JP2003524038A - Catalyst systems, methods for their preparation and their use in polymerization processes - Google Patents

Abstract

  (57) [Summary] Disclosed are polymerization processes that utilize low levels of dienes to control the melt index ratio of the polymer product independent of melt index and density. The method of the present invention produces a polymer having enhanced processability. More specifically, this method produces an ethylene-based polymer having enhanced melt strength and shear thinning properties produced by a gas phase polymerization process utilizing a bulky ligand metallocene polymerization catalyst. I do.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to polymerization processes. In particular, the present invention utilizes low levels of dienes to improve the processability of the polymer and independently controls the melt index ratio of the polymer to process bulky ligand metallocene catalyzed polymers. To improve sex.

[0002] polymers produced by the background bulky ligand metallocene catalysts of the present invention has excellent properties such as mechanical strength and transparency. However, these polymers are typically difficult to process. Processability means that the polymer can be economically processed and uniformly shaped. The processability factor is the melt strength, ie the strength of the polymer at the extrusion temperature,
Includes shear thinning, ie the ease with which the polymer will flow and whether the extrudate is strain free.

Ethylene-based polymers produced by bulky ligand metallocene catalysis (mPe) are generally more processable than, for example, low density polyethylene (LDPE) produced by high pressure polymerization. Have difficulty. Typically mPe requires higher motor power and produces higher extrusion pressure to match the LDPE output. This is because the polymer has a low melt index ratio (MIR, which is the ratio I ₂₁ / I ₂ where I ₂ is the MI measured at 190 ° C. according to ASTM-1238 condition E, and I ₂₁ is 190 ° C and ASTM-1238 condition F
Is a flow index measured according to). In addition, mPe generally has a lower melt strength that adversely affects bubble stability during inflation, and thus is more susceptible to melt fracture at commercial shear rates. The relatively low melt strength and relatively low melt viscosity of mPe make blown bubble extrusion fabrication of films more difficult and less prone to manufacture than other types of polymers processed by the same technique. Slow down.

One way to improve the processability of mPe (both shear thinning and melt strength) is to introduce long chain branching (LCB) into the polymer. In LCB, the polymer has branches that are long enough that the chains are entangled, that is, branches whose branch length is long enough to entangle with other polymer molecules or with other polymer molecules. Contains enough carbon to be entangled. In general, long chain branches include chain lengths of at least 6 carbons and usually contain 10 or more carbons. Long chain branching
It can be as long as the polymer backbone. Polyethylene containing long chain branching has good strength and low viscosity under high shear conditions which allows high throughput. Furthermore, polyethylenes containing long chain branches often exhibit strain hardening, so films made from such polyethylenes tend to fail during manufacture.

At present, there is no effective method for independently controlling the LCB in a polymerization method, particularly a gas phase polymerization method. In addition, current gas phase reactors are solely concerned with controlling the melt index (MI) and density of polymer products. As a result of this two-dimensional control of polymer product properties, the product M that measures shear thinning ability is measured.
It is difficult for IR to control MI and density independently. This is because the MIR varies with different MI and density targets. For example, as MIR increases, MI decreases and density increases.

US Pat. No. 5,492,986 issued to Feb. 20, 1996 (Bay et al.) Describes ethylene, one or more α-olefins and one or more non-conjugated dienes under polymerization conditions utilizing a vanadium catalyst. Disclosed is a method for producing a homogeneous polyethylene having excellent strain hardening characteristics by contacting with a polyethylene.

European patent application EP 0543119A2 discloses a prepolymerization catalyst consisting of α-olefins and polyenes.

European Patent Application EP-0743327A2 discloses polyethylenes with enhanced processability made by utilizing the racemic and meso stereoisomers of bridged metallocene-type catalysts with planar chirality.

European Patent Application EP-0784062A2 (EP'062) describes polyethylene having long chain branching in an amount sufficient to provide chain entanglement or long chain branching in the presence of a polyene or hydrocarbon linking compound. Discloses a method of manufacturing.
This EP'062 application describes a sufficient amount of diene levels as about 8000-35000 ppm. However, this diene concentration results in a polymer product with a gel. Furthermore, the EP '062 application does not control the feed of the dienes independently, but rather dissolves the dienes in the hexene comonomer and feeds the combined mixture into the reactor. Therefore, the method of the EP'062 application combines the LCB and density of the polymer product.

[0010] P. Pietikainene et al. (Helsinki Institute of Technology, Espoo, Finland) "Study on the copolymerization and terpolymerization of ethylene and dienes using metallocene catalysts" (Polymer Technology Publication Series No. 16, 1993) , Are reviewing the use of metallocene catalysts in ethylene copolymerization and terpolymerization.

Naga Naofumi et al. “Copolymerization of propene and non-conjugated dienes including intermolecular cyclization with metallocene / metalminoxanes” (Macromolecules, 32 (1999), 13).
48-1355) discloses a cyclization reaction of an incorporated diene prepared by copolymerization of propene with a non-conjugated diene (1,5-hexadiene and 1,7-octadiene) utilizing a stereospecific metallocene catalyst. is doing.

[0012] P. Pietikainene et al., "Copolymerization of ethylene and non-conjugated dienes with a Cp ₂ ZrCl ₂ / MAO catalyst system" (European Polymer Journal 35 (1999), 104).
7-1055) discloses the cyclization of hexadiene to form a 5-membered ring in polyethylene produced by metallocene catalysis.

Although the prior art has described these polymerization methods, it improves the processability of mPe,
There is a need for a method for improving the MIR of mPe and providing discrete control of MI, density and MIR of polymer products.

SUMMARY OF THE INVENTION The present invention relates to a method for improving the processability of bulky ligand metallocene catalyzed polymers.

In one aspect, the present invention is directed to improving processability of bulky ligand metallocene catalyzed polyethylene by utilizing low levels of dienes to improve the melt index ratio of the polymer. To provide a method.

Viewed from another aspect, the present invention makes the melt index ratio of polyethylene bulk catalyzed by a bulky ligand metallocene independent of melt index and density by introducing low levels of dienes into the gas phase polymerization process. To provide a way to control.

[0017] DETAILED DESCRIPTION Introduction The present invention of the present invention, a low level of diene in order to introduce long chain branching into the polymer produced in gas phase polymerization process using a bulky ligand metallocene polymerization catalyst Regarding to use. The present invention also relates to the use of low levels of dienes to control the melt index ratio of the polymer product independent of melt index and density. Polymers produced by this method, especially polyethylene, including homopolymers, copolymers and terpolymers of ethylene, have increased melt strength and Has shear thinning behavior. This enhanced processability includes ease in both extrusion and fabrication methods, such as blown film, blow molding, extrusion coating and wire and cable extrusion operations.

Bulky Ligand Metallocene Catalyst Compounds The process of the present invention provides polymers with enhanced processability by the addition of low levels of dienes during polymerization. In particular, the process of the present invention improves the processability of polyethylene polymers produced by gas phase polymerization processes catalyzed by bulky ligand metallocene catalyst compounds. Generally, these catalyst compounds include half and whole sandwich compounds in which one or more bulky ligands are bound to at least one metal atom. Typical bulky ligand metallocene compounds are described as containing one or more bulky ligands bound to at least one metal atom and one or more leaving groups. In one preferred embodiment, at least one bulky ligand is η- on the metal atom.
Bonded, most preferably η ⁵ -bonded to the transition metal atom.

Bulky ligands are generally represented by one or more open, acyclic or fused rings or ring systems or combinations thereof. The rings or ring systems of these bulky ligands are typically composed of atoms selected from atoms of Groups 13-16 of the Periodic Table of the Elements. Preferably, this atom is selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron and aluminum or combinations thereof. Most preferably, the ring or ring system is composed of carbon atoms, such as for example cyclopentadienyl ligands or cyclopentadienyl type ligand structures or pentadiene, cyclooctatetraenedyl or imide ligands. And other similar functional ligand structures, but is not limited thereto. The metal atom is preferably selected from groups 3 to 15 of the Periodic Table of the Elements and the lanthanide or actinide series. Preferably the metal is in groups 4-12, more preferably groups 4, 5 and 6.
Transition metals from the Group, and most preferably, the transition metals are from Group 4.

[0020] In one embodiment, the low level diene, the following _{^{formula: L A L B MQ n (}} I) ( wherein, M is a metal atom from the Periodic Table of the Elements, the period of the elements 3rd of the table
It may be from a Group 12 metal or from the lanthanide or actinide series, preferably M is a Group 4, 5 and 6 transition metal, more preferably M
Is zirconium, hafnium or titanium. ) Is added to the polymerization process utilizing a bulky ligand metallocene catalyst compound. The bulky ligands L ^A and L ^B are open, acyclic or fused rings or ring systems which are unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl type coordinations. Any ancillary ligand system, including cyclopentadienyl-type ligands containing child, heteroatom-substituted and / or heteroatoms. Examples of bulky ligands are cyclopentadienyl ligands, cyclopentaphenanthrenyl ligands, indenyl ligands,
Benzoindenyl ligand, fluorenyl ligand, octahydrofluorenyl ligand, cyclooctatetraenediyl ligand, cyclopentacyclododecene ligand, azenyl ligand, azulene ligand, pentalene Ligands, phosphoryl ligands, phosphoimines (WO99 / 40125), pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, etc. (hydrogenated versions of these,
(Including, for example, tetrahydroindenyl ligands), but is not limited thereto. In one embodiment, L ^A and L ^B are any other ligand structure capable of η-bonding to M, preferably η ³ -bonding to M, and most preferably η ⁵ -bonding. be able to. In yet another embodiment, the atomic and molecular weight (MW) of L ^A and L ^B is 60.
It exceeds amu, preferably 65 a.mu or more. In another embodiment, L ^A and L ^B are composed of one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur and phosphorus, and are open, acyclic or fused with carbon atoms. Or a ring system can be formed, for example a heterocyclopentadienyl ancillary ligand. Other L ^A and L ^B bulky ligands include, but are not limited to, bulky amides, phosphides, alkoxides, aryl oxides, imides, carbolides, borolides, porphyrins, phthalocyanines, cholines and other polyazo macrocycles. . Independently, each L ^A and L ^B can be the same or different type of bulky ligand attached to M. In one embodiment of formula (I), only one of L ^A or L ^B is present.

Independently, each L ^A and L ^B can be unsubstituted or substituted with a combination of substituents R. Examples of the substituent R are hydrogen or a linear or branched alkyl group or alkenyl group, alkynyl group, cycloalkyl group or aryl group, acyl group, aroyl group, alkoxy group, aryloxy group, alkylthio group,
Dialkylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
It includes, but is not limited to, one or more selected from the group selected from a carbomoyl group, an alkyl or dialkylcarbamoyl group, an acyloxy group, an acylamino group, an aroylamino group, a linear, branched or cyclic alkylene group, or a combination thereof. In a preferred embodiment, the substituent R has up to 50 non-hydrogen atoms, preferably 1 to 30 carbons, which can also be substituted with halogens or heteroatoms and the like. Examples of alkyl substituents R are methyl, ethyl, propyl,
Including, but not limited to, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like (including all isomers thereof such as tert-butyl, isopropyl and the like). Other hydrocarbyl groups are
Fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromhexyl, chlorobenzyl, and hydrocarbyl-substituted organic semimetal groups such as trimethylsilyl, trimethylgermyl, and methyldiethylsilyl, and tris (trifluoromethyl) silyl, methyl-bis (difluroyl). Ormethyl) Cyril,
Organic semimetal groups substituted with halocarbyl including bromomethyldimethylgermyl and disubstituted boron groups including dimethylboron and dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen groups (
Disubstituted pnictogen groups, including (including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide and ethyl sulfide). Non-hydrogen substituent R
Include carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium atoms and the like, including but not limited to vinyl terminated ligands such as 3-butenyl, 2-propenyl, 5-hexenyl and the like. Including olefins such as olefinically unsaturated substituents. Further, at least two kinds of R groups, preferably two kinds of adjacent R groups are bonded to each other to form carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum,
Form a ring structure having 3 to 30 atoms selected from boron or a combination thereof. Also, a substituent R such as 1-butanyl can form a carbon sigma bond to the metal M.

Other ligands, such as at least one leaving group Q, can be attached to the metal M. For the purposes of this patent specification and the appended claims, the term "leaving group" is used to form a bulky ligand metallocene-catalyzed cation capable of polymerizing one or more olefins. Bulky Ligand Any ligand that can be withdrawn from the metallocene catalyst compound. In one embodiment, Q is a monoanionic labile ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2 so that formula (I) above represents a neutral bulky ligand metallocene-type catalyst compound.

Examples of Q ligands are amines, phosphines, ethers, carboxylates, dienes, 1
Includes, but is not limited to, weak bases such as hydrocarbyl groups having -20 carbon atoms, hydrides or halogens, and the like, or combinations thereof. In another embodiment, two or more Q form part of a fused ring or ring system. Other examples of Q ligands include the substituent R as described above and include cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis, (N-methylanilide), dimethylamide, dimethylphosphide group and the like are included.

In a preferred embodiment, low levels of dienes have the following formula: L ^A AL ^B MQ _n (II) where L ^A and L ^B are bridged to each other by at least one bridging group A.
Of the bulky ligand metallocene type catalyst compound.

These bridged compounds represented by formula (II) are known as bridged bulky ligand metallocene catalyst compounds. L ^A , L ^B , M, Q and n are as defined above. Examples of bridging groups A are often referred to as divalent moieties such as, but not limited to, carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atoms or at least one of combinations thereof, At least one first
Includes bridging groups containing Group 3 to 16 atoms. Preferably the bridging group A contains carbon, silicon or germanium atoms, most preferably A contains at least one silicon atom or at least one carbon atom. The bridging group A can also contain substituents R as defined above, including halogen and iron. Crosslinking group A
Examples of include but are not _{limited, R '2 C, R'} 2 Si, R '2 SiR' 2 Si, R '2 Ge, R
'P (where R'is independently hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organic semimetal,
Halocarbyl is a substituted organic semi-metal, a disubstituted boron, a disubstituted pnictogen, a group which is a substituted chalcogen) or a halogen or two or more R's are combined to form a ring or ring system. be able to. In one embodiment, the formula (II
The crosslinked bulky ligand metallocene catalyst compound (1) has two or more kinds of crosslinkable groups A (E
P664301B1).

In another embodiment, the bulky ligand metallocene catalyst compound has a bulky ligand L ^A and L ^{B of} formulas (I) and (II) wherein the R substituent is on each bulky ligand. It is substituted with the same or different number of substituents. In another embodiment, formulas (I) and (II)
Of the bulky ligands L ^A and L ^B are different from each other.

Other bulky ligand metallocene catalyst compounds and catalyst systems useful in the present invention are US Pat. Nos. 5,064,802, 5,145,819, 5149819, 524.
No. 3001, No. 5239022, No. 5276208, No. 5296434,
5321106, 5329031, 5304614 and 56774.
No. 01, No. 5723398, No. 5735578, No. 5854363, No. 5
No. 856547, No. 5858903, No. 5859158, No. 5900517.
And 5939503 and PCT patent applications WO 93/08221, WO 9
3/08199, WO95 / 007140, WO98 / 11144, WO98 /
41530, WO98 / 41529, WO98 / 46650, WO99 / 025.
40 and WO 99/14221 and European patent application EP-A-0578838,
EP-A-0578838, EP-B1-0638595, EP-A1-081
6372, EP-A2-0839834, EP-B1-0632819, EP-
They may include those described in B1-0748821 and EP-B1-0757996, the specification of which is incorporated herein by reference in its entirety.

In another embodiment, the bulky ligand metallocene catalyst compounds useful in the present invention include bridged heteroatom monobulky ligand metallocene compounds. These types of catalysts and catalyst systems are described, for example, in PCT patent applications WO 92/00333, WO 94/0792.
8, WO91 / 04257, WO94 / 03506, WO96 / 00244, W
O97 / 15602 and WO99 / 20637 and US Pat. No. 5,057,475.
No. 5096868, 50505438, 519841 and 522.
7440 and 5264405 and European patent application EP-A-042043.
6 are described. This specification refers to all of these.

In this embodiment, low levels of dienes are obtained from the formula: L ^C AJMQ _n (III) where M is a metal atom of Groups 3 to 16 of the Periodic Table of the Elements or a group of actinides and lanthanides. The metal of choice, preferably M is a Group 4-12 transition metal, more preferably M is a Group 4, 5 and 6 transition metal, and most preferably M is A Group 4 transition metal in any oxidation state, especially titanium,
L ^C is a substituted or unsubstituted bulky ligand bound to M, J is bound to M, A is bound to M and J, J is a heteroatom ancillary ligand, and A is a bridging group, Q is a monovalent anionic ligand, and n is an integer 0, 1 or 2. ) Is added to the polymerization process utilizing a bulky ligand metallocene catalyst compound. In formula (III) above, L ^C , A and J form a fused ring system. In an embodiment, L ^C of formula (III) is as defined above for L ^A , and has the formula (III)
A, M and Q of are as defined above in formula (I).

In formula (III), J is a heteroatom-containing ligand, wherein J is an element with a coordination number of 3 from Group 15 of the Periodic Table of the Elements or 2 from Group 16 Is an element with a coordination number of. Preferably, J contains nitrogen, phosphorus, oxygen or sulfur atoms, with nitrogen being the most preferred.

In another embodiment, the bulky ligand type metallocene catalyst compound utilized is a metal,
Complexes of preferably a transition metal with a bulky ligand, preferably a substituted or unsubstituted π-bonded ligand, and one or more heteroaryl moieties, eg US Pat. No. 5,527,775.
Low levels of dienes are added to the polymerization process as described in Nos. 2 and 5747406 and EP-B1-0735057, which is incorporated herein by reference in its entirety.

[0032] In another embodiment, the low level diene has the formula: L ^D MQ ₂ (YZ) in X _n (IV) (wherein, M is a Group 3 to 16 metal, preferably a 4-12 Group A transition metal, most preferably a Group 4, 5 and 6 transition metal, L ^D is a bulky ligand bound to M, each Q independently bound to M, and Q ₂ (YZ) forms a monocharged polydentate ligand, A or Q is a monovalent anionic ligand that is also bound to M, and X is a monovalent anion ligand when n is 2. Is a divalent anion group or X is a divalent anion group when n is 1 and n is 1 or 2.). Added to the polymerization process.

In formula (IV), L and M are as defined above for formula (I). Q is as defined above for formula (I), preferably Q is-
O -, - NR -, - CR 2 - and is selected from the group consisting of -S-. Y is either C or S. Z _{is, -OR, -NR 2, -CR 3} , -SR, -SR 3, -
PR _2, is selected from the group consisting of -H, and substituted or unsubstituted aryl group, provided that when Q is -NR-, Z is _{-OR, -NR 2, -SR, -SR} 3,
It is selected from one of -PR ₂ and the group consisting of -H. R is carbon, silicon,
Selected from the group consisting of nitrogen, oxygen and / or phosphorus, preferably in this case R is
Hydrocarbon radicals containing 1 to 20 carbon atoms, most preferably alkyl, cycloalkyl or aryl radicals. n is an integer of 1 to 4, preferably 1 or 2. X is a monovalent anionic group when n is 2 or X is a divalent anionic group when n is 1. Preferably X is a carbamate, a carboxylate or another heteroallyl moiety described by a combination of Q, Y and Z.

In another embodiment of the present invention, the bulky ligand metallocene-type catalyst compound is a heterocyclic ligand in which the ring or ring system of the bulky ligand comprises one or more heteroatoms or combinations thereof. It is a complex. Examples of heteroatoms include, but are not limited to, Group 13-16 elements, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin. These bulky ligand metallocene catalyst compounds are disclosed in WO96 / 33202, WO9
6/34021, WO97 / 17379 and WO98 / 22486 and EP-
A1-0874005 and U.S. Pat. Nos. 5,637,660, 5,539,124,
No. 5554775, No. 5756611, No. 5233049, No. 57444.
17 and 5856258. This specification refers to all of these.

In another embodiment, the bulky ligand metallocene catalyst compound is a complex known as a transition metal catalyst based on a bidentate ligand containing a pyridine or quinoline moiety, eg, June 23, 1998. US patent application Ser. No. 09 / 103,620, which is hereby incorporated by reference. In another embodiment, the bulky ligand metallocene catalyst compound is PCT patent application WO 99/01481 and W
O98 / 42664. The present specification refers to them.

In another embodiment, low levels of the diene have the formula: ((Z) XA _t (YJ)) _q MQ _n (V) where M is the third to thirteenth element of the Periodic Table of the Elements. A group or a metal selected from the lanthanide and actinide series, Q is bound to M, and each Q is a monovalent, divalent or trivalent anion, and X and Y are bound to M. One or more of X and Y are heteroatoms, preferably both X and Y are heteroatoms, and
Is contained in a fluorocyclic ring J, where J consists of 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms, Z is bound to X, where Z is , 1
Consisting of 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms, preferably
Z is a cyclic group containing 3 to 50 atoms, preferably 3 to 30 carbon atoms, t is 0 or 1, and when t is 1, A is X, Y or Is a bridging group bonded to at least one of J, preferably X and J, and q is 1 or 2
And n is an integer from 1 to 4 depending on the oxidation state of M. ) Is added to the polymerization process utilizing a bulky ligand metallocene catalyst compound.

In one embodiment, the bulky ligand metallocene catalyst compound is also described in the article by Johnson et al., “A Novel Pd (II) and N for Polymerization of Ethylene with α-Olefins”.
"I (II) -based catalysts" (J. Am. Chem. Soc. 1995, 117, 6414-6415) and Johnson et al. "Ethylene and propylene with vinyl monomers functionalized with palladium (II) catalysts". Copolymerization "(J. Am. Chem. Soc. 1996, 118, 267-268)
And WO96 / 23010, WO99 / 024 published on August 1, 1996
72, US Pat. Nos. 5,852,145, 5,866,663 and 5,880,241.
It is also within the scope of this invention to include the complexes of Ni ²⁺ and Pd ²⁺ described in US ^Pat . These complexes can either be dialkyl ether adducts or the alkylation reaction products of the described dihalide complexes that can be activated to the cationic state by the activators of this invention described below.

Also included as bulky ligand metallocene catalyst is PCT patent application WO
96/23010 and WO 97/48735 and Gibson et al., Chem. Com
m, pp. 849 to 850 (1998), which is a ligand mainly composed of the group 8 to 10 metal compound diimine. This specification refers to all of these.

Other bulky ligand metallocene catalysts are imide complexes of Group 5 and 6 metals described in EP-A2-0816384 and US Pat. No. 5,851,945. This specification refers to these. Further, bulky ligand metallocene catalysts are described in D. H
． Organometallics 1195, 14, 5478-5480 by Maconville and others
Crosslinked bis (arylamide) Group 4 compounds described in. This specification refers to this. Further, a crosslinked bis (amide) catalyst compound is WO96 /
27439. This specification refers to this. Other bulky ligand metallocene catalysts are described in US Pat. No. 5,852,146 as bis (hydroxyaromatic nitrogen ligands). This specification refers to this. Other metallocene catalysts containing one or more Group 15 atoms include those described in WO98 / 46651. This specification refers to this. Still other metallocene bulky ligand metallocene catalysts include polynuclear bulky ligand metallocene catalysts such as those described in WO 99/20665. This specification refers to this.

Also, in one embodiment, the bulky ligand metallocene catalysts of the present invention described above are their structural or optical isomers or enantiomers (meso and racemic isomers, eg US Pat. No. 5,852,143). The present specification refers to this) and mixtures thereof.

Activator Compositions The bulky ligand metallocene polymerization catalyst compounds described above are typically activated by a variety of methods that result in compounds having free coordination sites for coordinating, inserting and polymerizing olefins. To be done. For the purposes of this patent specification and the appended claims, the term "activator" is defined to be any compound or component or process capable of activating any bulky ligand metallocene catalyst. It The activator can be converted to a bulky ligand metallocene catalyst cation which is active, for example, using a Lewis acid or a non-coordinating ionic activator or ionizable activator or a neutral bulky ligand metallocene catalyst as a catalyst. Other compounds can be included including, but not limited to, Lewis bases, aluminum alkyls, conventional promoters, and combinations thereof.

It is within the scope of the invention to use alumoxanes or modified alumoxanes as activators. There are various methods for making alumoxanes and modified alumoxanes. Examples of the method are described in US Pat. Nos. 4,665,208 and 4,952,540.
No. 5,091,352, No. 5206199, No. 5204419, No. 48747.
No. 34, No. 4924018, No. 4908463, No. 4968827, No. 5
No. 308815, No. 5329032, No. 5248801, No. 5235081
Nos. 5157137, 5103030, 5391793, 539.
No. 1529, No. 5693839, No. 5731253, No. 5731451,
Nos. 5744656, 5847177, 5854166, and 58562.
56 and 5939346 and European patent application EP-A-0561476,
EP-B1-0279586, EP-A-0594218 and EP-B1-05
86665 and PCT patent application WO 94/10180, but is not limited thereto. This specification refers to all of these.

In one embodiment, the alumoxane or modified alumoxane is mixed with a catalyst compound. In another specific example, under the trade name “modified methylalumoxane type 3A”,
A solution of modified methylalumoxane in heptane (MMA03A) commercially available from Akzo Chemical Co. of the Netherlands (see, for example, the alumoxane disclosed in US Pat. No. 5,041,584, which is hereby incorporated by reference). Are mixed with the catalyst compound to form a catalyst system.

Organoaluminum compounds useful as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.

Neutral or ionic neutralizing or stoichiometric activators that will ionize the bulky ligand metallocene catalyst compounds, eg tri (n-butyl) ammonium tetrakis (pentafluorophenyl) Boron, a semi-metal precursor of trisperfluorophenylboron or a semi-metal precursor of triperfluornaphthylboron,
It is within the scope of this invention to use a polyhalogenated heteroborane anion (WO98 / 43983) or combinations thereof. It is also within the scope of this invention to use the neutral or ionic activators alone or in admixture with the alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include trisubstituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituents are each independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy and halide. Preferably, the three groups are independently selected from halogen, mono- or polycyclic (including halo-substituted) aryl, alkyl and alkenyl compounds and mixtures thereof, with 1-20 preferred. Alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryl). ). More preferably,
The three groups are alkyl having 1 to 4 carbon groups, phenyl, naphthyl or mixtures thereof. Most preferably, the neutral stoichiometric activator is trisperfluorophenylboron or trisperfluoronaphthylboron.

The ionic stoichiometric activator compound may include some other cation that associates with the active protons or the rest of the ions of the ionizable compound, but does not or only slowly coordinates. Such compounds and the like are described in European patent applications EP-A-0570982, EP-A-0520732, EP-A-04953.
75, EP-B1-0500944, EP-A-0277003 and EP-A-.
0277004 and US Pat. Nos. 5,153,157, 5,1984,410 and 5,
066741, 5026197, 5241025, 5384299.
And U.S. Pat. No. 5,502,124 and U.S. patent application Ser. No. 08 / 285,380 filed Aug. 3, 1994. This specification refers to all of these.

In a preferred embodiment, the stoichiometric activator comprises cation and anion components,
And the following formula: (L-H) _d ⁺ (A ^d- ) (VI) (wherein L is a neutral Lewis base, H is hydrogen, and (L-H) ⁺ is Bronsted acid). And A ^d- is a non-coordinating anion having a charge d-, and d is 1
Is an integer of ˜3. ) Can be represented by.

The cation component, (L-H) _d ^+, is a cationic component that protonates or abstracts moieties such as alkyl or aryl from bulky ligand metallocenes or transition metal catalyst precursors containing Group 15 And a Bronsted acid, such as a protonated Lewis base or a reducing Lewis acid, capable of generating a transition metal species of

The activatable cation (L-H) _d ⁺ can be a Bronsted acid capable of donating a proton to a transition metal catalyst precursor to produce a transition metal cation, such as ammonium, oxonium. , Phosphonium, silylium and mixtures thereof, preferably methylamine, aniline, dimethylamine, diethylamine,
N-methylaniline, diphenylamine, trimethylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, ammonium p-nitro-N, N-dimethylaniline, triethylphosphine, triphenyl Includes phosphoniums from phosphines and diphenylphosphines, ethers such as dimethyl ether, diethyl ether, oxoniums from tetrahydrofuran and dioxane, thioethers such as sulfonium from diethyl thioether and tetrahydrothiophene, and mixtures thereof. The activating cation (L-H) _d ⁺ can also be an abstraction moiety such as silver, carbonium, tropylium, carbenium, ferrocenium and mixtures thereof, preferably carbonium and ferrocenium. Most preferably, (L-H) _d ⁺ is triphenylcarbonium.

A ^{d− of the} anion component has the formula: [M ^{k +} Q _n ] ^d− (where k is an integer of 1 to 3, n is an integer of 2 to 6, and n−k = d, M is an element selected from Group 13 of the Periodic Table of the Elements, and Q is independently hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl. , Substituted hydrocarbyl, halocarbyl,
Substituted halocarbyl and halosubstituted hydrocarbyl groups, wherein Q has up to 20 carbon atoms, provided that at most one occurrence Q is a halide.
) Is included. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is pentafluorinated. It is a ruaryl group.

Most preferably, the ionic stoichiometric activator (L-H) _d ⁺ (A ^d- ) is N, N-
It is dimethylanilinium tetra (perfluorophenyl) borate or triphenylcarbenium tetra (perfluorophenyl) borate.

Also, examples of suitable A ^{d −} are as disclosed in US Pat. No. 5,447,895,
Also includes diboron compounds. This specification refers to this patent.

In one embodiment, activation using an ionizable ionic compound that contains no active protons but is capable of producing bulky ligand metallocene catalyzed cations and their non-coordinating anions. Methods are also contemplated. This method is EP-A-0
426637, EP-A-0573403 and US Pat. No. 5,387,568. This specification refers to all of these.

Other activators include those described in PCT publication WO 98/07515, such as tris (2,2 ′, 2 ″ -nonafluorobiphenyl) fluoroaluminate. Also, combinations of activators, such as alumoxane and ionizing activators, are contemplated by the present invention, eg, EP-B1-0573120, PCT patent applications WO 94/07928 and WO 95/14044. And US Pat. Nos. 5,153,157 and 5,453,410.
See issue. This specification refers to these.

Other suitable activators are disclosed in WO 98/09996 (which is hereby incorporated by reference), the invention comprising perchlorates, periodates and iodic acid. The activation of bulky ligand metallocene catalyst compounds with salts (including their hydrates) is described. WO98 / 30602 and WO98 / 30603 (which are referenced herein) disclose lithium (2,2'-bisphenylditrimethylsilicate) .4T as an activator for bulky ligand metallocene catalyst compounds.
It describes the use of HF. WO 99/18135 (referenced herein) describes the use of organic-boron-aluminum activators. EP-B1
-0781299 describes the use of silylium salts in combination with a non-coordinating compatible anion. Also, radiation (EP-B referred to in this specification)
1-0615981), methods of activation such as using electrochemical oxidation, etc., also include bulky coordination capable of polymerizing olefins with neutral bulky ligand metallocene catalyst compounds or precursors. It is intended as an activation method for the purpose of becoming a child metallocene cation. Other activators or methods for activating bulky ligand metallocene catalyst compounds are described, for example, in US Pat. Nos. 5,849,852;
859653 and 5869723 and WO98 / 32775, WO99
/ 42467 (dioctadecylmethylammonium-bis (tris (pentafluorophenyl) borane) benzimidazolide). This specification refers to these inventions.

Supports , Carriers and General Supporting Techniques The catalysts and / or activators described above may be incorporated into one of the support methods well known in the art or as described below to form a supported catalyst system. Can be used to mix with one or more carrier materials or carriers. For example, the catalyst and / or activator can be supported on, brought into contact with, deposited with, bound to or incorporated into, incorporated into, adsorbed on or absorbed by a carrier or carrier.

For the purposes of this patent specification, the term “carrier” or “carrier” is used interchangeably and is any support material, including inorganic or organic support materials, preferably porous support materials. Is. Examples of inorganic support materials include, but are not limited to, inorganic oxides and chlorides. Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports such as polystyrene divinylbenzene polyolefin or polymeric compounds, zeolites, talc, clay or any other organic or inorganic support material, or the like. Including a mixture of.

Preferred carriers are inorganic oxides, including Group 2, 3, 4, 5, 13 or 14 metal oxides. Preferred carriers include silica, alumina, silica-alumina, magnesium chloride and mixtures thereof. Other useful carriers are magnesia,
It includes titania, zirconia, montmorillonite (EP-B1-0511665), phyllosilicate and the like. Also, combinations of these support materials such as silica-chromium, silica-alumina, silica-titania and the like can be used.
Additional support materials can include the porous acrylic polymers described in EP-B1-0767184, which is incorporated herein by reference.

The carrier, most preferably the inorganic oxide, has a surface area in the range of about 10 to about 700 m ² / g, a pore volume in the range of about 0.1 to about 4.0 cc / g, and About 5
It is preferred to have an average particle size in the range of about 500 μm. More preferably, the surface area of the carrier is in the range of about 50 to about 500 m ² / g and the pore volume is about 0.
． 5 to about 3.5 cc / g, and the average particle size is about 10 to 200 μm. Most preferably, the surface area of the carrier is in the range of about 100 to about 400 m ² / g, the pore volume is about 0.8 to about 3.0 cc / g, and the average particle size is about 5-100 μm. Is. The average particle size of the carrier of the present invention is typically 10 to 1
000Å, preferably 50 to about 500Å, and most preferably 75 to about 350
Pore size in the range of Å.

Examples of supported bulky ligand metallocene catalyst systems are described in US Pat.
No. 808561, No. 4912075, No. 4925821, No. 4937217
No. 5,082,228, 5,238,892, 5,240,894, and 533.
No. 2706, No. 5346925, No. 5422325, No. 5466649,
No. 5,466,766, No. 5,468,702, No. 5,529,965, and No. 55,547.
04, 5629253, 5639835, 5625015, 5
No. 643847, No. 5665665, No. 5698487, No. 5714424.
No. 5723400, No. 5723402, No. 5731261, No. 575
No. 9940, No. 5767032, No. 5770664, No. 5846895 and No. 5939348, and U.S. Patent Application No. 2 filed on July 7, 1994.
No. 71598, No. 788736 filed on January 23, 1997, and P
CT Patent Applications 95/32995, WO95 / 14044, WO96 / 06187
And WO 97/02297 and EP-B1-0685494. This specification refers to these inventions.

There are various other methods in the art for supporting the polymerization catalyst. For example, bulky ligand metallocene catalyst compounds are described in US Pat. Nos. 5,473,202 and 5,770,752.
Polymer-bound ligands may be included as described in US Pat. No. 5,648,310, which is incorporated herein by reference. Can be spray dried. The support used with the bulky ligand metallocene catalyst system of the present invention is described in European Patent Application EP-A.
-0802203 (herein referring to this invention) or at least one substituent or leaving group can be functionalized according to US Pat. No. 5,688,880 (herein incorporated by reference). (Referring to this invention).

In another embodiment, an antistatic agent or surface modification used in the manufacture of a supported catalyst system as described in PCT patent application WO 96/11960, which is herein incorporated by reference. Agents can be used. The catalyst system can be prepared in the presence of an olefin, for example 1-hexene.

In another embodiment, US patent application Ser. No. 09/1 filed June 10, 1998.
As described in 13216, catalysts include metal esters of carboxylates such as aluminum monostearate, aluminum distearate and aluminum tristearate, aluminum octanoate, aluminum oleate and aluminum cyclohexylbutyrate. It can be mixed with aluminum carboxylate.

Preferred methods for making supported bulky ligand metallocene catalyst systems are described below and filed on June 24, 1994, US Patent Application No. 265533 and June 24, 1994. No. 265532 and PCT patent application 9
6/00245 and WO 96/00243 (both published January 4, 1996). This specification refers to these inventions. In this preferred method, the catalyst compound is slurried in a liquid to form a catalyst solution or emulsion. Separate solutions containing the active agent and the liquid are made. The liquid can be any solvent or other liquid capable of making a solution that is compatible with the catalyst compound and / or activator and the like. In the most preferred embodiment, the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene. In the catalyst compound solution and the activator solution, the total volume of the bulky ligand metallocene catalyst compound solution and the activator solution or the bulky ligand metallocene catalyst compound and the activator solution is 4 times the pore volume of the porous carrier.
2 times or less, preferably 3 times or less, more preferably 2 times or less (the preferred range is 1.
In the range of 1 to 3.5 times, and most preferably 1.2 to 3 times). Is added to the solution.

Procedures for measuring the total pore volume of porous supports are well known in the art. Details of one of these procedures can be found in Experimental Methods in Catalytic Research (1968).
Annual Academic Press (see especially pages 67-96), Volume 1. This preferred procedure involves the use of classical BET equipment for nitrogen absorption. An alternative method known in the art is Analytical Chemistry 332-334, Vol. 28, No.
.3 "Total Porosity and Particle Density of Fluidized Catalysts by Liquid Titration" (March 1956).

[0067] The addition of the diene low concentrations of diene, the polymerization process of the present invention to improve the processability of the product, is preferably used for the gas phase polymerization process. Dienes, as known in the art, belong to the class of unsaturated hydrocarbons containing two carbon-carbon double bonds and each double bond is a CCC unit, a CC-CC unit or a CC- (CXY). _n- C
It is classified as cumulative, conjugated or isolated depending on whether it constitutes a C unit. In the present invention, low levels of dienes are introduced into the reactor to control and improve the melt index ratio of the polymer product independent of the melt index and density of the product, without gel formation. It appears to control long chain branching independently.

Any diene or mixture of dienes containing sufficient carbon atoms to incorporate long chain branching can be utilized in the method of the present invention. Preferably the diene is
It does not act as a poison to the catalyst or undergo cyclization which would prevent further chain growth. The diene utilized can be aliphatic, cycloaliphatic or aromatic,
And it is preferably aliphatic. More preferably, the dienes are aliphatic linear dienes containing non-conjugated double bonds, most preferably isolated double bonds. Most preferably, both of these double bonds of the dienes are capable of reacting and intercalating with the growing polymer chain to promote long chain branching.

For use in gas phase polymerization processes, the vapor pressure and boiling point of the diene must be sufficient to allow adequate dispersion in the reactor. If the diene doesn't disperse well,
It will result in gel formation, and purging of downstream products will also be problematic. Moreover, the dienes most suitable for use in the gas phase process of the present invention should have no odor. Thus, the diene is 5 to 12 carbon atoms, preferably 6 to
It is preferably an aliphatic linear or branched diene having 10 carbon atoms.
Examples of suitable dienes useful in the method of the invention are 1,4-hexadiene, 1,5
-Hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene and mixtures thereof. In a particularly preferred embodiment, the dienes are α, ω-dienes or contain double bonds at both ends. More preferably, the diene comprises 1,7-octadiene, 1,8-nonadiene or 1,9-decadiene, and most preferably 1,7-octadiene.

Any amount of the diene or mixture of dienes effective to produce LCB and / or enhance its shear thinning in the polymeric product catalyzed by the bulky ligand metallocene can be utilized. Preferably, in the gas phase polymerization process, the amount of diene utilized is from 1 to about 1000 ppm of diene based on the total weight of monomer feed to the process, or the total monomer feed. About 0.255 to about 255 pp based on mol
It is a m diene. By total weight or moles of monomer feed is meant the weight or moles of monomer utilized, eg, ethylene and does not include the weight or moles of comonomer.
More preferably, the amount of diene utilized is from about 10 to about 900 ppm by weight or from about 2.55 to about 229.5 ppm moles, more preferably from about 15 to about 8
50 ppm weight or about 3.82 to about 216.4 ppm moles, more preferably about 20 to about 800 ppm weight or about 5.1 to about 203.6 ppm moles, more preferably about 50 to about 750 ppm weight. Or about 12.7 to about 191 pp
mmol and more preferably about 100 to about 700 ppm weight or about 25.5.
To about 178.2 ppm mol, and most preferably about 150 to about 650.
ppm weight or about 38.2 to about 165.5 ppm mol of diene.

Polymerization Method The addition of dienes to control the processability of the polymer product can be utilized in any prepolymerization and / or polymerization method. The polymerization can be carried out in liquid, gas phase, slurry phase or high pressure processes or combinations thereof. Preferred is the gas phase or slurry phase polymerization of one or more olefins, at least one of which is ethylene or propylene. Most preferably, the polymerization is conducted by a gas phase polymerization method.

In the process of the present invention, the diene must be properly dispersed in the reactor.
Proper dispersion of the diene reduces the likelihood of gel formation and allows for uniform incorporation of the LCB and allows the MIR of the polymer product to be controlled independent of its MI and density. For example, for the same MI and density, MIR was found to increase by increasing the diene level, and the product had similar melt strength to the product made without the addition of dienes. Thus, without wishing to be bound by theory, the addition of the diene enhances the shear thinning properties sufficiently and does not significantly reduce the melt strength of the polymer product, so that the LCB looks like a star branch. It seems to cause.

Preferably the diene is dissolved in a suitable solvent such as hexane or isopentane to form a diene solution. This diene solution is then introduced into the reactor. More preferably, the introduction of the diene and / or diene solution into the reactor is independently controlled and can be introduced into the reactor by any suitable means as known in the art. By controlling the reactor diene level, the LCB present in the polymer product catalyzed by the bulky ligand metallocene can be controlled. Most preferably, and in order to achieve maximum diene dispersion, a controlled amount of diene or diene solution is added to the comonomer, inducible condensing agent (ICA) feed and / or prior to entering the reactor. Or added first to other feeds known in the art.

In one embodiment, the method of this invention comprises 2 to 30 carbon atoms, preferably 2
Directed to utilizing low levels of dienes in polymerization or copolymerization reactions, including the polymerization of one or more olefin monomers having -12 carbon atoms, and most preferably 2-8 carbon atoms. . The present invention includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene, 3-methyl-1-pentene, 3,5,5-. It is particularly suitable for the polymerization of two or more olefin monomers of trimethyl-1-hexene as well as cyclic olefins or combinations thereof. Other monomers useful in the polymerization process of the present invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers and cyclic olefins. including. Other monomers useful in the present invention include norbornene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl substituted styrene, ethylidene norbornene,
It can include dicyclopentadiene and cyclopentene.

In a preferred embodiment, the process of the present invention is directed to utilizing low levels of dienes to produce copolymers of ethylene. In this case, ethylene and 4-15
Carbon atoms, preferably 4-12 carbon atoms, and most preferably 4-8.
Polymerized with a comonomer having at least one α-olefin having 4 carbon atoms.

In another embodiment of the method of the present invention, low levels of dienes are utilized to form terpolymers when ethylene or propylene are polymerized with at least two different copolymers.

In one embodiment, the present invention is directed to polymerizing polyenes alone or with one or more other monomers including ethylene and / or other olefins having 4 to 12 carbon atoms. It relates to utilizing low levels of dienes in the polymerization process. Polypropylene polymers are described in US Pat. Nos. 5,296,434 and 5,278,264 (
The present specification may refer to these inventions) and may be prepared using, inter alia, bridged bulky ligand metallocene catalysts.

In a preferred embodiment, ethylene and an optional comonomer and diene compound are
The effective amount of bulky ligand metallocene catalyst is contacted as described above at a temperature and pressure sufficient to initiate polymerization. Typically in gas phase polymerization processes, continuous cycles are used. Here, in a part of the cycle of the reactor system, a circulating gas stream (otherwise known as a recycle stream or a fluid medium) is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor. Generally, in gas fluidized bed processes for producing polymers, a gas stream containing one or more monomers is continuously circulated through the fluidized bed in the presence of a catalyst under reactive conditions. It The gas stream is withdrawn from the fluidized bed and recycled back into the reactor. At the same time, the polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer (see, eg, US Pat. No. 45
No. 43399, No. 4588790, No. 5028670, No. 5317036, No. 535249, No. 5405922, No. 5436304, No. 5453.
See 471, 5462999, 5616661 and 5668228. This specification refers to these disclosures).

The pressure of the reactor in the gas phase process is from about 30 ° C. to about 120 ° C., preferably about 60.
C. to 115.degree. C., more preferably in the range of about 70.degree. C. to 110.degree. C., and most preferably in the range of about 70.degree. C. to about 95.degree.

The pressure of the reactor in the gas phase process is from about 100 psig (690 kPa) to about 5
00 psig (3448 kPa), preferably about 200 psig (1379 kP)
a) to about 400 psig (2759 kPa), more preferably about 250.
It can be changed in the range of psig (1724 kPa) to about 350 psig (2414 kPa).

The productivity of the catalyst or catalyst system is influenced by the partial pressure of the main monomers. The preferred mol% of the main monomer (ethylene or propylene, preferably ethylene) is 2
5 to 90 mol% and the partial pressure of the monomer is about 75 psia (517 kPa).
) To about 300 psia (2069 kPa), which are typical conditions for gas phase polymerization processes.

In a preferred embodiment, the reactor utilized in the process of the present invention is 50 reactors per hour.
0 lbs polymer (227 kg / hr) to 200,000 lbs / hr (90,9)
00 kg / hr) or higher polymer, preferably 1000 lbs / hr (4
55 kg / hr) or more, more preferably 10,000 lbs / hr (4540k)
g / hr) or more, more preferably 25,000 lbs / hr (11,300 kg)
/ Hr) or more, more preferably 35,000 lbs / hr (15,900 kg /
hr) or more, more preferably 50,000 lbs / hr (22,700 kg)
/ Hr) or more, and most preferably 65,000 lbs / hr (29,000 k
Polymers of g / hr) to 100,000 lbs / hr (45,500 kg / hr) or more can be produced.

Other gas phase processes contemplated by the process of the present invention include continuous or multi-stage polymerization processes. Also, the vapor phase method contemplated by the present invention is described in US Pat. No. 5,627,724.
No. 2, 5656818 and 5677375 and European patent application EP-
A-0794200, EP-B1-0649992, EP-A-0802220
And EP-B-0634421. This specification refers to these disclosures.

A preferred method of the present invention is that the method is in the presence of a bulky ligand metallocene catalyst system and triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylaluminum and diethylaluminum chloride, dibutylzinc, etc. The point is to operate in the substantial absence or absence of any scavengers such as. This preferred method is described in PCT patent application WO 96 /
08520 and US Pat. Nos. 5,712,352 and 5,763,543. This specification refers to these disclosures.

In one embodiment of the present invention, olefins, preferably C2-C30 olefins or α-olefins, preferably ethylene or propylene or combinations thereof, are prepolymerized prior to the main polymerization. The prepolymerization can be carried out batchwise or continuously at high pressure in the gas, liquid or slurry phase. The prepolymerization can be carried out with any olefin monomer or combination and / or in the presence of any molecular weight control agent such as hydrogen. For an example of a prepolymerization procedure, see US Pat. No. 474.
8211, 4789359, 4923833, 4918825,
Nos. 5283278 and 5705578 and European patent application EP-B-02.
See 79863 as well as PCT patent application WO 97/44371. This specification refers to these inventions.

Optionally, the unreacted dienes are treated, for example, by purging with an inert gas such as nitrogen, purging with an inert gas and steam or oxygen, heating under vacuum or a combination thereof. Can be removed from the polymer product by methods well known in the art.

Polymer Products The polymers produced by the process of the present invention can be used in a wide variety of products and end use applications and include linear low density polyethylene, elastomers, plastomers, high density polyethylene, Includes medium density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers.

The polymers of the present invention, preferably ethylene-based polymers, are ASTM-D-
0.01dg / min or less to 1000dg when measured by 1238-E
/ Min, more preferably about 0.01 dg / min or less to about 100 dg / min
, More preferably about 0.1 dg / min to about 50 dg / min, and most preferably about 0.1 dg / min to about 10 dg / min in melt index (MI) or (I ₂ ).

The polymer of the present invention in a preferred embodiment preferably has a melt index ratio (I) of 10 or higher, more preferably 30 or higher, even more preferably 40 or higher, even more preferably 50 or higher, and most preferably 65 or higher. ₂₁ / I ₂ ) (I ₂₁ is A
STM-D-1238-F). In one specific example,
The polymers of the present invention can have a narrow molecular weight distribution and a broad composition distribution or, conversely, a broad molecular weight distribution and a narrow composition distribution, and can be the polymers described in US Pat. No. 5,798,427. This specification refers to this invention.

The polymers of the present invention, typically ethylene-based polymers, have a concentration of 0.86 g / c.
c to 0.97 g / cc, preferably 0.88 g / cc to 0.965 g /
cc, more preferably 0.900 g / cc to 0.96 g / cc, more preferably 0.905 g / cc to 0.95 g / cc, still more preferably 0.910 g / cc to. It has a density in the range of 0.940 g / cc, and most preferably 0.915 g / cc or higher, preferably 0.920 g / cc or higher, and most preferably 0.925 g / cc or higher. Density is measured according to ASTM-1505.

In another embodiment, the polymer produced therein has a viscosity of 7 cN or higher, preferably 9 cN or higher, more preferably 10 cN or higher, as measured by an Instron capillary flowmeter coupled with a Goettfert Rheotens melt strength apparatus. Above, and more preferably 12c
It has a melt strength of N or more. The polymer melt strands extruded from the capillary die are gripped between counter rotating wheels on this device. Winding speed is 24mm / s
ec ² increases at a constant acceleration, which is the acceleration programmer (form 45917).
, 12 settings). The maximum tensile force (expressed in cN) achieved before the strand breaks or before the strand begins to exhibit stretching resonance is determined as the melt strength. The flowmeter temperature is set to 190 ° C. The capillary die has a length of 1 inch (2.54 cm) and a diameter of 0.06 inch (0.15 cm). The polymer melt is extruded from the die at a piston speed of 3 inches / minute (7.62 cm / minute). The distance between the die exit and the wheel contact point is 3.94.
Should be inches (100 mm).

The polymers produced by the method of the present invention are typically 1 to about 40, preferably 1.5 to about 15, more preferably about 2 to about 10, most preferably 2.0 to. It has a weight average molecular weight / number average molecular weight ( _Mw / _Mn ) molecular weight distribution of about 8.

Also, the polymers of the present invention typically have a narrow composition distribution as measured by the Composition Distribution Width Index (CDBI). The details of measuring the CDBI of a copolymer are well known to those skilled in the art. See, for example, PCT patent application WO 93/03093 published Feb. 18, 1993. This specification refers to this disclosure.

The polymers of the invention in one embodiment generally range from 50% to 100%,
C in the range of preferably 99%, preferably 55% to 85%, and more preferably 60% to 80%, more preferably 60% or more, even more preferably 65% or more.
It has a DBI value.

In another embodiment, the polymers produced by the method of the present invention have a CDBI value of 50% or less, more preferably 40% or less, most preferably 30% or less.

In yet another embodiment, propylene-based polymers are produced by the method of the present invention. These polymers include atactic polypropylene, isotactic polypropylene, hemiisotactic and syndiotactic polypropylene. Other propylene polymers include block or impact copolymers of propylene. These types of propylene polymers are well known in the art. For example, U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, and 503.
See 6034 and 5459117. This specification refers to these disclosures.

The polymers of the present invention can be blended and / or coextruded with any other polymer. Examples of other polymers include linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, polypropylene, etc. made with conventional Ziegler-Natta and / or bulky ligand metallocene catalysts. However, it is not limited to these.

The polymers produced by the method of the present invention and their blends are
It is useful for sheet and fiber extrusion and coextrusion as well as molding operations such as blow molding, injection molding and rotary molding. The film, in food contact and non-food contact applications, shrink film, wrap, uniaxially stretched film, sealing film, stretched film, snack packaging, heavy bags, food bags, heated and frozen food packaging, pharmaceutical packaging, industrial liners, Included are blown or cast films molded by coextrusion or lamination useful as membranes and the like. A particularly preferred method for casting the polymer into a film involves extrusion or coextrusion on a blown film or cast film line. Fibers include operations of melt spinning, solution spinning and melt blown fibers for use in woven or non-woven form to make filters, diaper fabrics, medical garments, ground sheets and the like. Extrudates include medical tubing, wire and cable coatings, geomembranes and pond liners. Molded articles include single and multi-layered structures in the form of bottles, tanks, large hollow articles, rigid food containers and toys.

In another embodiment, the film produced by the method of the present invention comprises a slip agent, an antiblocking agent, an antioxidant, a pigment, a filler, an antifog agent, a UV stabilizer, an antistatic agent, a polymer. Additives such as processing aids, neutralizing agents, lubricants, surfactants, dyes and nucleating agents can also be included. Preferred additives are silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearate, calcium stearate, zinc stearate, talc, BaSO ₄ , diatomaceous earth, wax, carbon black, flame retardant additives, Includes low molecular weight resins, hydrocarbon resins, glass beads and the like. Additives are typically effective amounts well known in the art, such as 0.00
It can be present at 1% to 10% by weight.

[0100]

【Example】

To better understand the invention, including the typical advantages of the invention, the following examples are provided for the polymerization process and the results of the polymerization.

These examples were carried out in a continuous gas phase fluidized bed reactor. Ten polyethylene polymer products were produced at six different diene levels. The experimental conditions for this method averaged over a period of time at steady state are shown in Table 1 and the polymer product characteristics for each experiment are shown in Table 2. The data obtained from Comparative Example 1b, which is further processed into a film, and from the four polymer products are shown in Tables 3-6. The amount of diene is reported in ppm based on total monomer feed weight as described above.

Comparative Example 1 (2MI / 0.920D) Prior to introducing the diene into the reactor, a control experiment for the condition of 2MI / 0.920D was conducted to establish a baseline. After a stable run for bed removal (BTO) of 7.2 and 1 box of product collected, the tetraethylaluminum (TEAL) pump in the reactor was flushed with hexane. As used herein, BTO (Production Weight / Bed Weight) may include polymer that is continuously produced and withdrawn from the reactor over a period of time at which time the reactor is present. It means the amount replaced by the amount of the product (in this example, about 300 lbs (136 kg))
. Further, as used herein, a box of product refers to about 600 to
It refers to 800 pounds of polymer. The reactor was shut down at 12.3 BTO for product discharge stuffing to flush the balance TEAL into the reactor and due to some bed weight control issues. The catalyst dimethylsilylbis (tetrahydroindenyl) zirconium dichloride was temporarily cut to stabilize the reactor. Catalyst productivity is 2.23MI / 0.918D
The average was 3.650 g / g (where g / g is g of polymer / g of catalyst).

Comparative Example 1b (Second Start) After the operation was stopped, the reactor was restarted under the condition of 2MI / 0.920D. There were no reactor continuity issues, and the reactor remained at this condition for 5.8 BTO. The productivity of the catalyst was 3366 g / g on average.

Example 2 (2MI / 0.920D, 50 ppm diene) After stabilization under a controlled condition of 2MI / 0.920D, the reactor was 1% 1,7.
-A hexene solution of octadiene was transferred to a 50 ppm diene condition by starting using a TEAL pump. The diene controlled flow ratio to ethylene feed rate to maintain a weight ratio of 50 ppm diene to ethylene.
The hydrogen concentration and the flow rate ratio of hexene were kept constant under the 2MI control condition. 5 reactors
Lined out at 1.5 MI with 0 ppm diene and collected 1 box of product. The 50 ppm condition of dienes was carried out with an average productivity of 4130 g / g for 5.6 BTO.

Example 3 (2MI / 0.920D, 100 ppm diene) After completion of the 50 ppm condition (Example 2), the reactor was brought to 100 ppm by increasing the flow rate of the diene while keeping the hydrogen and hexene concentrations constant. Was transferred to the condition. The bed weight still fluctuated due to product discharge packing, so the reactor was shut down at 2.5 BTO. Catalyst productivity was about 3850 g / g before shutdown.

Comparative Example 1c (Third Start) The reactor was restarted at controlled conditions (2MI / 0.920D) and tested for 4.8 BTO without any skin temperature activation or chip formation. Catalyst productivity is 33
It was 00-3600 g / g. The product MIR is 1.93 MI / 0.9178.
It was 34 in D.

Example 4 (1 MI / 0.920D, 150 ppm diene) After stabilizing the reactor at 2MI / 0.920D conditions, the reactor was started with diene flow and the hydrogen concentration increased from 950 to 1000 ppm. It was transferred to the condition of 150 ppm. The catalyst productivity was about 3750 g / g.
One box of product was collected at 50.9 MIR at 0.95 MI / 0.9181D.

Example 5 (0.75MI / 0.920D, 150ppm Diene) Reactor hydrogen was reduced to 950ppm to obtain a product of 0.75MI at a diene level of 150ppm. There was no problem of continuity. The average catalyst productivity was 3650 g / g. 0.82 MI / 0.917 in 1 box of product
Collected at 54.73 MIR at 9D.

Example 6 (1 MI / 0.920D, 250 ppm diene) The reactor was converted to 250 ppm diene conditions by increasing the diene feed rate. Increase the concentration of the diene solution to 8% and increase the pump speed to 200-400
Maintained at cc / hr. The hydrogen level was increased from 950 ppm to 1075 ppm to compensate for the increased diene level. The reactor was at this condition for 4.47 BTO. And one box of product 1.01MI / 0.9200D
At 55.53 MIR at.

Example 7 (0.75 MI / 0.920 D, 250 ppm diene) To obtain a product of 0.75 MI with a hydrogen concentration of 250 ppm diene 1075
Reduced from ppm to 1000 ppm. The catalyst productivity was 3400 g / g on average. One box of product at 60.03M at 0.86MI / 0.9205D
Collected by IR.

Example 8 (0.75 MI / 0.920 D, 400 ppm diene) A reactor was prepared by increasing the diene flow with 1000 ppm hydrogen to 40
It was transferred to 0 ppm condition. After the MI drifted down to 0.56, hydrogen was raised to 1100 ppm. Then MI started to return to 0.71. However, the diene solution was exhausted in 2 hours. MI jumped from 0.71 to 1.41 and eventually to 1.67 with a rapid response when the diene was gone. When the diene solution was returned to the line, the MI was 1075p
It was settled to 0.75 g / 10 min with pm of hydrogen. This appearance indicates that dienes are able to bind chains and reduce MI. Average catalyst productivity is 3850 g / g, 1 box product 0.75 MI / 0.92
Collected at 74.71 MIR at 06D.

Example 9 (0.75 MI / 0.920D, 600 ppm diene) The reactor was transferred from 400 ppm to 600 ppm diene conditions by increasing the diene flow and raising the hydrogen level to 1200 ppm. The hydrogen level was further raised to 1300 ppm to reach the target of 0.75 MI. The average catalyst productivity was 3400 g / g. 0.80 MI / 0 for 1 box of product
． Collected at 82.09 MIR at 920D.

Example 10 (1MI / 0.920D, 600 ppm diene) The hydrogen level was further increased to 1400 ppm to reach the targeted 1MI product.
Due to the slow response of MI to hydrogen, the hydrogen level was raised to 1500 ppm. This clearly exceeded hydrogen levels, so the MI rose to 1.49 at some point and eventually settled around 1 MI with 1350 ppm hydrogen. The average catalyst productivity was 3800 g / g. 1 box of product
Collected at 75.12 MIR at 12 MI / 0.9218D.

Reactor Continuity Reactor continuity was reasonably good throughout the examples. There was no exclusion of skin temperature and no significant sheeting. Some small chips occasionally appeared, but in low amounts (0.1-0.2% per product) and did not cause major continuity breaks. There were two outages in the early part of the experiment, but none of them were directly involved in the diene infusion. The first stop occurred before the diene condition and the balance tetraethylaluminum (
Caused by flashing out TEAL) and by floor weight control issues. The second stop occurred at the 100 ppm diene condition, which is likely caused by bed weight control issues. The majority of condition (7) was completed after the third start, and the experiment was completed by a scheduled shutdown. Upon completion of the experiment, the reactor and cooler were opened for inspection and found to be clean. Some coating formed on the wall of the swollen part but was easily blown off.

Catalyst productivity The catalyst productivity was 3500 g / g to 4000 g / g and there was no significant activity loss due to dienes. In fact, all the diene experimental activities were higher than the control experiments at the beginning of the diene experiment. This may have occurred due to differences in catalyst batch.

[0116] Gel Gel formation if you try particular use of polymers for the production of films, is a major concern. In the above example, the diene solution was dispersed in the hexene feed before it was placed in the reactor to achieve good dispersibility. Special care was taken during the experiment to avoid entering the gel area very quickly. This is because it can take a long time for the gel to disappear. Gel tapes were run under each condition to help determine the next diene level. As shown in Table 2, gel levels were baseline up to 400 ppm diene. At 600 ppm, some partially melted gel particles appeared in the gel tape. However, after compounding the granules and pelletizing with a twin screw extruder, the tape was virtually gel free. The partially melted gel is probably caused by the heterogeneous dispersion of dienes in the gas phase, since even at the 600 ppm level there is only about 0.1 dienes per chain. This could be minimized by good diene dispersion.

Purging and Odor Problems The diene levels during the experiment were monitored for any exposure and / or odor problems. Compared to aromatic dienes (such as ethylidene norbornene (ENB)), the aliphatic dienes used had no noticeable odor during processing. Furthermore, using the conventional gas phase reactor purging run, the polymer product had no significant odor and no diene was detected in the headspace gas chromatographic analysis of the 600 ppm diene experimental particulate product. Was not done.

[0118]Product processability   Twin screw with standard additive container well known in the art for eight products
Pelletized by extruder. However, the MI of pellets is the MI of granules.
Higher, the difference increased with increasing diene levels. This difference is grain
When measuring body MI, the lack of homogeneity in the melt indexer causes
It must have been awakened. MI of pellets can be used to characterize film products.
used. Table 3 lists the results of the pelletized diene product characteristics.
. Increasing the diene level from 0 to 600 ppm, even if the number average molecular weight (M _n ) Is almost the same or slightly less, the light as is known in the art.
Weight measured by scattering and viscometer detectors (M_W) And Z average molecular weight (M_Z ) Was significantly increased. Without wishing to be limited by theory, light scattering and viscosity
Since the detector of the densitometer is more sensitive to the high MW fraction, the diene remixing is largely
Minutes seem to have occurred in the higher MW part.

The pellet product from the representative examples (1b, 5, 7, 8, 9) was further blown into 1 mil film using a blown film line. Controls of the same MI / density produced by the same catalyst in an industrial reactor were run under the same conditions. Table 4 compares the processability of diene products at standard extrusion rates (118 lb / hr or 85.3 kg / hr) on a pilot scale blown film line. At the same MI and density (1MI / 0.920D), the processability of the product improves with increasing diene levels. Comparing the 400 ppm diene product with the standard, the motor load was reduced from 51.6% to 41.7%, the die press was reduced from 3460 to 2710 psi (23856-18685 kPa) and the melt temperature was 378 °. F (192.2 ° C) to 369 ° F (187.2 ° C)
) Has fallen to. Specific extrusion rates range from 11.79 to 13.96 lb / hr (5
． 35 to 6.33 kg / hr).

Table 5 compares the maximum extrusion rates of different diene products. The extruder was not powder limited, so its maximum speed was primarily determined by bubble stability.
At maximum output, the melting temperature and pressure were 385 ° F (19 ° C) for the control.
6 ° C.) and 4440 psig (30613 kPa) to 374 ° F. (190 ° C.) and 2340 psig (15918 kPa) for the 400 ppm diene sample.
It showed a significant shearing property with increasing diene level. 400 pp
294 lb / hr (133 kg / hr) for the standard at a diene level of m
A maximum production of 323 lb / hr (147 kg / hr) is obtained in comparison with.

Film Properties Table 6 compares the product properties of films produced at an extrusion rate of 188 lb / hr (85.3 kg / hr). The best balance between processability and film properties is
It is believed to be achieved with about 250 ppm to about 400 ppm diene. 250 pp
In m-diene, processability is increased by 20-25% as measured by maximum speed, specific extrusion rate (1b / hp-hr), motor load, head pressure and melt temperature. The overall film properties of the 250 ppm diene product were similar to the no diene control. The film hardness is basically the same as the control (MD / TD module, MD / TD yield). The film strength (MD / TD tension, breaking force / breaking energy) and film appearance (haze and gloss) are also similar to the control.
The dart impact of the 250 ppm diene product is slightly better than the control (10%
). The MD and TD tear of the 250 ppm diene product somehow protects against the control. By varying the diene level, the processability of the product can be significantly improved without including most of the film properties.

Conclusion By using small amounts of dienes, the shear thinning properties of bulky ligand metallocene-catalyzed polymer products can be 50-100 without significant impact on process continuity or catalyst productivity. % Improved. This method provides a novel means of controlling the product LCB by controlling the reactor diene level and is utilized to widen the product window of existing bulky ligand metallocene catalysts. be able to. The method of the present invention extends the control of product properties from the conventional two dimensions (MI and density) to three dimensions (MI, density and LCB). For example, at the same MI and density, it was found that MIR was increased by increasing diene levels.
At 250-600 ppm diene, the MIR is increased by 50-100% compared to the product made without the diene. For example, the MIR of the 1MI / 0.920D product increases from 38.2 without dienes to 63.2 with 400 ppm (wt) dienes. The processability of the product is improved by increasing the diene level, as measured by the specific extrusion rate, pressure drop and melt temperature. The melt strength of the product is similar to the product produced without the addition of dienes. Most film properties (hardness, toughness and dart impact) are similar to the control, and MD / TD tear is defensive against the control.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

Although the present invention has been described and illustrated with reference to particular embodiments, those skilled in the art will appreciate that the invention is susceptible to modifications that are not necessarily illustrated herein. Ah For example, one or more dienes can be added and / or one or more bulky ligand metallocene-type catalyst compounds can be utilized. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

[Procedure amendment]

[Submission date] January 8, 2003 (2003.1.8)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Contents of correction]

Title: Catalyst system, process for its production and its use in polymerization processes

─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA15 AA88 AF16 BC01 BC07                 4J011 AA05 BB01                 4J100 AA02P AS11Q CA04 DA04                       DA12 DA42 FA10 FA39                 4J128 AA01 AB00 AB01 AC28 AD06                       AD13 AD16 AD17 AD18 BA01A                       BA01B BB01A BB01B BC12B                       BC13B BC15B BC25A BC25B                       CA16C CA27C CA28C CA29C                       EA01 EB02 EB16 EC02 EC04                       GA05 GA06 GA07 GA08 GA09                       GB01

Claims (10)

[Claims] 1. A method of polymerizing an ethylene monomer and optionally one or more comonomers, comprising introducing an amount of a diene into a polymerization reactor, wherein the amount of diene is ethylene monomer. A polymerization process wherein the amount is less than 1000 ppm based on the total weight of the monomers or less than 255 ppm based on the total moles of ethylene monomer. 2. An olefin polymerization process for independently controlling the melt index ratio of a polymer product comprising introducing an amount of a diene into a polymerization reactor, wherein a diene feed amount is polymerized. 1000ppm based on total weight of monomer
Less than 255 ppm based on the total moles of diene or polymerized monomers. 3. A process for olefin polymerization for producing polyethylene from an ethylene monomer and optionally one or more comonomers, comprising introducing an amount of a diene into a polymerization reactor. , The amount of diene supplied is 10 based on the total weight of the monomers.
An olefin polymerization process which is less than 255 ppm based on total moles of diene or monomer less than 00 ppm, and whose diene feed rate is independently controlled. 4. The diene is first introduced into the monomer feed, the inducing condensing agent (ICA) feed or another feed before being introduced into the polymerization reactor.
The method described in any one of. 5. The method according to claim 1, wherein the diene is an aliphatic diene containing a non-conjugated double bond. 6. The process according to claim 1, wherein the polymerization takes place in a gas phase reactor in the presence of a catalyst system comprising a bulky ligand metallocene polymerization catalyst. 7. The catalyst system comprises a crosslinked bulky ligand metallocene polymerization catalyst.
The method according to claim 1. 8. A process according to claim 1, wherein the diene feed comprises linear or branched aliphatic dienes having 5 to 12 carbon atoms. 9. The aliphatic diene is 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene,
4. The method according to any one of claims 1 to 3, selected from the group consisting of 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene and combinations thereof. 10. Introducing an amount of a diene into the polymerization reactor, wherein the amount of diene is less than 1000 ppm based on the total weight of monomers polymerized or the total moles of monomers polymerized. A film or injection molded article consisting of a polymer produced by a polymerization process which is less than 255 ppm based on.