CN1153786A - Process for preparing in situ polyethylene blend - Google Patents
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- CN1153786A CN1153786A CN 96121675 CN96121675A CN1153786A CN 1153786 A CN1153786 A CN 1153786A CN 96121675 CN96121675 CN 96121675 CN 96121675 A CN96121675 A CN 96121675A CN 1153786 A CN1153786 A CN 1153786A
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Abstract
A process for the production of an in situ polyethylene blend comprising contacting at least one metallocene based catalyst system with one or more alpha-olefins in each of two or more reactors connected in series, in the gas phase, under polymerization conditions, with the provisos that: (a) ethylene is introduced into each reactor; (b) optionally, an alpha-olefin having at least 3 carbon atoms or a diene is introduced into at least one reactor; (c) - the mixture of ethylene polymer matrix and catalyst formed in the first reactor in the series is transferred to the subsequent reactors in the series;and (d) the polymerization conditions in each reactor are such that a high molecular weight polymer is formed in at least one reactor and a low molecular weight polymer is formed in at least one other reactor.
Description
The application is US08/470, the part subsequent application of 838 (1995.6.6 applications), and US08/470, and 838 is again US08/171 successively, the subsequent application of 272 (in December, 1993,21 days applications).
The present invention relates to a kind of method for preparing the on-the-spot adulterant of polyethylene, it is to use under the condition of at least a metalloscene catalyst to carry out in placed in-line two or more reactors.
People prepared the polyethylene of various density and it is changed into have excellent tensile strength, the film of high extensibility, good resistance to impact shock and superior splitting resistance feature.When poly molecular weight was higher, these performances were enhanced together in company with toughness.Yet when poly molecular weight increased, the processibility of resin reduced usually.By the adulterant of a kind of high-molecular weight and low-molecular-weight polymkeric substance is provided, can keeps the performance characteristic of high molecular weight resin, and can improve processibility, particularly extrudability (feature of lower molecular weight composition).
At US5, the fusion of these polymkeric substance in the grading reactor method has been described in 047,468 and 5,149,738.Very fast, this method becomes one of method of on-the-spot blending of polymers, wherein prepares the high-molecular weight ethylene copolymer in a reactor, and prepare low-molecular-weight ethylene copolymer in another reactor.This method typically is included under the polymerizing condition the mixture of ethene and one or more α alkenes and catalyst system in placed in-line two gas phases, carry out Continuous Contact in the fluidized-bed reactor, said catalyst system comprises: (i) magnesium on carrier/Ti-base catalyst precursor; (ii) one or more contain the aluminum compound of activator; (iii) alkyl aluminium co-catalyst.
Found the on-the-spot adulterant that as above prepares and had a lot of advantageous characteristic feature that the content height of resulting not dispersive high molecular weight material (often being called " gel ") has usually limited the industrial application of these granular bimodal polymkeric substance by the film that it forms.In addition, the very wide molecular weight distribution of known specific catalyst system's generation, it has brought certain disadvantageous effect for the accurate control of polymer architecture and performance.
Therefore, purpose of the present invention provides a kind of novel method that can overcome the on-the-spot adulterant of preparation of some shortcomings of former system.
The inventive method is included in the catalyst system that will contain at least a metallocenyl catalyzer under gas phase and the polymerizing condition in two or more placed in-line reactors and contacts with one or more α alkenes.
Ethene is incorporated in each reactor; At random, alpha-olefins and/or the diene that one or more is had at least 3 carbon atoms is incorporated at least one reactor; In first reactor, form at least a active catalyst; Ethene polymers matrix that will form in placed in-line first reactor and mixture of catalysts move on in the placed in-line next reactor, and the polymerizing condition in each reactor is such, promptly at least one reactor, form high molecular weight polymers, forming low-molecular-weight polymkeric substance in another reactor at least.At least a catalyzer is a metallocenes.
Polymer blend can be produced in two or more placed in-line reactors, preferably in two placed in-line reactors, produce simultaneously, wherein the mixture of resin and catalyst precursor is shifted to second reactor from first reactor, in second reactor, prepare another kind of polymkeric substance and it is carried out on-the-spot fusion with the polymkeric substance that comes from first reactor.When using more than two reactor, people should be understood that the resin and the catalyst mixture that come from first reactor are shifted in another reactor from a reactor with the resin that forms in each subsequent reactor that coexists.Therefore, this is a kind of continuous fusion.
For to this detailed description, term " reactor " can refer to that reactor independently can refer to a certain section in a reactor again.Therefore, this process can be at two or more independently in the reactor; In in a reactor two sections or the multistage; Or in the combination of reactor and some section of reactor, carry out.Yet preferably, method of the present invention is independently carried out in the reactor at two.
The polymkeric substance that forms in any reactor can be the homopolymer of ethene, or ethene and at least a multipolymer with alpha-olefins of at least 3 carbon atoms.Preferably ethene and at least a alpha-olefins, and/or a kind of multipolymer with diene of 4-12 carbon atom with 3-12 carbon atom.Alpha-olefins most preferably has 3-8 carbon atom, and can be, for example, and propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene or 1-octene.Also have, except ethene, suggestion has the alpha-olefins of no more than a kind or two kinds in each reactor.Typically, formed adulterant be homopolymer/-the homopolymer adulterant, homopolymer/multipolymer adulterant, and multipolymer/multipolymer adulterant.
People should be understood that on-the-spot adulterant can be a feature with the multi-peak resin, preferably bimodal or three peaks.This resin can be multi-peak aspect molecular weight distribution and/or the comonomer distribution.The performance of multi-peak resin depends on each components in proportions of on-the-spot adulterant consumingly.
Metalloscene catalyst used in this invention is an organometallic compound, and they are cyclopentadienyl derivatives of transition metal, preferably IVB in the periodictable, VB, VIB or VIII family metal, and comprise the list of transition metal, two and three cyclopentadienyl compounds and their derivative.Satisfied especially is IVB and VB family metal such as titanium, zirconium, the metallocene complex of hafnium and vanadium.Known in the prior art Lv oxane and boron compound are as the activator of metallocenes and use too in the present invention.
Preferred metallocenes can be represented with following general formula:
(C
5R
x)
yR′z(C
5R
m)MQ
n-y-1 (I)
In the formula:
M is an IIIB-VII family metal in the periodic table of elements;
(C
5R
x) and (C
5R
m) be identical or different and the cyclopentadienyl of M bonding or the cyclopentadienyl of replacement; R is identical or different and is hydrogen, or alkyl such as alkyl, alkenyl, aryl, alkaryl, perhaps contains 1-20 carbon atom or two carbon atoms and is connected with each other and forms C
4-C
6The aralkyl of ring.
R ' is C
1-C
4That replace or unsubstituted alkylidene group, dialkyl group or diaryl germanium or silicon, or two (C of bridge joint
5R
x) and (C
5R
m) ring alkyl or aryl phosphine or amido; Q is an alkyl, as has the aryl of 1-20 carbon atom, alkyl, and alkenyl, alkaryl, or aralkyl have the-oxyl of 1-20 carbon atom or halogen, and can be identical or different each other.
Z is 0 or 1;
Y is 0,1 or 2; Z is 0 when y is 0
N is 0,1,2,3, or 4, it depends on the valence state of M; And n-y 〉=1.
With the representative of above general formula be used to illustrate rather than the example of the metallocenes that limits is that metal diaikyl is luxuriant, for example, dimethyl two (cyclopentadienyl) closes titanium, phenylbenzene two (cyclopentadienyl) closes titanium, dimethyl two (cyclopentadienyl) closes zirconium, phenylbenzene two (cyclopentadienyl) closes zirconium, dimethyl two (cyclopentadienyl) closes hafnium and phenylbenzene two (cyclopentadienyl) closes hafnium, di neo-pentyl two (cyclopentadienyl) closes titanium, di neo-pentyl two (cyclopentadienyl) closes zirconium, dibenzyl two (cyclopentadienyl) closes titanium, and dibenzyl two (cyclopentadienyl) closes zirconium, and dimethyl two (cyclopentadienyl) closes vanadium; The monoalkyl metallocenes, close titanium as methyl chloride two (cyclopentadienyl), ethyl chloride two (cyclopentadienyl) closes titanium, phenyl-chloride two (cyclopentadienyl) closes titanium, methyl chloride two (cyclopentadienyl) closes zirconium, ethyl chloride two (cyclopentadienyl) closes zirconium, and phenyl-chloride two (cyclopentadienyl) closes zirconium, and monobromomethane two (cyclopentadienyl) closes titanium; Trialkyl metal is luxuriant, closes titanium as the trimethylammonium cyclopentadienyl, and the triphenyl cyclopentadienyl closes zirconium, close zirconium with three neo-pentyl cyclopentadienyls, the trimethylammonium cyclopentadienyl closes zirconium, and the triphenyl cyclopentadienyl closes hafnium, three neo-pentyl cyclopentadienyls close hafnium and the trimethylammonium cyclopentadienyl closes hafnium; It is luxuriant that monocyclopentadienyl closes titanium, closes titanium as trichlorine pentamethyl-cyclopentadienyl, and trichlorine five ethyl cyclopentadienyls close titanium; Phenylbenzene two (pentamethyl-cyclopentadienyl) closes titanium, uses general formula CH
2The carbene and the derivative thereof of=two (cyclopentadienyl) representative; Two (cyclopentadienyl) that replace closes titanium (IV) compound, closes titanium or dichloro two (indenyl) closes titanium as phenylbenzene two (indenyl), and phenylbenzene two (methyl cyclopentadienyl) closes titanium or dihalo-two (methyl cyclopentadienyl) closes titanium; Dialkyl group, trialkyl, tetraalkyl and five alkyl cyclopentadienyls close titanium compound, as phenylbenzene two (1,2-dimethyl cyclopentadienyl) closes titanium or dichloro two (1,2-dimethyl cyclopentadienyl) and close titanium, phenylbenzene two (1,2-diethyl cyclopentadienyl) closes titanium or dichloro two (1,2-diethyl cyclopentadienyl) and close titanium; Use silicon, phosphine, amine or carbon bridged ring pentadiene title complex, close titanium or dichloro-dimethyl silyl dicyclopentadienyl closes titanium as phenylbenzene dimetylsilyl dicyclopentadienyl, diphenyl methyl phosphine dicyclopentadienyl closes titanium or dichloromethyl phosphine dicyclopentadienyl closes titanium, and phenylbenzene methylene radical dicyclopentadienyl closes titanium or dichloro methylene radical dicyclopentadienyl closes titanium and other dihalo-title complex etc.; And the Metallocenic compound after being bridged, close zirconium as two chloro isopropyls (cyclopentadienyl) (fluorenyl), two chloro isopropyls (cyclopentadienyl) (octahydrofluorenyl) close zirconium, dichloro phenylbenzene methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium, dichloro di-isopropyl methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium, dichloro diisobutyl methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium, and dichloro di-t-butyl methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium; Dichloro cyclohexylene (cyclopentadienyl) (fluorenyl) is closed zirconium, dichloro di-isopropyl methylene radical (2,5-dimethyl cyclopentadienyl) (fluorenyl) closes zirconium, two chloro isopropyls (cyclopentadienyl) (fluorenyl) close hafnium, dichloro phenylbenzene methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium, dichloro di-isopropyl methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium, dichloro diisobutyl methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium, dichloro di-t-butyl methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium, dichloro cyclohexylene (cyclopentadienyl) (fluorenyl) is closed hafnium, dichloro di-isopropyl methylene radical (2,5-dimethyl cyclopentadienyl) (fluorenyl) closes hafnium, and two chloro isopropyls (cyclopentadienyl) (fluorenyl) close titanium, dichloro phenylbenzene methylene radical (cyclopentadienyl) (fluorenyl) closes titanium, dichloro di-isopropyl methylene radical (cyclopentadienyl) (fluorenyl) closes titanium, and dichloro diisobutyl methylene radical (cyclopentadienyl) (fluorenyl) closes titanium, and dichloro di-t-butyl methylene radical (cyclopentadienyl) (fluorenyl) closes titanium, dichloro cyclohexylene (cyclopentadienyl) (fluorenyl) is closed titanium, dichloro di-isopropyl methylene radical (2,5-dimethyl cyclopentadienyl fluorenyl) closes titanium, and racemize-dichloro ethylenebis (1-indenyl) is closed zirconium (IV), racemize-dichloro ethylenebis (4,5,6,7-tetrahydrochysene-1-indenyl) closes zirconium (IV), racemize-dichloro-dimethyl silyl two (1-indenyl) closes zirconium (IV), racemize-dichloro-dimethyl silyl two (4,5,6,7-tetrahydrochysene-1-indenyl) closes zirconium (IV), racemize-dichloro 1,1,2,2-tetramethyl-silicylene two (1-indenyl) closes zirconium (IV), racemize-dichloro 1,1,2,2-tetramethyl-silicylene two (4,5,6,7-tetrahydrochysene-1-indenyl) closes zirconium (IV), two chlorethylidenes (1-indenyl tetramethyl-ring pentadienyl) close zirconium (IV), racemize-dichloro-dimethyl silyl two (the 2-methyl-4-tertiary butyl-1-cyclopentadienyl) closes zirconium (IV), and racemize-dichloro ethylenebis (1-indenyl) is closed hafnium (IV), racemize-dichloro ethylenebis (4,5,6,7-tetrahydrochysene-1-indenyl) close hafnium (IV), racemize-dichloro-dimethyl silyl two (1-indenyl) closes hafnium (IV), racemize-dichloro-dimethyl silyl two (4,5,6,7-tetrahydrochysene-1-indenyl) closes hafnium (IV), racemize-dichloro 1,1,2,2 tetramethyl-silicylene two (1-indenyl) close hafnium (IV), racemize-dichloro 1,1,2,2-tetramethyl-silicylene two (4,5,6,7-tetrahydrochysene-1-indenyl) closes hafnium (IV), two chlorethylidenes (1-indenyl-2,3,4,5-tetramethyl--1-cyclopentadienyl) close hafnium (IV), racemize-dichloro ethylenebis (1-indenyl) is closed titanium (IV), racemize-dichloro ethylenebis (4,5,6,7-tetrahydrochysene-1-indenyl) closes titanium (IV), racemize-dichloro-dimethyl silyl two (1-indenyl) closes titanium (IV), racemize-dichloro-dimethyl silyl two (4,5,6,7 tetrahydrochysenes-1-indenyl) close titanium (IV), racemize-dichloro 1,1,2,2-tetramethyl-methylene silane two (1-indenyl) closes titanium (IV), racemize-dichloro 1,1,2,2-tetramethyl-silicylene two (4,5,6,7-tetrahydrochysene-1-indenyl) closes titanium (IV), with two chlorethylidenes (1-indenyl-2,3,4,5-tetramethyl--1-cyclopentadienyl) closes titanium (IV).
Another preferred catalyzer is catalyst precursor and the co-catalyst by the general formula I that will represent below or general formula I I, forms as the reaction of the methyl aluminium oxane of methyl aluminium oxane or modification.
In the formula:
M is a transition metal, is preferably Zr or Hf;
L be replace or unsubstituted and M coordinate π-key ligand, preferably the cyclopentadienyl ligand of Qu Daiing.
Q can be identical or different, and is independently selected from-O-,-NR-,-CR
2With-S-, preferably oxygen;
Y is C or S, is preferably carbon;
Z is selected from-OR ,-NR
2,-CR
3,-SR-,-SiR
3,-PR
2Or-H, condition be when Q be-during NR-, then Z is selected from-OR ,-NR
2,-SR ,-SiR
3,-PR
2Or-H, preferably Z is selected from-OR ,-CR
3, and NR
2
N is 1 or 2;
When n is 2, W be monovalent anion or when n is 1 W be two valency negatively charged ion, preferably W is a first propylhomoserin root, carboxylate radical or by with Q, Y and Z in conjunction with and form other mix (heterpallyl) part and
R can be identical or different, and be respectively to contain carbon, silicon, nitrogen, oxygen, and/or the group of phosphorus, wherein one or more R bases can link to each other with the L substituting group, and preferably R is the alkyl that contains 1-20 carbon atom, is most preferably alkyl, cycloalkyl or aryl, and one or more can linking to each other with the L substituting group.
In the formula
M is a transition metal, is preferably Zr or Hf;
L is that replace or unsubstituted, with M coordinate π-key ligand, is preferably the cyclopentadienyl ligand of replacement;
Q can be identical or different and be independently selected from-O--NR--CR
2-and-S-, be preferably oxygen;
Y is c or s, is preferably c;
Z is selected from-OR-,-NR
2,-CR
3,-SR ,-SiR
3,-PR
2Or H, condition be when Q be-during NR-, then z is selected from-OR ,-NR
2,-SR ,-SiR
3,-PR
2Or-H, preferably Z is selected from-OR ,-CR
3With-NR
2
N is 1 or 2;
W is a monovalent anion when n is 2, or W is two valency negatively charged ion when n is 1, first propylhomoserin root preferably, carboxylate radical or by Q, T and Z in conjunction with and form mix (heterpallyl) part;
R can be identical or different and be independently selected from carbon containing, silicon, nitrogen, oxygen, and/or the group of phosphorus, wherein one or more R bases can link to each other with the L substituting group, preferably R is the alkyl that contains 1-20 carbon atom, be most preferably alkyl, cycloalkyl, or aryl and one or more can linking to each other with the L substituting group;
B is the bridged group that is selected from alkylidene group or arylidene, and it is individual with carbon or heteroatoms that they contain 1-10, germanium, the carbon atom that silicon and alkylphosphines replace arbitrarily; And
M is 1-7, is preferably 2-6, is most preferably 2 or 3.
By Q, Y is a uncharged polygamy position polymerization of olefin using catalyst body with the substituting group of the Z-shaped support that becomes because its higher polarity, with cp ' base class seemingly, it plays the electronics effect.In the most preferred technical scheme of the present invention, use disubstituted first propylhomoserin root,
And carboxylate radical,
The particularly preferred technical scheme of the present invention is that three (diethyl methyl carbamic root) indenyl closes zirconium.
Catalyst precursor of the present invention can prepare with any ordinary method; The preparation method is not crucial.In the preferred method of this catalyzer of preparation, be M (NR with the source material and the general formula of cyclopentadienyl ligand
2)
4Metallic compound reaction so that on metallic compound, introduce the cyclopentadienyl type ligand, wherein M and R as above define.Then resulting product is dissolved in inert solvent, in toluene and assorted cumin alkene (heterocummulene), as under the situation of assorted cumin alkene, CO
2Thereby contact with the dissolved product and to insert one or more M-NH
2Key is so that form first propylhomoserin root in this case.With these precursors and activator, react so that form the activatory catalyzer then as the Lv oxane.
The example of other catalyst precursor comprises that three (PIVALIC ACID CRUDE (25) root) indenyl closes zirconium or three (right-the toluic acid root) indenyl and closes zirconium, three (benzoate anion) indenyl closes zirconium, three (PIVALIC ACID CRUDE (25) roots) (1-methyl indenyl) close zirconium, three (diethyl methyl carbamic root) (2-methyl indenyl) closes zirconium, three (PIVALIC ACID CRUDE (25) root) (methyl cyclopentadienyls) close zirconium, three (PIVALIC ACID CRUDE (25) root) cyclopentadienyl closes zirconium, and three (benzoate anions) (pentamethyl-cyclopentadienyl) close zirconium.
As mentioned above, thus these catalyst precursors with the activation co-catalyst use the catalyst composition that is formed for producing polyalkenes.Preferably, the activation co-catalyst is a kind of of following material: (a) cladodification or cyclic contain oligomeric poly-(the alkyl aluminium oxide compound) of general formula for-(Al (R) O)-repeating unit, wherein R is the alkyl that contains about 12 carbon atoms of 1-, or aryl, as that replace or unsubstituted phenyl or naphthyl, or (b) borate, as boric acid three (pentafluorophenyl group) ester, four (pentafluorophenyl group) triethyl borate etc.
Preferably, the activation co-catalyst is cladodification or annular oligomeric poly-(alkyl aluminium oxide compound).More preferably, activation co-catalyst Shi Lv oxane is as the methyl Lv oxane of methyl Lv oxane or modification.
According to the present invention, this catalytic active material can be dissolved in the suitable solvent so that as solution it is offered reaction zone.Certainly, as mentioned above, metallocenes He the catalytically active material of Lv oxane reaction product be most preferred and by just before mixture joins reactor with metalloscene catalyst with Lv oxane co-catalyst mixes expediently forms, provide the grace time that reacts so that form catalytically active material simultaneously.Although this technical scheme with form earlier and the separate solid reaction product also is introduced in reaction zone by its solution that forms subsequently and compares more satisfactoryly, the latter is still within the scope of the invention.
No matter this active material is on-the-spot that form or form rightly in advance and join in the reactor with liquid form when it is introduced in Gas-phase reactor, the quantity of suitable De Lv oxane and metallocenes can change in very wide scope in the catalytically active material preparation.Aluminium atom contained in the Zai Lv oxane is generally about 2 with the mol ratio of contained atoms metal in metallocenes: 1-about 10,000: 1, be preferably about 10: 1-1,000: 1, more preferably about 50: about 200: 1 of 1-.
Metallocene catalyst system can be admitted in first reactor or second reactor as one or more metalloceness.In another technical scheme, different metallocene catalyst systems can be admitted in each reactor.Another technical scheme is metallocene catalyst systems to be sent in the reactor and with the Ziegler/Natta catalyzer of routine send in another reactor.In the technical scheme of this back, the Ziegler/Natta catalyzer is preferably at US4, in the catalyst system of describing in 302,565 with its magnesium/Ti-base catalyst as example.
Picture is at US5, the such metallocene catalyst systems that can use the carrier free form that is proposed in 317,036, or picture US197, the such metallocene catalyst systems that can use to spray-dired powder that is proposed in 922 (applications on February 17th, 1994).Preferably catalyst system uses with DNAcarrier free form.Wish that at those catalyst precursor Huo Lv oxane has under the situation of carrier, silicon-dioxide is preferred carrier.Other suitable carriers is an inorganic oxide, as aluminum phosphate, aluminum oxide, silica/alumina mixture and with being the aluminum compound of aluminum alkyls class and aluminium halogenide class with the reagent such as the example of surface silicon alkanol reaction, boron alkyl and boron halogenide, the silicon-dioxide of dialkyl group zinc and hexamethyldisilazane modification, typical carrier is solid-state, the grain type, porous is the inert material to polyreaction substantially.It uses as dried powder, and powder has the about 250 μ m of about 5-, the median size of the about 100 μ m of preferably about 10-; Be at least 50m
2/ g is preferably at least about 250m
2The surface-area of/g; With at least about 50 dusts (), be preferably aperture at least about 200 dusts.For example by being that 80 μ m and particle diameter distribution width are that to obtain median size be that 75 μ m and particle diameter distribution width are the typical silica supports of 0.9-1.5 for 1.9 silica supports classification with median size.
Be in the typical method of resin of multi-peak aspect producing molecular weight, will comprise that the whole catalyst system of precursor or active precursor and co-catalyst joins in first reactor.Can add with the form that carrier is arranged also and can add with the form of solution.Catalyst pack is embedded in the multipolymer that in first reactor, forms and this mixture is shifted in second reactor.With regard to related catalyst system, have only co-catalyst to join from the outside in second reactor.Substantially not to deleterious poisonous substance of catalyzer such as moisture, oxygen, carbon monoxide carries out polymerization under the condition of carbonic acid gas and acetylene.
In first reactor, can prepare polymkeric substance, and in second reactor, can prepare the polymkeric substance of higher melt index (or lower molecular weight) than low-melt-index (or high molecular).This mode that can be known as forward.In addition, low-molecular-weight polymkeric substance can prepare in first reactor, and high-molecular weight polymer can prepare in second reactor, thisly can be known as reverse manner.
Usually, the mixture of polymkeric substance and active catalyst is shifted in second reactor by first reactor as the middle coupling device of transfer medium by the recycle gas that uses nitrogen or second reactor.
In the reactor (forward manner) of higher molecular weight: flow index can restrain/10 minutes for about 0.01-about 100, is preferably about about 20 grams of 0.2-/10 minutes.The molecular weight of this polymkeric substance is normally about 30, and 000-about 500,000.This density polymer can be 0.860g/cm at least
3, and be preferably 0.900-0.940g/cm
3The melt flow ratio of this polymkeric substance can be about 70 for about 16-, and be preferably about 16-about 45.
At ASTMD-1238, determine melt index under the condition of conditionE.It is measured and with gram expression in/10 minutes under the condition of 190 ℃ and 2.16 kilograms.At ASTMD-1238, under the condition of conditionF, determine flow index.It is measured with decupling under the condition of determining weight used in the melt index at 190 ℃, and with gram expression in/10 minutes.Molten fluidisation is a flow index and the ratio of melt index.
In the lower molecular weight reactor, melt index can restrain/10 minutes for about 0.2-about 3000, and is preferably about about 1000 grams of 2-/10 minutes.It is about 15 that the molecular weight of higher melt index polymkeric substance is generally, and 000-about 500,000.Density polymer prepared in this reactor can be at least 0.900 gram per centimeter
3, and be preferably 0.910-0.975 gram/cubic centimetre.The melt flow ratio of this polymkeric substance can be about 70 for about 16-, and be preferably about 16-about 45.
When shifting out from second reactor, adulterant or final product can have about 20 grams of about 0.02-/10 minutes, and were preferably about/10 minutes melt index of about 5.0 grams of 0.04-, or had/10 minutes flow index of about 165 grams of about 4-.It is about 25 that melt flow ratio is at least, and be preferably about 25-about 100.The molecular weight of final product is generally 50,000 about 500,000.The density of this adulterant is at least about 0.900 gram/cubic centimetre, and is preferably 0.910-0.960 gram/cubic centimetre.
In implementing process of the present invention, preferably fine powder is removed substantially, for example, it can be finished by sieving this adulterant in a usual manner.It has been generally acknowledged that fine powder is the particles of those particle diameters less than about 200 μ m.
As mentioned above, this adulterant can have the narrow molecular weight distribution to broadness that is characterized as multi-peak.Molecular weight distribution recently shows with the Mw/Mn of about 2.5-about 40 preferred about 3.0-about 30.Mw is a weight-average molecular weight; Mn is a number-average molecular weight; And the scope of Mw/Mn can be called heterogeneity index, and it is a kind of parameter of weighing the molecular weight distribution width.The polymkeric substance for preparing in the higher molecular weight reactor is about 0.4 with the weight specific energy of the polymkeric substance for preparing in the lower molecular weight reactor: about 2: 1 of 1-, and be preferably about 0.7 5: about 1.6: 1 of 1-.Best weight ratio is about 1: 1.This is known as splitting ratio or streaming rate.
In the typical method of blending of polymers, with catalyst system, ethene, alpha-olefins and hydrogen are sent in first reactor continuously at the scene; Polymkeric substance/catalyst mixture is shifted to from first reactor in second reactor continuously; Ethene, alpha-olefins, and hydrogen, and co-catalyst is fed in second reactor continuously.From second reactor, shift out final product.
In the reactor than low-melt-index, just as what showed in the flow index reactor, people wish to form a kind of multipolymer, and the mol ratio of α alkene and ethene can be about 0.001: about 0.4: 1 of 1-, and be preferably about 0.001: about 0.2: 1 of 1-.Hydrogen (if use) can be about 0.0003 with the mol ratio of ethene: about 0.3: 1 of 1-, and be preferably about 0.0007: about 0.1: 1 of 1-.Service temperature is generally about 60 ℃-Yue 100 ℃.Preferred service temperature is with desired variable density, the promptly lower lower temperature of density correspondence, the temperature that higher density is corresponding higher.
In the reactor of higher melt index:
Here people wish to form a kind of multipolymer, and the mol ratio of alpha-olefins and ethene can be about 0.001: about 0.6: 1 of 1-also is preferably about 0.01: about 0.42: 1 of 1-.The mol ratio of hydrogen and ethene is approximately 0.003: 1-3: 1, be preferably about 0.007: about 2.2: 1 of 1-.Service temperature is generally about 70 ℃-Yue 110 ℃.As mentioned above, temperature is preferably with desired variable density.
Can comprise the enhanced linear low density polyethylene with the polymeric articles that the present invention produces and have be similar to the polyethylene feature of producing through high-pressure process new LDPE (film grade) the two.
Pressure, promptly the total pressure in each reactor can be about 450 pools (PSi) of about 200-and is preferably about 350 pools (PSi) of about 280-.Thereby ethylene partial pressure in first reactor and the ethylene partial pressure in second reactor determine to reach above-mentioned splitting ratio according to the amount of polymer that requires to form in each these reactor.The remainder of total pressure is provided by the alpha-olefins except that ethene and rare gas element such as nitrogen.
Polyreaction is preferably carried out in the gas phase of two or more placed in-line fluidized-beds, but also can carry out in one or more agitator tank reactors.Typical fluidized-bed reactor can be described below: fluidized-bed is formed by formed identical granular resin in this reactor usually.Therefore, between polymerization period, fluidized-bed comprises established polymer beads, just in growing polymer particles, with be aggregated fluidizing and improve the granules of catalyst of gaseous state composition, this gaseous state composition is to be enough to causing particle separation and to become a kind of fluidic flow or speed is introduced into.Fluidizing agent is by initial feeding gas, replenishes feeding gas, and circulation (recirculation) gas, promptly comonomer and, if desired, properties-correcting agent and/or inert carrier gas are formed.
The essential part of reactive system is a container, fluidized-bed, and gas panel, the entrance and exit pipe, compressor, recycle gas cooler and product draw off system.In container, a deceleration area is arranged above bed, and a reaction zone is arranged in bed.They are all above gas panel.At US4, a kind of typical fluidized-bed reactor has been described in 482,687, and at US4, typical fluidized bed polymerization process has been described in 302,565.
Ethene, other gaseous state alpha-olefins, and hydrogen, when using, its feed stream and liquid alpha-olefins and co-catalyst solution preferably are admitted in the reactor cycles pipeline.At random, the liquid co-catalyst directly can be sent in the fluidized-bed.Part catalyst precursor that be activated or that be activated fully preferably is injected in the fluidized-bed as solid or mineral oil suspension.Under part activatory situation, activator is added in the reactor.The product composition can be incorporated into the mole variation recently of the comonomer in the fluidized-bed by change.When the state of bed reached the condition of polyreaction, product drew off from reactor continuously with granular or particle form.Recently control productive rate by adjusting dividing potential drop.Can adjust hydrogen: the mole of ethene is recently controlled molecular-weight average.The amount of alpha-olefins (except the ethene) can reach 20% (in the weight of multipolymer), and, if use, be preferably incorporated in the multipolymer in the total amount of about 1%-about 15% (with the weight of multipolymer).
Comprise gaseous state and liquid reactant, the retention time of the mixture of catalyzer and the resin in each fluidized-bed can be about 1-about 12 hours, and was preferably about 2-about 5 hours.
For this reason, a kind of exemplary stir jar reactor and method are described below.Agitator tank reactor is two-phase (Gu gas /) agitated bed, the contrary reactor that mixes." the plough tool " of 4 one covers flatly is installed so that make the particle in the reactor keep mechanical type to be fluidized in central axis with 200 rev/mins (rpm) rotation.Cylinder is that plough tool that 40.6 centimetres of (16 inches), diameters are 39.7 centimetres (15.6 inches) is scraped and swept by these through measuring length, forms the mechanical type fluidization regions of 46 liters (1.6 cubic feet).Because the vertical cylinder chamber, gas volume is greater than the volume of mechanical type fluidization regions.Be total up to 54.6 liters (1.93 cubic feet).A separator vessel is installed on the top of the vertical cylinder on the reactor.This container has the gas volume of 68 liters (2.41 cubic feet), greater than two times of the gas volume of reactor.Circulate continuously by reactor and separator through blower gas, so that gas composition is fully uniformly.
Employed reactor pressure is generally 300-450 pound/square inch (psig).Through control valve monomer and hydrogen (being used for molecular weight control) are sent into reactor continuously.Monomeric dividing potential drop is generally at 150-300 pound/square inch.Come the content of comonomer in the controlling polymers (no matter any) by adjusting feed rate, thereby keep comonomer stable in the gas phase/monomeric mol ratio.Measured a gas composition every 4-6 minute with gas chromatograph.Come the molecular weight of controlling polymers by the feed rate of adjusting hydrogen, thereby keep constant hydrogen and monomeric mol ratio in the gas phase.The remainder of nitrogen make-up gas composition, it enters with catalyzer and leaves through the aperture of gas reactor.Thereby the opening of adjusting the hole with computer keeps constant total pressure in the reactor.
With refrigerative ethylene glycol overcoat cooling reactor.Measure the temperature of bed with the RTD temp probe in the thermometer sleeve pipe, it becomes 60 ° of angles to put in the bed and at a cover of the inside downwards to plough between the tool with level.Temperature of reactor can be controlled between 10 °-110 ℃.Catalyst precursor can be used as dry powder or slip adds.The metering per injection in 0.5-1 Pounds Per Hour the nitrogen gas stream dried catalyst precursor and through 1/8 inch pipe it is fed in the reactor.The slip catalyst precursor of metering per injection in the continuous flow of the iso-pentane in 1/8 inch pipe or co-catalyst/isopentane solution, and the nitrogen gas stream of this mixture with 0.5-1 Pounds Per Hour joined in the reactor, can prevent that like this polymkeric substance from forming in syringe.In each case, with vertical become about 45 ° angle with catalyst injection before and after the bed in the central section between the plough tool.
Every batch of output of general granular polymer is the 20-25 pound, but its upper limit amount 30-35 pound.Periodical operation generally continues 3-6 hour.In addition, reactor can be operated in a continuous manner, and wherein granular polymer is discharged with the inventory that is typically 0.4 pound, and polyreaction is still in process simultaneously.In the successive mode, bed weight reach typically be the 15-25 pound after the starting product draw off system, and change and to draw off speed so that make the weight of bed keep constant.
Be added into the reactor and adjust charging from monomer and begin typically to operate up to reaching desired gas composition.In order to remove any Toxic that exists adds initial Intake Quantity before catalyst precursor begins charging co-catalyst in reactor.After the catalyst precursor charging begins, in reactor, add the monomer that is enough to keep gas concentration and ratio.When reaching the Intake Quantity of catalyzer, polymer yield increases to 5-10 Pounds Per Hour, adjusts the charging of catalyst precursor this moment so that keep the constant polymer yield.Remain with the catalyst precursor feed rate feed rate of co-catalyst proportional.Initial period in operation can use movable bed so that stir and dispersed catalyst.After forming desired batch weight, the hole of opening reactor rapidly, and nitrogen is removed monomer from resin.Then batch of material is discharged into box that atmosphere communicates in, unless regulation detects the inactivation of other catalyzer.For the multicomponent operation, as on-the-spot fusion, the desired resin part of preparation under the initial action condition fades to the condition of polyreactions at different levels subsequently that is fit to condition, and continues reaction.Should be noted that this method can look like at US5 588,790; What proposed in 5,352,749 and 5,436,304 operates in condensing mode like that.
The resin adulterant that where method obtains in order to take up an official post can be extruded to be fit to its purpose in conventional (level and smooth or tree-like pipe) extrusion machine.At US4,814,135; 4,857,600; Extrusion machine and the method that is used to push described in 5,076,988 and 5,153,382.The example that can be used to form the various extrusion machines of film is a simple helix type extrusion machine, as uses the blown film mould, air ring and the continuous improved extrusion machine of transfer device, blown film extrusion machine and concentrated flow extrusion machine.Typical simple helix extrusion machine can be described as be at the extrusion machine that the upper reaches end has a hopper and a mould is arranged at dirty end.Hopper feeds in the drum, and drum contains spiral.At dirty end, between spiral end and mould a folded dividing plate and a block buffering liner plate.It is believed that the extrusion machine spiral part is divided into three parts, feeding part, pressures partially, and metering section, and also have a plurality of heating zone from the post-heating district to preceding heating zone, from flowing to dirty a plurality of parts and zone.If it has the cylinder more than, cylinder is placed in-line.The length-to-diameter ratio of each cylinder is about 16: about 30: 1 of 1-.Extrude and under about 160 °-Yue 270 ℃ temperature, to carry out, and preferably under the about 240 ℃ temperature of about 180-, carry out.
At US4,684,703; 4,293,673; Also can find the above various features of putting forward in 4,354,009.
The example that can be incorporated into the conventional compound in the adulterant is an antioxidant, UV light absorber, static inhibitor, pigment, dyestuff, nucleator, filler, slippage agent, fire retardant, softening agent, processing material, lubricant, stablizer, resistance fumicants, viscosity control agent, and linking agent, catalyzer, and secondary accelerator, tackifier, and release agent.Except that filler, in per 100 parts of (weight) polymer blends, the amount of additive can be about 0.1-about 10 parts (weight).Filler can add up to 200 parts (weight) or more in per 100 parts of (weight) adulterants.
With following embodiment the present invention is described.
Embodiment 1
Be prepared as follows the catalyst precursor of dipping: ethyl chloride two (cyclopentadienyl) is contained the zirconium mixture soak trivial in silica supports from solution (toluene).At first anhydrate and the most surfaces silanol to remove, and it is carried out chemical treatment to advance-to go on foot the remaining silanol of passivation with aluminium three ethane (TEAL) 600 ℃ of following dried silica.Carrier after the processing has the median size of 80 μ m and 1.2 average particle size distribution width.The precursor of not slipper dip of exsiccant afterwards is used for polyreaction.
The polyreaction of each embodiment is classified to carry out in above-mentioned agitator tank reactor.By have more than each adding 8 grams catalyst precursor of carrier and continuously with co-catalyst in company with ethene, thereby 1-hexane and hydrogen are sent into initiated polymerization in the reactor together.When forming the first step resin of institute's requested number, reaction conditions is changed so that form second stage composition.Adjust temperature of reaction and ethene, the ratio of 1-hexane and hydrogen is so that form final product and the desired second stage component composition with desired each component proportions.If reactivity begins to descend, in the second stage of polyreaction, also introduce other catalyzer.At the on-the-spot adulterant of the multipolymer of producing is particle shape.Reaction conditions is represented in Table I in each order reaction in second order reaction:
Table I
The catalyst type metal metallocene is luxuriant
The reactor first step second stage
Stagnation pressure (pool, psig) 350 350
Temperature (℃) 70 85
H
2/ C
2(mol ratio) 0.000 0.001
C
6/ C
2(mol ratio) 0.025 0.025
C
2Dividing potential drop (pool PSi) 250 180
In Table II, represented resin property.They are the polyvinyl resin performance of production in first step reaction and the performance of final adulterant.
Table II
Example I
The final adulterant melt index of the first step (restraining/10 minutes) 0.05 1.6 flow index (restraining/10 minutes) 1 90 melt flow ratios 20 56 density (gram per centimeters
3) 0.920 0.920 volume density (1 pound/cubic feet) ... 22 APS (inch) ... 0.032 streaming rate (% weight) 50 50
The resins that will obtain from embodiment under 200 ℃ are at the 20mmBrabender that is furnished with 150mm bar mould
TMBe squeezed into the thick film of 35 μ m on the extrusion machine.Determine in each film 100 successive gels and determine the size and the distribution of gel through videomicroscopy.Mark and draw the occurrence rate of the gel of intended size (diameter of gel or area) according to the size of gel.On 150 square centimeters membrane area, calculate the quantity of big gel (greater than 75 μ m) and the quantity of less gel (less than 75 μ m).The replicate measurement secondary is got its mean value.
Above resin, the feature of promptly on-the-spot adulterant and film.Be illustrated in the Table III.
Table III
Embodiment 1
Melt index (restraining/10 minutes) 1.4
Melt flow ratio 58
Melt index changes 1.1-1.7
APS(μm) 980
Fine powder (less than 200 μ m) percentage amounts 1.8
Gel number (every 150cm
2) 22
HMW/LMW 6.62
Width 1.4
Embodiment 2
Be prepared as follows spray-dired catalyst precursor: three (PIVALIC ACID CRUDE (25) root) indenyl in fragrant substance solution is closed the zirconium solution spraying drying, and this solution is from containing the atresia of disregarding pore volume, the colloid silica slip of hydrophobic colloidal silica.Extent of dilution is that solid accounts for 7% (weight), and has the weight ratio of 50: 50 metal-salt and filler.The resulting spraying drying precursor of sieving separating.The resin property of the grain size of catalyst precursor and the final adulterant of companion that distributes is illustrated in the Table IV.In the Gas-phase reactor that is stirring under basic and identical described in the table 1 condition, form polymkeric substance.
Table IV
Embodiment 5 catalyzer drive width 1.5 flow indexs (restraining/10 minutes) 1.7 density (gram/cubic centimetre) the 0.920HMW/LMW 5.68 number of gels (gel content/150cm of body lower part of screen branch (sieving) catalyst precursor APS (μ m) 10 catalyst precursors
2) 90
Embodiment 3
The metallocenes precursor that use is submerged in the silica supports with median size as follows carries out polyreaction in the secondary streams fluidized bed reactor.At first silicon-dioxide dewaters down at 600 ℃, and passivation.Employed content of metal is that 0.22-0.25 mmole Zr/ gram precursor and Al/Zr ratio are about 200.
Thereby by causing first step polyreaction in the fluidized-bed that continuously above impregnated precursor and co-catalyst is joined polyethylene particle together with gaseous comonomers and hydrogen.The gaseous composition that uses the reaction of the nitrogen or the second stage will comprise that as transfer medium the newborn multipolymer and the final particle of dispersive active catalyst discharge and shift in the reactor of the second stage from first step reactor.Begin the fluidized-bed that polymer beads is also contained at the part place at second stage reactor.Gaseous comonomers and hydrogen are incorporated in the reactor of the second stage, they begin to contact with particle from the fs herein again.Also introduce other co-catalyst.Discharge the polymer beads of the mixture that contains the first step and second stage reacted constituent continuously.The variable of in Table V, having represented the performance of catalyst precursor and reaction conditions and resin product.The 1-hexene is as comonomer.
The preparation film, and determine its optical property as mentioned above.
Table V
Embodiment 3 catalyst precursors: carrier, (APS) 75 carriers, the luxuriant reaction conditions of (width) 0.91 reactor, 12 catalyst type metal metallocenes: temperature, (℃) 60 85 pressure, (PSi) 350 300 H
2/ C
2Mol ratio 0.000 0.0005 C
6/ C
2Mol ratio 0.04 0.018 C
2The final admixture melt index (MI) of dividing potential drop 250 100 streaming rates (% by weight) 60 40 resin properties (restraining/10 minutes) 0.03 0.4 flow index (restraining/10 minutes) 0.6 20.8 melt flow ratios, 20 52 density (g/cc) 0.905 0.915 remaining zirconium (ppm) 2.4 1.7 HMW/LMW, 5.92 APS (inch), 0.05 0.043 FAR+40/50 gel number/150cm214
Embodiment 4
The metallocenes precursor that uses Ziegler-Natta and be submerged in the silica supports with median size as follows and width carries out polyreaction in the secondary streams fluidized bed reactor.At first dewater at 600 ℃ of following silicon-dioxide, and passivation.Employed content of metal is that the ratio of 0.22-0.25 mmole Zr/ gram precursor and Al/Zr is about 200.
Thereby by initiated polymerization in the fluidized-bed of continuously the Ziegler-Natta precursor and the co-catalyst of above dipping being sent into polyethylene particle together in company with gaseous comonomers and hydrogen.Use the gas composition of nitrogen or second stage reactor will from first step reactor, discharge by the final particle that newborn multipolymer and dispersive active catalyst are formed, and shift in the reactor of the second stage as transfer medium.Begin the fluidized-bed that a polymer beads is also contained at the part place at second stage reactor.Gaseous comonomers and hydrogen are incorporated in the reactor of the second stage, they begin to contact with particle from first step reactor herein again.With the metallocenes precursor He Lv oxane (MAO) activator be incorporated in the reactor of the second stage.Discharge the polymer beads that contains the first step and second stage reacted constituent continuously.Catalyst precursor and reaction conditions and resin product changes of properties in Table VI, have been represented.The 1-hexene is as comonomer.
The preparation film, and determine its optical property as mentioned above.Table VI embodiment 4 catalyzer drive body: carrier (APS) 75 carriers (width) 0.91 reactor 12 catalyst type metallocenes Ziegler-Natta reaction conditionss: temperature (℃) 60 90 pressure (pool), 350 300H
2/ C
2Mol ratio 0.0015 0.060C
6/ C
2Mol ratio 0.040 0.050C
2Dividing potential drop 250 50 streaming rates, the final admixture melt index (MI) of (% by weight) 50 50 resin properties, (restraining/10 minutes) 0.05 1.6 fluid index, (restraining/10 minutes) 1.4 99 melt flow ratios, 28 62 density, (g/cc) 0.905 0.915 remaining Zr, (ppm) 3.0 1.5HMW/LMW 8.60APs, (inch) 0.05 0.043FAR+40/50 gel number/150cm2The explanation of 18 his-and-hers watches:
1. at ASTMD-1238, determine melt index (restrain/10 minutes) under the condition of ConditionE, under 190 ℃, measure and represented in/10 minutes with gram.
2. at ASTMD-1238, determine flow index under the condition of ConditionF.Measure in the condition that decuples the used weight of above melt index test, flow index changes: the flow index from (greater than 10 orders) of maximum to least (being less than 140 orders) screened part.
3. melt flow ratio is a flow index and the ratio of melt index.
4. density (g/cm
3) be the density of ethene/1-hexene copolymer product, it is represented with gram/cubic centimetre.
5. the volume density of every kind of resin (non-adulterant) provides with pound/cubic feet.
6. splitting ratio (weight %): it is every kind of poly percentage ratio (in adulterant weight) in the adulterant.
7. from Malvern
TM2600 particle size analyzers obtain catalyst precursor particle diameter and polymer beads particle diameter.Also can be from Rotap
TMScreening plant obtains polymkeric substance particle diameter analytical value.
8. number of gels is the mean value of secondary calculating, and comprises the big and little gel that influences the FAR value.Calculating number is every 150cm
2Film in the gel number.
9.APS two median sizes.
10.HMW two high molecular.
11.LMW two lower molecular weights.
12.FAR be the ocular estimate of film, evaluation is obtained by the range estimation to film, as mentioned above.
Claims (8)
1. method for preparing the on-the-spot adulterant of polyethylene is included under the polymerizing condition at least a metallocenyl catalyst system is contacted in gas phase in two or more placed in-line each reactors with one or more alpha-olefins, and condition is:
(a) ethene is incorporated in each reactor;
(b) at random, alpha-olefins and the diene copolymers that one or more is had at least 3 carbon atoms is incorporated at least one reactor.
(c) the ethene polymers matrix and the mixture of catalysts that form in placed in-line first reactor are shifted in the placed in-line next reactor; And
(d) polymerizing condition in each reactor is such, and promptly final polymkeric substance is a multi-peak in molecular weight distribution or comonomer composite distribution, or the two all is multi-peaks.
2. the process of claim 1 wherein and only the metallocenyl catalyst system is joined in first reactor.
3. the process of claim 1 wherein that the metallocenyl catalyst system is added in each reactor.
4. the process of claim 1 wherein metallocene-based catalyst systems joined in the poly reactor that forms lower molecular weight and with the Ziegler/Natta catalyst system and join in the poly reactor that forms higher molecular weight.
5. the process of claim 1 wherein that metallocenes is first propylhomoserin root or the carboxylate radical of representing in general formula I or II.
6. the process of claim 1 wherein that the metallocenyl catalyst system is DNAcarrier free system.
7. the method for claim 5, wherein the metallocenyl catalyst system is DNAcarrier free system.
8. the method for claim 7, wherein metallocenes is that three (diethyl methyl carbamic root) indenyl closes zirconium.
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|---|---|---|---|
| CN 96121675 CN1153786A (en) | 1995-10-26 | 1996-10-25 | Process for preparing in situ polyethylene blend |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US548,593 | 1995-10-26 | ||
| CN 96121675 CN1153786A (en) | 1995-10-26 | 1996-10-25 | Process for preparing in situ polyethylene blend |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336876C (en) * | 2003-01-28 | 2007-09-12 | 博里利斯技术有限公司 | Coating composition, method of preparation thereof and substrate coated therewith |
| CN100369729C (en) * | 2001-06-14 | 2008-02-20 | 英尼奥斯制造业比利时有限公司 | Method of compounding multimodal polyethylene composition |
| CN101796083B (en) * | 2007-09-03 | 2013-02-06 | 英尼奥斯制造业比利时有限公司 | Slurry phase polymerization process |
| CN101796081B (en) * | 2007-09-03 | 2013-02-06 | 英尼奥斯制造业比利时有限公司 | Slurry phase polymerization process |
-
1996
- 1996-10-25 CN CN 96121675 patent/CN1153786A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369729C (en) * | 2001-06-14 | 2008-02-20 | 英尼奥斯制造业比利时有限公司 | Method of compounding multimodal polyethylene composition |
| CN100336876C (en) * | 2003-01-28 | 2007-09-12 | 博里利斯技术有限公司 | Coating composition, method of preparation thereof and substrate coated therewith |
| CN101796083B (en) * | 2007-09-03 | 2013-02-06 | 英尼奥斯制造业比利时有限公司 | Slurry phase polymerization process |
| CN101796081B (en) * | 2007-09-03 | 2013-02-06 | 英尼奥斯制造业比利时有限公司 | Slurry phase polymerization process |
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