 races of periodic chart or the transition metal of 5 races,

N is the positive number of 0≤n of satisfaction ＜ 5, and m is the positive number of 0≤m of satisfaction ＜ 5, and q is the positive number of satisfaction 1≤q≤4；

Q(CpR_n)(CpR'_m)ML_q (2)

Wherein, Cp, R, R', M, L have and above-mentioned formula (1) identical implication, Q for C interannulars bridging key, represent dialkyl group, The alkyl of alkylaryl, diaryl silicon or carbon number 1~20, n is the positive number of 0≤n of satisfaction ＜ 4, m be 0≤m of satisfaction ＜ 4 just Number, q is the positive number of satisfaction 1≤q≤4.

4. ethylene copolymer according to claim 2, it is characterised in that in above-mentioned metallocene catalyst, above-mentioned (B) non-halogen It is the compound represented by following formulas (3) to change the race's metallic compound of monocyclopentadienyl 4：

Wherein, x is 0,1,2,3 or 4, y are 0 or 1,

R is hydrogen, the alkyl of carbon number 1~20, silicyl, germyl, cyano group, halogen or their compound group, represents tool There is the substituent group of 1~20 non-hydrogen atoms,

Y' represents-O- ,-S- ,-NR*- or-PR*-, wherein, R* be hydrogen, the alkyl of carbon number 1~12, the oxyl of carbon number 1~8, Silicyl, the haloalkyl of carbon number 1~8, the halogenated aryl of carbon number 6~20 or their compound group,

Z represents SiR*₂、Si(OR*)R*、Si(OR*)₂、Si(NR*)R*、Si(NR*)₂、CR*₂、SiR*₂SiR*₂、CR*₂CR*₂、 CR*=CR*, CR*₂SiR*₂Or GeR*₂, R* as described above defined in,

L represents independently of one another the alkyl of carbon number 1~30,

M represents Ti or Zr.

5. ethylene copolymer according to claim 2, it is characterised in that above-mentioned metallocene is urged in above-mentioned metallocene catalyst Agent composition (A) represents than (A/B) with the use of the race's metallic compound (B) of non-halogenated monocyclopentadienyl 4 with mol ratio, is 0.01：1 to 100：1.

6. ethylene copolymer according to claim 2, it is characterised in that (C) above-mentioned in above-mentioned metallocene catalyst is activated Co-catalyst component is the aikyiaiurnirsoxan beta in linear alumoxanes I oligomer and Cyclic aluminoxane oligomer.

7. ethylene copolymer according to claim 2, it is characterised in that (C) above-mentioned in above-mentioned metallocene catalyst is activated Co-catalyst component is by formula AlR_nX_(3―n)The organo-aluminum compound of expression, wherein, R is the alkyl of carbon number 1~16, and X is halogen Prime element, 1≤n≤3.

8. ethylene copolymer according to claim 2, it is characterised in that (C) above-mentioned in above-mentioned metallocene catalyst is activated Co-catalyst component is the Ionizing activators in the compound represented selected from following formulas (4), (5) or (6)：

B(R^a)₃‥‥‥(4)

[R^b]⁺[BR^a]^-‥‥‥(5)

[R^c-H]⁺[BR^a]^-‥‥‥(6)

Wherein, B represents boron atom, R³Represent phenyl or phenoxy group, the phenyl or phenoxy group can be selected from fluorine atom, can be by fluorine Substituted or unsubstituted C1~C20 the alkyl of atom or and then can be replaced by fluorine atoms or unsubstituted carbon number 1~20 alcoxyl The substituent group of 3~5 in base replaces, R^bFor the group of naphthene base of carbon number 5~7, (C1~C20) alkyl (C6~C20) aryl Group or (C6~C30) aryl (C1~C20) alkyl group, [R^c-H]⁺It is by 1~3 (C1~C20) alkyl-substituted ammonium Huo Phosphonium ions.

9. ethylene copolymer according to claim 2, it is characterised in that (D) carrier is flat in above-mentioned metallocene catalyst Granularity is 10~250 μm, is with average diameter Fine pores, fine pores volume be 0.1~ 10ml/g, surface area are 5~1000m²The silicon dioxide of/g.

10. ethylene copolymer according to claim 1, it is characterised in that above-mentioned ethylene copolymer is by using above-mentioned cyclopentadienyl Metallic catalyst, in the presence of the hydrocarbon as reaction dissolvent, combines to the gas-phase polymerization comprising hydrogen, ethylene and comonomer Thing carries out gas-phase polymerization and manufactures.