CZ20012224A3 - Catalyst mixture for polymerization of olefins, polymerization process and polymer produced in such a manner - Google Patents

Abstract

This invention relates to an olefin polymerization catalyst system comprising at least one activator and one of: a) at least two transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, as described below as represented by formula (I), (II), (III) or (IV); b) the product of the combination of an activator and a transition metal catalyst based on bidentate ligands containing pyridine or quinolines moieties, such as those described as represented by formula (III) or (IV), that has been allowed to react prior to the introduction into the reactor, preferably for at least 15 minutes, and/or c) the product of combination of an additive and a transition metal catalyst based on bidentate ligands containing pyridine or quinoline moieties, such as those described below as represented by formula (I) or (II). This invention further relates to a polymer produced therefrom, particularly to unique polyethylene resins, more preferably bimodal high density polyethylene resins produced by this invention.

Description

Technical field

The present invention relates to olefin polymerization catalyst systems comprising activating agents and catalysts based on transition metal compounds including bidentate ligands containing pyridine or quinoline groups and mixtures thereof, polymerization processes using such catalyst systems and polymers produced by said processes.

BACKGROUND OF THE INVENTION

The intensive commercial use of metallocene catalysts for the production of polyolefins has led to increased interest in the development of non-metallocene catalysts that could be used in homogeneous catalysis. This is more than just an academic interest, as new, non-metallocene catalysts could provide an easier way to products that are already available, as well as the possibility to prepare such products and to implement production methods that exceed the capabilities of metallocene of catalysts. In addition, some non-metallocene ligands may be more economical because it is relatively easy to synthesize various substituted analogs of these ligands.

Therefore, there is a demand in the art for new olefin polymerization catalysts and unique ones

polymers which could be produced by such catalysts. Further, there is a need for catalyst systems that can be easily modified by adding an additive to a one-component catalyst to form a bimodal product. Further, there is a need for the development of catalysts that can produce both monodal and bimodal polyolefins. The present invention describes a unique group of catalysts, which can be used alone or in a mixture, to prepare unique polyolefins, in particular for the production of bimodal polyethylene.

In published international applications no

WO 96/23101, WO 97/02298, WO 96/33202 and Furhmann et al., Inorg. Chem. 35: 6742-6745 (1996), single site catalyst systems containing a nitrogen atom have been described. US Patent Application Serial No. 09 / 103,620, published as International Application No. WO 99/01460 on January 14, 1999, describes the use of transition metal compounds including bidentate ligands containing pyridine or quinoline groups and mixtures thereof with activating agents. in olefin polymerization. In particular, the formation of a gas phase mixture of [[1- (2-pyridyl) N1-methylethyl] [1'-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl with modified methylalumoxane has been described, this mixture enables the preparation of ethylene hexene polymers. In the development of the present invention, it has been found that U.S. Patent Application Serial No. 09 / 103,620 can be modified by directly adding an additive to produce bimodal products from mono-component catalysts.

«• ·

For the purpose of filing a patent application in the United States of America, the following reference materials are incorporated herein: United States Patent Nos. US 4,845,067; US 4,999,327; Japanese Patent No. JP 1126111; U.S. Patent No. 4,508,842 and British Patent Number

UK 1015054.

SUMMARY OF THE INVENTION

The present invention relates to an olefin polymerization catalyst system comprising at least one activating agent and one of the components selected from the group consisting of:

(a) at least two, transition metal containing bidentate ligand catalysts containing pyridine or quinoline groups as described below and whose chemical structure can be represented by formulas (I), (II), (III) or (IV) below;

b) mixing the activating agent and a transition metal-containing catalyst based on bidentate pyridines containing pyridine or quinoline groups, such as catalysts of formulas (III) or (IV), the activating agent being reacted with said catalyst before being injected into the reactor, preferably for at least 15 minutes, and / or

(c) the mixing product of the additive and the transition metal containing:

catalysts based on bidentate ligands containing pyridine or quinoline groups, such as catalysts of formulas I or II.

The present invention further relates to a polymer produced by these catalysts, in particular special polyethylene

polymers, preferably bimodal high density polyethylene polymers produced according to the present invention.

A. One aspect of the present invention is an olefin polymerization catalyst system comprising at least one activating agent and at least two transition metal containing bidentate ligand catalysts containing pyridine or quinoline groups. The activating agent may be any known catalyst activating agent and in one embodiment the activating agent is an aluminum alkyl, alumoxane, modified alumoxane, polyalumoxane, non-coordinating anion, Lewis acid, borane or mixture thereof.

There are many processes for the preparation of alumoxane and modified alumoxanes, and a specific example of such a process is disclosed in U.S. Pat.

US 4,665,208;

US 4,952,540;

US 5,091,352;

US

5,206,199;

US

5,204,419;

US

US

US

4,908,463;

US

4,968,827;

US

US

5,329,032;

US

US

5,235,081;

US

5,157,137;

US

5,103,031;

US

5,391,793;

US

5,391,529;

US

US

5,731,253 a

US

No. 5,731,451, published European patent applications EP-A-0 561 476, EP-A-0 594 218, European patent EP-B1-0 279 586 and published international application WO 94/10180, without limitation the above examples, all of the above-mentioned documents being incorporated herein by reference. Preferably, methylalumoxane, modified methylalumoxane, triisobutylalumoxane and polymethylalumoxane is used as activating agent according to the present invention.

Ionizing compounds (or non-coordinating anions) may contain active hydrogen, or any other cation that is associated but not coordinated or only weakly coordinated with the remaining ion of said ionizing compound. Such compounds and the like have been described in published European patent applications no

EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375

EP-A-0 426 637; EP-A-500 944; EP-A-0 277 003 a

EP-A-0 277 004, in patents

United States of America number

US 5,153,157; US 5,198,401;

US 5,066,741; US 5,206,197;

US 5,241,025; US 5,387,568;

US 5,384,299 and US 5,502,124 and in U.S. patent application Ser

No. 08 / 285,380, filed Aug. 3, 1994, the contents of all documents cited above being incorporated herein

A group of other activating agents of the States of America serial number as reference material.

in the published international application, the reagents disclosed in WO 98/07515, the activating agents of which are incorporated herein by reference in their entirety, exemplified by tris (2,2 ', 2' '- nonafluorobiphenyl) fluoroaluminate. The present invention also encompasses the use of compositions such as mixtures of alumoxanes and reagents such as those described in International Applications Nos. WO 94/07928 and WO 95/14044 and in U.S. Pat. Nos. 5,153,157 and ionizing activators disclosed in U.S. Pat.

US 5,453,410, the contents of all of which are incorporated herein by reference. Various methods of activation such as exposure to radiation and the like can also be used as the activating agent of the present invention.

• ·

In a preferred embodiment, the activating agent is selected from the group consisting of tris (2,2 ', 2' '-nonafluorobiphenyl) fluoroaluminate, alumoxane, triphenylbor, triethylbor, tri-n-butylammonium tetraethylborate, triarylborane, tri (n-butyl) ammonium tetrakis pentafluorophenyl) boron or trisperfluorophenylbor or diethylaluminum chloride.

In one embodiment of the present invention, the transition metal containing the bidentate ligand catalyst containing pyridine or quinoline groups is represented by the general formula (I):

((Z) XA _t (YJ)) _q MQ _n (I) where

M is a metal selected from Group 3 to Group 13 or from the group of lanthanides or actinoids of the Periodic Table of the Elements;

Q is a group bound to M and each Q is a monovalent, divalent or trivalent anion;

X and Y are groups attached to the group M and independently represent a carbon atom or a heteroatom, ✓

wherein at least one of X and Y is a heteroatom and preferably both X and Y are heteroatoms; Y is part of the heterocyclic ring J;

J is a heterocyclic ring containing from 2 to 50 atoms, which are not hydrogen atoms, preferably the ring contains from 2 to 30 carbon atoms;

Z is a group bound to X, wherein Z contains from 1 to 50 non-hydrogen atoms, preferably from 1 to 50 carbon atoms, or represents a silyl group, an alkylsilyl group such as a trialkylsilyl group; preferably Z represents a cyclic group containing from 3 to 50 atoms, preferably from 3 to 30 carbon atoms;

is the number 0 or 1, where t is 1

A is a bridging group bonded to at least one of X, Y or J, preferably to X and J;

q is 1 or 2;

is the oxidation state of the group M - q

1, if the group

Q is a monovalent anion;

is (oxidation state of group M - q) / 2, if group

Q is a divalent anion; or is (oxidation state of group M - q) / 3, if group

Q is a trivalent anion; typically an integer from 1 to 4, depending on the oxidation state of the M group.

In one embodiment of the present invention, when X is O or S, Z may or may not be present. In another embodiment of the present invention, when X is nitrogen or phosphorus, then Z is present. In an embodiment of the present invention, Z is preferably an aryl group, more preferably a substituted aryl group. In a preferred embodiment of the present invention, T represents an oxygen atom and is bonded to an alkyl, aryl or alkaryl group.

In another embodiment of the present invention, a catalyst comprising a transition metal compound is represented by the general formula (II):

((R ' _m Z) XA (Y' R '' _p )) _q MQ _n (II) where

M is a metal selected from group 3 to 13 of the Periodic Table of the Elements, preferably selected from the group of transition metals of group 4 to 12, preferably metal from the group of transition metals of group 4, 5 or 6, most preferably metal selected from group Group 4 transition metals such as titanium, zirconium or hafnium and most preferably zirconium;

Q are groups bound to M and each Q is a monovalent, divalent or trivalent anion; in a preferred embodiment, Q groups are independently selected from the group consisting of halogen atoms, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarbyl or phenoxy from 1 to 20 carbon atoms. Each of Q may also represent an amide group, a phosphide group, a sulfide group, a silylalkyl group, a diketone group, and a carboxylate group. Optionally, each of the Q groups may contain one or more heteroatoms, more preferably the Q group is selected from the group consisting of halides, alkyl groups and arylalkyl groups. Most preferably, each of Q is selected from the group consisting of arylalkyl groups such as a benzyl group;

X and Y are groups bound to M and are independently of one another a carbon atom or a heteroatom, wherein at least one of X and Y is a heteroatom and preferably both X and Y are heteroatoms, more preferably X and Y are independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, more preferably selected from the group consisting of nitrogen or phosphorus, and most preferably both X and Y are nitrogen; Y is part of a heterocyclic ring or cyclic system J;

J is a heterocyclic ring or a cyclic system containing from 2 to 30 carbon atoms, preferably from 2 to 7 carbon atoms, more preferably from 3 to 6 carbon atoms, and Most preferably 5 carbon atoms. Optionally, the heterocyclic ring J containing group Y may contain additional heteroatoms. The group J may be substituted by groups R '', which are independently selected from hydrogen or linear, branched, cyclic alkyl or alkenyl, alkynyl, alkoxy, aryl or aryloxy groups. Two or more R groups may also be linked to form a cyclic group such as an aliphatic or aromatic ring. The group R '' preferably represents a hydrogen atom or an aryl group, more preferably the group R '' represents a hydrogen atom. When R 'is an aryl group and Y is a nitrogen atom, a quinoline group is formed. The group R '' may optionally be bonded to group A;

Z is a hydrocarbyl group bonded to the group X, preferably Z is a hydrocarbyl group having from 1 to 50 atoms, preferably Z is a cyclic group having from 3 to 30 carbon atoms, preferably Z is a substituted or unsubstituted cyclic group having from 3 to 50 30 carbon atoms optionally containing one or more heteroatoms i

more preferably Z represents an aryl group, most preferably a substituted aryl group, in another embodiment of the present invention Z may be a silyl group or an alkylsilyl group, preferably a trialkylsilyl group;

Z may optionally be substituted with R 'groups independently selected from the group consisting of hydrogen atom or linear, branched alkyl or cyclic alkyl, alkenyl, alkynyl or aryl groups. Two or more R 'groups can also be linked to form a cyclic group such as an aliphatic or aromatic ring. R 'is preferably an alkyl group having from 1 to 20 carbon atoms, more preferably R' is methyl, ethyl, propyl, butyl, pentyl and the like, including all isomers of said groups, more preferably R 'is methyl or a primary, secondary or tertiary hydrocarbon, the group of which is an isopropyl group, a target, a butyl group and the like, most preferably the group R 'is an isopropyl group. The group R 'may optionally be bonded to group A. Preferably at least one of the groups R' is ortho bonded to group X;

A is a bridging group bonded to at least one of the groups, preferably to both X and J. The bridging group A comprises one or more elements from Groups 13-16 of the Periodic Table of the Elements. More preferably, group A contains one or more elements of group 14 of the Periodic Table of the Elements and most preferably group A is a substituted carbon group, a disubstituted carbon group or a vinyl group; and the maps are independently integers from 0 to 5, preferably m is 2;

is the oxidation state of the group M - q

1, if the group

Q is a monovalent anion;

is (oxidation state of group M - q) / 2, if group

Q is a divalent anion; or is (oxidation state of group M - q) / 3, if group

Q is a trivalent anion; preferably n is an integer from 1 to 4; and q is the number 1 or 2, wherein when q is 2, the two groups ((R ' _m Z) XA (YJR'' _m )) in formula (II) are linked together via a bridging group, preferably a bridging group containing the element 14 group of the periodic system of elements.

In a preferred embodiment of the present invention, when n in formula (I) or (II) is 2 or 3, the second catalyst is identical to the first catalyst except that one group y

Q represents a hydrocarbyl group, a boronate group or an amide group. In a particularly preferred embodiment of the present invention wherein n in formula (I) or (II) is 2 or 3, the second catalyst is the same as the first catalyst except that one Q is an alkoxide, a phenoxide, an acetylacetonate group, A carboxylate group, a cyclopentadienyl group, a fluorenyl group or an indenyl group. In another particularly preferred embodiment of the present invention wherein n in formula (I) or (II) is 2 or 3, the second catalyst is the same as the first catalyst except that one group Q in said second catalyst is a hydrocarbon adduct analogous to group Q of said first catalyst, preferably group Q in this case represents an alkoxide adduct, boronate adduct, phenoxide adduct, acetylacetonate adduct, carboxylate adduct, amide adduct, cyclopentadienyl adduct, fluorenyl adduct or indenyl adduct.

In a preferred embodiment of the present invention, the catalyst containing the transition metal compound is represented by the general formula (III):

((Z) X A _t (Y _J )) _q MQ _m T _s (III) where

M is a metal selected from Groups 3 to 13 of the Periodic Table or from the group of lanthanides and actinoids;

T is a group bound to the group M and represents an element of z

Groups 13 to 16 of the Periodic Table of the Elements, preferably an oxygen atom, a boron atom, a nitrogen atom, a silicon atom, a phosphorus atom, a sulfur atom or an aluminum atom, wherein T may also be bonded to one or more groups containing 1 to 50 atoms carbon atoms which optionally contain one or more heteroatoms;

preferably T represents a hydrocarbyl group, a boronate group or an amide group, preferably an alkoxide group, a phenoxide group, an acetylacetonate group or a carboxylate group or a cyclopentadiene group such as cyclopentadienyl groups, fluorenyl groups and indenyl groups;

Q are groups bound to M and each Q is a monovalent, divalent or trivalent anion;

X and Y are groups bonded to the group M and independently represent a carbon atom or a heteroatom, wherein at least one of X and Y is a heteroatom and preferably both X and Y are heteroatoms; Y is part of the heterocyclic ring J;

J is a heterocyclic ring containing from 2 to 50 non-hydrogen carbon atoms, preferably containing from 2 to 30 carbon atoms;

Z is a group bound to X, wherein Z contains from 1 to 50 non-hydrogen atoms, preferably Z contains from 1 to 50 carbon atoms, preferably Z represents a cyclic group containing from 3 to 50 atoms, preferably from 3 to 30 carbon atoms; in another embodiment of the present invention, Z may be a silyl group, preferably an alkylsilyl group;

• · • 99 t is the number 0 or 1, where t is 1

A is a bridging group bonded to at least one of X, Y or J, preferably to X and J;

q is 1 or 2;

m is the oxidation state of the group M - q - s, if the group

Q is a monovalent anion;

m is (oxidation state of group M - q - s) / 2 when group Q is a divalent anion; or m is (oxidation state of group M - q - s) / 3 when group Q is a trivalent anion; in the usual case m is an integer from 1 to 3, s is a number 1, 2 or 3, preferably 1 or 2.

In one embodiment of the present invention, when X is O or S, Z may or may not be present. In another embodiment of the present invention, when X is nitrogen or phosphorus, then Z is present. In a preferred embodiment of the present invention, T represents an oxygen atom and is bonded to an alkyl, aryl or alkaryl group.

In another embodiment of the present invention, at least one catalyst comprising a transition metal compound is represented by the general formula (IV):

((R ' _m Z) X A (Y J R'' _p )) _q MQ _n T _s (IV) where

M is a metal selected from group 3 to 13 of the Periodic Table of the Elements, preferably selected from the group of transition metals of group 4 to 12, preferably metal from the group of transition metals of group 4, 5 or 6, most preferably metal selected from group Group 4 transition metals such as titanium, zirconium or hafnium and most preferably zirconium;

T is a group bound to the group M and represents an element of z

Groups 13 to 16 of the Periodic Table of the Elements, preferably an oxygen atom, a boron atom, a nitrogen atom, a silicon atom, a phosphorus atom, a sulfur atom or an aluminum atom, wherein T may also be bonded to one or more groups containing 1 to 50 atoms carbon which optionally contains one or more heteroatoms; preferably T represents a hydrocarbyl group, a boronate group or an amide group, preferably an alkoxide group, a phenoxide group, an acetylacetonate group or a carboxylate group or a cyclopentadiene group such as cyclopentadienyl groups, fluorenyl groups and indenyl groups;

Q are groups bound to M and each Q is a monovalent, divalent or trivalent anion; in a preferred embodiment, the groups Q are independently selected from the group consisting of halogen atoms, the atom 9, 9, 9, 9, 9, 9, 9, 9, 9, 9, 9 S 9 9 9 9f 9 hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkylaryl group, an arylalkyl group, a hydrocarbyl group or a phenoxy group containing from 9 to 9; 1 to 20 carbon atoms. Each of Q may also represent an amide group, a phosphide group, a sulfide group, a silylalkyl group, a diketone group, and a carboxylate group. Optionally, each of Q may contain one or more heteroatoms, more preferably Q is selected from the group consisting of halides, alkyl groups and arylalkyl groups. Most preferably, each of Q is selected from the group consisting of arylalkyl groups such as a benzyl group;

X and Y are each independently a carbon atom or a heteroatom, wherein at least one of X and Y is a heteroatom and preferably both X and Y are heteroatoms, more preferably X and Y are independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, more preferably selected from the group consisting of nitrogen or phosphorus, and most preferably both X and Y are nitrogen; Y is part of a heterocyclic ring or cyclic system J;

J is a heterocyclic ring or a cyclic system containing from 2 to 30 carbon atoms, preferably from 2 to 7 carbon atoms, more preferably from 3 to 6 carbon atoms, and most preferably 5 carbon atoms. Optionally, the heterocyclic ring J containing group Y may contain additional heteroatoms. The group J may be substituted by R '' groups, which are independently selected from hydrogen or linear, branched alkyl, cyclic alkyl or alkenyl, alkynyl, alkoxy, aryl or aryloxy groups. Two or more R 'groups can also be linked to form a cyclic group such as an aliphatic or aromatic ring. The group R '' preferably represents a hydrogen atom or an aryl group, more preferably the group R '' represents a hydrogen atom. When R 'is an aryl group and Y is a nitrogen atom, a quinoline group is formed. The group R '' may optionally be bound to group A;

Z is a hydrocarbyl group bonded to the group X, preferably Z is a hydrocarbyl group having from 1 to 50 atoms, preferably Z is a cyclic group having from 3 to 30 carbon atoms, preferably Z is a substituted or unsubstituted cyclic group having from 3 to 50 30 carbon atoms optionally containing one or more heteroatoms, Z may be a silyl group, an alkylsilyl group, or a trialkyl group; in another embodiment of the present invention, Z is not an aryl group;

the Z group may optionally be substituted by a group of groups. · ··· ··························

R 'are independently selected from the group consisting of hydrogen or linear, branched alkyl or cyclic alkyl, alkenyl or alkynyl. Two or more R 'groups can also be linked to form a cyclic group such as an aliphatic or aromatic ring. R 'is preferably an alkyl group having from 1 to 20 carbon atoms, more preferably R' is methyl, ethyl, propyl, butyl, pentyl and the like, including all isomers of said groups, more preferably R 'is methyl or a primary, secondary or tertiary hydrocarbon, the group of which is an isopropyl group, a target, a butyl group and the like, most preferably R 'is an isopropyl group. The group R 'may optionally be bonded to group A. Preferably at least one of the groups R' is ortho-bonded to group X;

A is a bridging group bonded to at least one of the groups, preferably to both X and J. The bridging group A comprises one or more elements from Groups 13-16 of the Periodic Table of the Elements. More preferably, group A contains one or more elements of group 14 of the Periodic Table of the Elements and most preferably group A is a substituted carbon group, a disubstituted carbon group or a vinyl group; and the maps are independently integers from 0 to 5, preferably m is 2;

s is an integer from 1 to 3;

q the number 1 or 2;

n is the oxidation state of the group M - q - s, if group

Q is a monovalent anion;

n is (oxidation state of group M - q - s) / 2 when group Q is a divalent anion; or n is (oxidation state of group M - q - s) / 3 when group Q is a trivalent anion; wherein when q is 2, the two groups ((R ' _m Z) XA (Y JR'' _m )) in formula (IV) are linked together via a bridging group, preferably a bridging group comprising a group 14 element of the Periodic Table of the Elements.

In one embodiment of the present invention, in all of the above formulas, J is pyridine.

The transition metal compounds of the present invention are ✓

can be prepared by any method known in the art. Methods for preparing such compounds have been described, for example, in United States Patent Application Serial No. 09 / 103,620, filed June 23, 1998, which claims priority of Serial Application Serial No. 60 / 051,581, filed June 2, • ······························

1997 and which is equivalent to International Publication No. WO 99/01460.

In a preferred embodiment, the transition metal compound is [[1- (2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl. In another preferred embodiment of the present invention, [[1- (2-pyridyl) N-1-methylethyl] [1'-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-] is used in the gas phase or slurry polymerization reactor. propoxy] zirconium dibenzyl in admixture with alumoxane, preferably in admixture with methylalumoxane, more preferably in admixture with modified methylalumoxane, the product of this process being polyethylene, preferably high density polyethylene. In another preferred embodiment of the present invention, a mixture of a non-coordinating anion, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) bor or trisperfluorophenylbor, with [[1- (2-pyridyl) N1- methylethyl] [1'-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl. In another embodiment, the activating agent is selected from the group consisting of tris (2,2 ', 2' '- nonafluorobiphenyl) fluoroaluminate, alumoxane, triphenylbor, triethylbor, tri-n-butylammonium tetraethylborate, triarylborate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) ) bor, z

trisperfluorophenylbor or diethylaluminum chloride.

In one embodiment of the present invention, two or more catalysts are selected to prepare the desired product. Said catalysts, the number of which is two or more, are selected from the group consisting of catalysts of all the above formulas. Thus, for example, two different catalysts of formula (I) may be selected, or a compound of formula (I) or (II) may be combined with a compound of formula (III) or (IV). Similarly, two different catalysts may be selected, represented by the general formula (IV).

whose structure is

In a preferred embodiment of the present invention, a compound of formula (I) or (II) is used together with at least one compound of formula (III) or (IV). By selecting catalysts known to produce products of different molecular weights, a bimodal product can be obtained.

In another embodiment of the present invention, the two catalysts are injected separately into the reactor.

In a preferred embodiment of the present invention, the first catalyst is represented by the general formula (I) or (II) wherein at least one Q group is not selected from the group consisting of oxy adducts, and the second catalyst is identical to said first catalyst system except that two or all three Q groups are oxy adducts selected from the same group as for the Q group present in said first catalyst. For example, if [1- (2-pyridyl) N1-methylethyl] [1-N2, β-diisopropylphenylamido] zirconium tribenzyl is selected as the first catalyst, the second catalyst may be [[1- (2-pyridyl) N1-methylethyl] [ 1-N2, β-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl.

For the purposes of this invention and for the following claims, the term oxyaduct means a group of the general formula

0-R where

O is an oxygen atom; and

R is a group containing from 1 to 50 carbon atoms, which may optionally contain one or more heteroatoms.

Preferred R groups include target, butyl, target, amyl, target, hexyl, isopropyl, 2- [2-methyl-1-phenylpropyl], 2- [2-benzylbutyl], 3- [ 3-benzylpentyl] group. Further, R may be selected from the group consisting of benzyl, methylbenzyl, ethylbenzyl, and the like.

In another embodiment of the present invention, said oxyaduct may be represented by the general formula

O-B-R where

O is an oxygen atom;

B is boron and z

R is a group containing from 1 to 50 carbon atoms, which may optionally contain one or more heteroatoms.

A group of preferred R groups includes a target, butyl, target, amyl, target, hexyl, isopropyl, 2- [2-methyl-1 phenyl-propyl], 2- [2-benzylbutyl], 3- [3-benzylpentyl]. Further, R may be selected from the group consisting of benzyl, methylbenzyl, ethylbenzyl, and the like.

In a preferred embodiment of the present invention, the two catalysts, i.e. [1- (2-pyridyl) N1-methylethyl] [IN-2,6-diisopropylphenylamido] zirconium tribenzyl, and [[1- (2 -pyridyl) N-1-methylethyl] [1N-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl, mixed with alumoxane, preferably mixed with methylalumoxane, more preferably mixed with modified methylalumoxane, whereby polyethylene, preferably high density polyethylene, or alternatively low density polyethylene.

In another preferred embodiment of the present invention, a non-coordinating anion, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or trisperfluorophenyl boron, is used in a gas phase or slurry reactor in admixture with the two catalysts, i.e. 1- (2-pyridyl) N1-methylethyl] [1'-2,6-diisopropylphenylamido] zirconium tribenzyl and [[1- (2-pyridyl) N1-methylethyl] [1'-2,6-diisopropylphenylamido]] [2-methyl- 1-phenyl-2-propoxy] zirconium dibenzyl, in which case a polyolefin, which is preferably polyethylene, is formed.

In a preferred embodiment of the invention, the two catalyst compounds are typically mixed in a ratio of from 0.001: 1 to about 10,000: 1, preferably in a ratio of from 0.5: 1 to 1,000: 1. In a preferred embodiment of the invention, said first catalyst is present in an amount of from about 0.5 weight percent to about 99.5 weight percent, and said second catalyst is present in an amount of from about 99.5 weight percent to about 0.5 weight percent based on the total weight of the two catalysts without the weight of activating agents and carriers, more preferably said first catalyst is present in an amount of 5 weight percent to 95 weight percent % by weight and said second catalyst is present in an amount of up to 5% by weight, yet the first catalyst is present in an amount of from% to 90% by weight and said second catalyst of from 95% by weight is more preferably .

In a preferred embodiment of the present invention said first catalyst is present in an amount of from about

0.5 weight percent to about 99.5 weight percent, and said second and third catalysts are present in an amount of from about 99.5 weight percent to about 0.5 weight percent based on the total weight of the three catalysts excluding the weight of activating agents and carriers. more preferably, said first catalyst is present in an amount of from 5 weight percent to weight percent, even more preferably said first of said catalysts

the catalyst is present in an amount of from 10 weight percent to weight percent.

B. Another aspect of the present invention is an olefin polymerization catalyst system comprising at least one activating agent and the product of mixing the above activating agent with a transition metal catalyst having the structure represented by the above-described general formula (III) or (IV) together allowed to react before being injected into the reactor, the reaction time preferably being 15 minutes. In such an embodiment of the present invention, a single transition metal compound of formula (III) or (IV) may be used to prepare unique, preferably bimodal, polyolefins. It has been observed that temperature obviously affects the properties of the catalysts of formula (III) or (IV) and obviously affects the production of other compounds. Without wishing to be bound by any theory, it appears that this conversion provides these catalysts with the ability to produce bimodal products. Thus, it has been found that in the case of catalyst systems in which one transition metal-containing compound is used, a higher amount of bimodal product is produced at a higher temperature. Similarly, it has been observed that by allowing the transition metal compound of the present invention to react with the activating agent for a period of time, a system is formed by which a bimodal or multimodal polymer can be produced. Therefore, in a preferred embodiment of the present invention, said transition metal compound is allowed to react for at least 15 minutes, preferably for at least 30 minutes, preferably for at least 1 hour, preferably for at least 4 hours, prior to contacting the olefin with said activating agent. However, it has also been found that flash activation of [1- (2-pyridyl) N-1-methylethyl] [1N-2,6-diisopropylphenylamido] zirconium tribenzyl just prior to its injection into the reactor leads to the formation of a very active catalyst system. a bimodal polymer is formed. In another embodiment of the present invention, said polymerization occurs at a temperature of at least 80 ° C, preferably at a temperature of at least 85 ° C, preferably at a temperature of at least 85 ° C. a temperature of at least 90 ° C and more preferably at a temperature of at least 100 ° C.

C. Another aspect of the present invention is an olefin polymerization catalyst system comprising at least one activating agent as described above and a product of admixing a transition metal containing bidentate pyridine or quinoline containing bidentate ligand catalyst, the structure of which can be represented by the above general formula (I). or (II).

Said additive is preferably an alkoxy compound. The term alkoxy compound refers to compounds of the general formula

R = O where

R is a group containing from 1 to 100 carbon atoms, wherein the oxygen atom may be bonded at any point along the entire chain of the R group.

The group R may also contain heteroatoms in addition to 1 to 100 carbon atoms. Preferred alkoxy compounds include aldehydes and ketones. Particularly preferred alkoxy compounds include acetone, benzophenone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tert. butyl ketone, acetophenone, cyclohexanone, cyclopentanone, benzaldehyde, pivaldehyde, ethyl-n-propylketone, ethylisopropylketone and the like.

Preferably, the additive is mixed with the transition metal compound of the present invention in an amount of from about 0.5 weight percent to about 90 weight percent based on the total weight of the transition metal compound catalyst and the additive without the weight of activating agents and carriers. preferably, said additive is added in an amount of from 1 weight percent to about 80 weight percent and even more preferably in an amount of from 10 weight percent to 60 weight percent. The additive may be mixed with the transition metal compound catalyst of the present invention (with or without an activating agent) before being added to the polymerization reactor. In one embodiment, the additive is added to the transition metal catalyst of the present invention directly in the feed tube.

In a preferred embodiment, the activating agent is allowed to react with a transition metal catalyst (which has already been reacted with the additive) for at least 5 minutes prior to mixing with the olefin, preferably for at least 10 minutes and even more preferably for at least 15 minutes. minutes. It has been found that if said catalyst based on the transition metal compound is simply mixed with said additive and then directly added to the reactor, a less bimodal product is formed. When said additive is allowed to react for a period of time with the transition metal compound of the present invention, a more bimodal product is formed.

• 9

9 • 9

In a preferred embodiment of the invention said additive and the catalyst based on the transition metal compound of the present invention are mixed together prior to the addition of the activating agent. In another embodiment of the present invention, the polymerization reactor already comprises a mixture of a transition metal catalyst compound of the present invention, an olefin and an activating agent, and the additive is added to the mixture. In embodiments of the invention where the additive is added after mixing of the activating agent and the transition metal compound catalyst of the present invention, wherein the activating agent is an alumoxane, there may be a need to use a larger amount of the additive.

Various additives can be used to achieve different effects on the polymer produced. For example, using diethyl ketone as an additive produces a higher molecular weight polymer than methyl ethyl ketone as an additive. Similarly, using methyl ethyl ketone as an additive produces a higher molecular weight polymer than when acetone is used as the additive.

In a preferred embodiment of the present invention, a transition metal catalyst according to polymer is used in the gas-phase or slurry-phase polymerization reactor.

of the present invention, i.e. [1- (2-pyridyl) N-1-methylethyl] [1-N-

2,6-diisopropylphenylamido] zirconium tribenzyl, and said additive, which is acetone, in admixture with an alumoxane, preferably methylalumoxane, more preferably modified methylalumoxane, to produce polyethylene, preferably high density polyethylene. In another preferred embodiment of the present invention, t is t. T is t. A non-coordinating anion such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or trisperfluorophenylbore in admixture with a transition metal compound catalyst is used in the gas phase or slurry polymerization reactor. according to the present invention, ie [1- (2-pyridyl) N 1 -methylethyl] [1 N-2, β-diisopropylphenylamido] zirconium tribenzyl, and acetone.

The additive of the present invention may or may not be present in the mixture when said activating agent is added to a Group 15 transition metal compound, wherein the activating agent is mixed with said compound before or after the compound is injected into the compound. reactor. In another preferred embodiment of the present invention, a mixture of two different transition metal compounds, an activating agent and an additive is used in one reactor. In another preferred embodiment of the present invention, the transition metal catalyst of the present invention and the activating agent are fed to the reactor separately from said additive. Without wishing to be bound by any theory, it appears that the additive reacts with the transition metal compound catalyst of the present invention to form other active catalyst compounds. In carrying out the present invention, it has been observed that the temperature is likely to affect the equilibrium between the two forms of the catalyst of the invention. The higher temperature appears to promote the conversion of the transition metal catalyst of the present invention in the presence of the additive to the aforementioned second catalyst compounds. By choosing an appropriate amount of additive and the choice of a suitable temperature at which • ♦ ··· · »· ι <- * • * · L * 9 99 4 9 · <9» ·· »·« '- - ¹ - 99,999 * «999 ♦>

J 9 · 9

When the components are mixed and / or used, it is possible to select the desired end products.

In a preferred embodiment of the present invention, the catalyst component, which produces lower molecular weight polymers, is used in an amount of from 10 ppm to 70 weight percent based on the weight of all catalysts without the weight of activating agents and carriers; 100 ppm to 8 weight percent, even more preferably from 100 ppm to 5 weight percent. In another embodiment of the present invention, the compound which produces lower molecular weight polymers is used in an amount of from weight percent to 70 weight percent based on the weight of all catalysts without the weight of activating agents and carriers, preferably from 40 to 70 weight percent. weight percent to 60 weight percent, even more preferably in an amount of from 45 weight percent to weight percent. In another embodiment of the present invention, a compound that produces lower molecular weight polymers is used in an amount sufficient to provide from about 20 weight percent to about 70 weight percent of the final polymer product.

If more than one catalyst is used, then two or more catalysts may be activated at the same time or separately, either before or after injection into the reactor and before or after the support is applied. In one embodiment of the present invention, multiple catalysts are activated with the same activating agent prior to addition to the reactor. In another embodiment of the present invention, one catalyst is activated prior to its addition to the reactor, and the other catalyst is added, optionally without activating agent, to the same or other activating agent. In another embodiment, the catalysts are applied to the same support and subsequently activated with the same activating agent prior to addition to the reactor. In another embodiment of the present invention, the two catalysts are activated with the same or different activating agents and subsequently applied to the support prior to addition to the reactor.

Similarly, one or more of the catalyst systems of the present invention may be supported on an organic or inorganic carrier. Typically, the carrier may be any solid, porous carrier. Commonly used carriers include talc; inorganic oxides such as silica, magnesium chloride, alumina, silica-alumina; polymeric carriers such as polyethylene, polypropylene, polystyrene; etc. Preferred carriers include silica, clay, talc, magnesium chloride, and the like. Preferably, the carrier is used in finely divided form. In a preferred embodiment, said carrier is partially or completely dehydrated prior to use. Said dehydration may be carried out by a physical method, i.e. by annealing, or by a chemical method, i.e. by conversion of all or part of the active hydroxyl groups. A more detailed description of the method of deposition of catalysts on ✓

the support can be found in U.S. Patent No. 4,808,561, which discloses a method for applying a metallocene catalyst system to a support. The methods described in this patent are generally applicable in the practice of the present invention.

• · · ·

The catalysts of the invention may be applied to separate supports or to the same support. Similarly, the activating agent of the present invention may be applied to the same support as the catalyst or to a separate support. The one or more catalyst systems of the present invention and / or components thereof need not be added to the reactor in the same manner. For example, one catalyst or components thereof may be stirred in the reactor in the form of a suspension of the support on which the catalyst is deposited, while the other catalyst or components thereof may be added in the form of a solution.

In a preferred embodiment, the catalyst system of the present invention is added to the reactor in solution or slurry. Hydrocarbons are suitable for forming solutions or suspensions. For example, a solution may be formed in toluene, hexane, isopentane, or a mixture of said hydrocarbons, such as a mixture of toluene and isopentane, or a mixture of toluene and pentane. The solution typically contains from 0.02 mol to 0.05 mol catalyst in said hydrocarbon carrier, which is preferably isopentane or hexane.

In a preferred embodiment of the present invention, a supercritical fluid such as ethane or propane is used as the support of the catalyst system of the present invention or components thereof. More information regarding supercritical fluids used as catalyst carriers can be found in published European patent application EP 0 764 665 A2.

In another preferred embodiment of the present invention, the one or more catalysts of the present invention are mixed with up to about a percent by weight, preferably with 2 weight percent to weight percent metal stearate (preferably aluminum stearate, more preferably aluminum distearate) based on the total weight of said catalyst, carriers and said stearate. In another embodiment, a solution of said metal-containing stearate is added to the reactor. These agents may be dry blended with the catalyst of the present invention or may be added to the reactor in solution form with or without the catalyst system of the present invention or components thereof. In a preferred embodiment, the catalysts of the invention mixed with activating agents are mixed with a weight percent aluminum distearate and / or a weight percent antistatic agent such as a methoxy amine, exemplified by the Witco product sold under the tradename Kemamine AS-990 by ICI Specialties, based in Bloomington, Delaware, USA. Said metal-containing stearate and / or said antistatic agent may be added to the reactor as a slurry in mineral oil, ground to a powder, suspended in mineral oil and then added to the reactor or directly inflated into the reactor as a powder.

More information on the use of aluminum stearate type additives can be found in U.S. Patent Application Serial No. 09 / 113,216 of July 10, 1998, the contents of which are incorporated herein by reference.

The polymerization process according to the present invention and the catalyst systems which have been described for use in solution polymerization in

The above catalysts are suitable gas phase or in suspension or a combination thereof, most preferably the catalysts and catalyst systems described above are used in gas phase or slurry polymerization.

One aspect of the present invention are solution, slurry, or gas phase polymerization reactions comprising the polymerization of one or more monomers containing from 2 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and more preferably from 2 to 8 carbon atoms. Preferred monomers of the present invention include one or more compounds selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, or mixtures thereof. include vinyl polyene monomers, norbornadiene monomers,

3-methyl-1-pentene and cyclic olefins. The group of other monomers may be monomers, diolefins such as dienes, norbornene monomers, vinylnorbornene monomers, ethylidennorbornene monomers. Preferably, an ethylene homopolymer is produced according to the present invention. In another embodiment of the present invention, a copolymer of ethylene and one or more of the above monomers is produced.

In another embodiment of the present invention, ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer. A group of preferred comonomers according to the invention comprises a mixture of α-olefin monomers containing from 4 4 4 4 4 44 4 4 44 4 44 4 444 4 444 · 4

444 4444 444

44 44 44 44 444 to 10 carbon atoms, more preferably from 4 to 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers of the present invention include such mixtures as ethylene / 1-butene / 1-hexene, ethylene / propylene / 1-butene, propylene / ethylene / 1-hexene, ethylene / propylene / norbornene, and the like.

A particularly preferred embodiment of the present invention relates to the polymerization of ethylene and at least one comonomer containing from 4 to 8 carbon atoms, preferably from 4 to 7 carbon atoms. Examples of such comonomers are 1-butene,

4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene and 1-octene, with 1-hexene, 1-butene and 1-octene being the most preferred comonomers.

The gas phase polymerization process of the present invention typically utilizes a continuous cycle in which one portion of the cycle consisting of a reactor system circulating a gas stream, referred to as a recycle stream or fluid, is heated in the reactor by the heat released by the reactor. polymerization. This heat is removed from the recycle mixture in another part of the circuit by means of a cooling system located outside the reactor. Typically, in a fluidized bed gas phase polymerization process, a gas stream containing one or more monomers is continuously circulated through the fluidized bed in the presence of a catalyst and under conditions where the desired reaction occurs. The gas stream is removed from the fluidized bed and recycled back to the reactor. In parallel to this process, removal of the polymer product from said reactor and injection of fresh monomer to replace the polymerized monomer takes place. (See, for example, patents <* ·

No. 4,543,399; US 4,588,790;

US 5,028,670; US 5,317,036; US 5,352,749; US 5,405,922;

US 5,436,304; US 5,453,471; US 5,462,999; US 5,616,661 and

US 5,668,228, which are incorporated herein by reference).

The pressure in the gas-phase polymerization reactor may vary from about 69 kilopascals (about 10 psig) to about 3448 kilopascals (about 500 psig), preferably from about 690 kilopascals (about 100 psig) to about 3448 kilopascals (about 500 psig). 500 psig), preferably in the range of about 1379 kilopascals (about 200 psig) to about 2759 kilopascals (about 400 psig), more preferably in the range of about 1724 kilopascals (about 250 psig) to about 2414 kilopascals (about 350 psig).

The temperature in the gas-phase polymerization reactor may vary from about 30 ° C to about 120 ° C, preferably from about 60 ° C to about 115 ° C, more preferably from about 70 ° C to about 110 ° C. C, and most preferably in the range of about 70 ° C to about 95 ° C. In an embodiment of the present invention wherein the desired product is high density polyethylene, the reactor temperature is typically from 70 ° C to 105 ° C.

of

The productivity of the catalyst or catalyst system of the present invention in a gas phase system is affected by the partial pressure of the main monomer. The preferred content, expressed in mole percent, of the main monomer of the present invention, i.e. ethylene or propylene, preferably ethylene, is from about 25 mole percent to about 90 mole percent. The comonomer pressure is (approx

300 psia), (about psia) preferably psia), ranging from about to about ranging from about to about percent, with a partial of about 138 kilopascals.

517 kilopascals (approximately approximately 517 kilopascals)

2069 kilopascals (approximately 300 psia), which are the usual conditions of a gas phase polymerization process. In some systems, it is also possible to increase productivity by the presence of a comonomer.

of the present invention with the aid of the present invention and the invention can be produced from more than

In a preferred embodiment of the reactor used in the process of the present invention

227 kilograms of polymer / hour (i.e., greater than 500 lb of polymer / hour) to about 90,900 kilograms or more of polymer / hour (ie about 200,000 lb or more of polymer / hour), preferably from more than 455 kilograms of polymer / hour ( more than 1000 lb of polymer / hour), more preferably from more than 4540 kilograms of polymer / hour (i.e., more than 10,000 lb of polymer / hour), even more preferably from more than 11,300 kilograms of polymer / hour (i.e., more than 25 000 lb of polymer / hour), more preferably from more than 15,900 kilograms of polymer / hour (i.e. more preferably more (i.e., more than 50,000 to 29,000 kilograms of

% of polymer per hour) to more than 45,500 kilograms of polymer / hour (i.e., greater than 100,000 lbs polymer / hour), most preferably greater than 45,500 kilograms of polymer / hour (i.e. greater than 100,000 lbs polymer / hour).

more than 35,000 lb polymer / hour), more than 22,700 kilograms of polymer / hour lb polymer / hour) and more preferably from more polymer / hour (i.e., more than 65,000 lb β)

• · · · · · · · · · ·

A group of other polymerization methods of the present invention which are considered to be methods of the present invention include those described in U.S. Patent Nos. 5,627,242; US 5,665,818 and US 5,677,375, in US European patent applications EP-A-0 794 200;

202 and EP-B-634 421, the contents of all of which are incorporated herein by reference.

Slurry polymerization typically uses a pressure in the range of 103 kilopascals to 5068 kilopascals (i.e., from about 1 atmosphere to about 50 atmospheres, or from 15 psi to 735 psi) and even more, with a temperature range of 0 ° C to 120 ° C. In the polymerization, the solid, particulate polymer is suspended in a solvent-containing polymerization medium, the suspension being liquid to which ethylene is added along with the comonomers and the catalyst. Said solvent-containing slurry is intermittently or continuously removed from the reactor, where the volatile components are separated from the polymer, which are recycled, optionally after distillation, back into the reactor. The liquid solvent used in said polymerization medium is an alkane having from 3 to 7 carbon atoms, preferably an alkane. The medium used should be a propane medium under the conditions of a branched polymerization, the process must be carried out at a pressure and temperature that is above the critical temperature and the critical liquid and relatively inert. If used from

the pressure of said reaction solvent.

According to one embodiment of the present invention, the preferred polymerization process of the present invention is polymerization,

4 to form solid polymer particles or slurry polymerization at a lower temperature than would dissolve the polymer. Such procedures are well known in the art and have been described, for example, in U.S. Patent No. 5,768,549

US 3,248,179, which is incorporated herein by reference. In the method for forming solid polymer particles, the temperature is preferably maintained in the range of about 85 ° C (about 185 ° F) to about 110 ° C (about 230 ° F). In slurry polymerization, two methods are preferably used, one of which uses a loop reactor, while the other uses several stirred reactors connected in series, in parallel, or a combination of the individual reactor connections. Examples of slurry polymerization processes include, but are not limited to, a continuous loop process and a stirred reactor process. Other examples of suspension polymerization methods have also been described in U.S. Patent No. 4,613,484, which is incorporated herein by reference.

In another embodiment of the present invention, the slurry polymerization is carried out continuously in a loop reactor. The catalyst in the form of a suspension in isobutane or in the form of a free-flowing powder is regularly injected into a reactor loop which is itself filled with a circulating suspension of increasing polymer particles in a solvent which is an isobutane containing monomer and comonomer. Optionally, hydrogen may be introduced into the system to control the molecular weight of the polymer formed. The pressure in the reactor is maintained at about 3620 kilopascals

525 psig) to about 4309 kilopascals (625 psig), and the temperature in the reactor ranges from about 60 ° C (about 140 ° F) to about 104 ° C (about 220 ° F), depending on the desired polymer density. Reaction heat is dissipated through the loop wall, since most of this reactor is in the form of a double-jacketed pipeline. The slurry is allowed to leave the reactor at regular intervals or continuously to a heated low pressure evaporator, rotary dryer and nitrogen purge column to remove the isobutane solvent and any unreacted monomer and comonomers. The resulting hydrocarbon-free powder is subsequently used in various products.

With the slurry polymerization reactor and the process, more than 907 kilograms of polymer / hour (i.e., more than 2000 lb of polymer / hour), more preferably more than 2268 kilograms, can be produced by the slurry polymerization reactor. and more preferably more than 4540 kilograms of polymer / hour (i.e., greater than 10,000 lb of polymer / hour). In another embodiment, in the slurry polymerization reactor of the present invention, it is possible to produce from more than 6804 kilograms of polymer / hour (i.e., more than 15,000 lbs polymer / hour), preferably from more than 11,340 kilograms of polymer per hour (i.e., greater than 25,000 lbs polymer / hour) to about 45,500 kilograms of polymer / hour (i.e. greater than 100,000 lbs polymer / hour).

φ

In another embodiment of the slurry polymerization process of the present invention, the total reactor pressure is in the range of 2758 kilopascals (ie 400 psig) to 5516 kilopascals (ie 800 psig), preferably in the range of 3103 kilopascals (ie 450 psig) to about 4827 kilopascals (ie, about 700 psig), more preferably in the range of 3448 kilopascals (ie, 500 psig) to about 4482 kilopascals (ie, about 650 psig), and most preferably in the range of about 3620 kilopascals (ie, about 525 psig) to 4309 kilopascals (i.e., about 625 psig).

In another embodiment of the slurry polymerization of the present invention, the concentration of ethylene in said reactor fluid medium is in the range of about 1 weight percent to 10 weight percent, preferably in the range of about 2 weight percent to about 7 weight percent, more preferably in the range of about 2 weight percent. 5 weight percent to about 6 weight percent, most preferably in the range of about 3 weight percent to about 6 weight percent.

Another method of the present invention is a process, preferably gas phase or slurry polymerization, which is carried out in the absence or substantially free of any scavengers such as triethyl aluminum, trimethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and diethylaluminum chloride, dibutylzinc and the like. . Such a method has been described in WO 96/08520 and US 5,712,352, the contents of which are incorporated herein by reference.

• · • ·

In another embodiment, the process of the present invention is carried out in the presence of scavengers. Commonly used scavengers include trimethyl aluminum, triisobutyl aluminum and an excess of alumoxane or modified alumoxane.

The relative proportions of the individual components contained in the catalyst feed can be varied to change the molecular weight and other properties of the product. For example, by varying the ratio of the individual catalysts, it is possible to change the melt index, the melt index ratio at different loads, and / or the density of the product formed. An example is a system in which the catalyst of formula (I) and the catalyst of formula (IV) are mixed together. In this system, if the proportion of the catalyst of formula (IV) is increased, a lower molecular weight material is formed, thereby reducing the melt flow index and changing the molecular weight distribution. In a preferred embodiment of the present invention, the catalyst that produces the lower molecular weight component is present in an amount sufficient to produce from about 45 weight percent to about weight percent end product. For some products, such as foils, it has been found that an effective combination for this purpose is a mixture of 55 weight percent up to 5% by weight

by weight of component A, which is [1- (2-pyridyl) N-1-methylethyl] [1N-2,6-diisopropylphenylamido] zirconiumtribenzyl, and 45 to 65% by weight of component B, which is [1- (2-pyridyl) N1-methylethyl] [1'-2,6-diisopropylphenylamido] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl.

Another method of changing the molecular weight involves adding hydrogen to said system by increasing the hydrogen to ethylene ratio. Product density can be controlled by varying the content of the comonomer.

The present invention further relates to a method for controlling the molecular weight distribution (M _w / M _n ), melt flow index and / or density, which comprises making changes directly in a gas phase polymerization reactor (wherein the volume of the reactor is 42.5 m ³ or more (ie 1500 ft ³ or more)), making these changes. including changing the reaction temperature and / or changing the amount of catalyst of the present invention in a well-mixed catalyst solution and / or changing the hydrogen concentration and / or changing the ratio of the amount of activating agent of the invention to the amount of transition metal such as aluminum / zirconium.

The feed and mixing temperatures also represent means by which the properties of the product can be varied since the temperature affects the activation and / or evaporation of the solution, thereby altering the composition of the catalyst and hence the properties of the final product.

Sequence and timing of activation also provide an opportunity to • change the catalyst composition and thus the properties of the final z

product. For example, higher concentrations of methylalumoxane in a system comprising component A, which is [1- (2-pyridyl) N-1-methylethyl] [1N-2,6-diisopropylphenylamido] zirconium tribenzyl, and component B, which is [[1- (2-pyridyl) ) N1-methylethyl] [IN-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl

of the two catalysts. The above concentration increase includes increasing the concentration during activation and / or mixing and / or transfer and / or injection of the mixture into the reactor. Similarly, it has been observed that increasing the amount of hydrocarbon support in the catalyst feed leads to an increase in the amount of the lower molecular weight fraction formed.

The product properties can also be varied by changing the reaction temperature. It has been found that as the reaction temperature increases, the amount of the higher molecular weight component increases and, unusually, the two signals found in the chromatogram obtained by chromatographic separation based on molecular sizes are shifted closer together (i.e., the ratio by weight the molecular weight to the number average molecular weight (M _w / M _n ), i.e. the molecular weight distribution, is smaller compared to the product obtained using the same system at a lower temperature).

The molecular weight distribution can also be varied by varying the temperature in the reactor, changing the temperature of the catalyst system of the present invention before it enters the reactor, changing the ratio of catalyst to activating agent, changing the volume of the above support and / or contacting the transition metal compound. of the invention with a solvent prior to activation from above

said activating agent.

In a preferred embodiment of the present invention, the ratio of the amount of the first catalyst of the invention to the amount of the second catalyst of the invention or the amount of additional catalyst is from 5:95 to 95: 5, preferably from 25:75 to 75:25, more preferably from 40:60 to 60:40.

In another embodiment of the present invention, the catalyst system of the present invention is in liquid form and injected into the reactor in a zone that is free of polymer particles. More information on methods for injecting a liquid catalyst system into a fluidized bed in a polymer particle-poor zone can be found in U.S. Pat.

US 5,693,727, the contents of which are incorporated herein by reference.

Typically, the polymerization process of the present invention is arranged as follows: a modified methylalumoxane in a hydrocarbon such as hexane or isopentane (containing about 1 percent to 10 percent aluminum) and 10 percent by weight to 30 percent by weight [1- (2-pyridyl)] N1-methylethyl] [1N-2,6-diisopropylphenylamido] zirconium tribenzyl and 70 weight percent to 90 weight percent [[1- (2-pyridyl) N1-methylethyl] [1-N2,6-diisopropylphenylamido]] [2-methyl- The 1-phenyl-2-propoxy] zirconium dibenzyl is suspended in the solution, dried, and this mixture is subsequently mixed with 2 weight percent aluminum distearate and suspended in a gas-phase fluidized bed reactor maintained at a temperature from z

about 85 ° C to 100 ° C, wherein the ratio of aluminum to zirconium is about 500: 1 to about 1000: 1, then ethylene gas is fed to the reactor to maintain an ethylene partial pressure in the range of 0.5 megapascal to 0.7 megapascal (i.e., from 70 psi to 100 psi) and the reactor is allowed to run for 30 minutes. In this way

it produces polyethylene having a melt index ranging from 0.01 grams / 10 minutes to 10 grams / 10 minutes.

In a preferred embodiment of the present invention, the melt index, measured according to ASTM D-1238, Condition E, at 190 ° C, of the isolated polyolefin is usually 1 gram / 10 minutes or less. Preferably, the polyolefin is an ethylene homopolymer or copolymer. Preferably, the comonomer is a linear, branched or cyclic monomer containing from 3 to 20 carbon atoms, in one embodiment of the invention the comonomer is a linear or branched α-olefin containing from 3 to 20 carbon atoms, preferably propylene, hexene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene and the like.

In a preferred embodiment of the present invention, the catalyst system described above is used to produce high density polyethylene having a density of from 0.925 grams / cm ³ to 0.965 grams / cm ³ (measured according to ASTM 2839) and / or a melt flow index of 1.0 grams / 10 minutes or less (measured according to ASTM D-1238, Condition E, at 190 ° C). In another embodiment, the catalyst system described above is used to produce polyethylene having a density of from 0.85 grams / cm ³ to 0.924 grams / cm ³ .

In another embodiment, the polymer produced according to the present invention has a molecular weight distribution (M _n / M _n ) of at least 10, preferably at least 15, preferably at least 20, and even more preferably at least 30.

«• •« «« «« «« ««

Further, without being bound to any theory, it is believed that the polymers produced according to the present invention have the unique advantage that the two polymer products are mixed together so thoroughly that the particles leaving the reactor contain the two polymers whose the distribution throughout the structure of these particles is the same. The unprocessed, unprocessed granulated polymer is referred to herein as the polymer itself. The polymer itself is then fractionated using standard size sieves according to Method A of ASTM D 1921, which relates to particle size (sieve analysis) of plastic materials, or according to PEG Method 507.

Sieve size Collected faction Fraction designation 10 mesh > 2000 micrometers Fraction 1 18 mesh 2000 to 1000 micrometers Fraction 2 35 mesh <1000 to 500 micrometers Fraction 3 60 mesh <500 to 250 micrometers Fraction 4 120 mesh <250 to 125 micrometers Fraction 5 pan <125 micrometers Fraction 6

The individual fractions (fractions 1, 4, 6) are then tested to determine their physical properties. The melt index is measured in accordance with ASTM standard 1238, Condition E, at 190 ° C. Crystallinity is measured by X-ray diffraction as described in Example 13 below.

A unique attribute of the polymer produced according to the present invention is the fact that the melt indexes of the above-mentioned different fractions do not differ significantly from each other. In a preferred embodiment of the present invention, the melt flow indexes of fractions 1, 4 and 6 do not relatively differ by more than 20 percent, preferably do not differ by more than 15 percent preferably, they do not differ by more than 10 percent, preferably do not differ by more than 8 percent, preferably do not differ by more than 6 percent, preferably do not differ by more than 4 percent. By relative is meant relative to the mean value of the melt index of fractions 1, 4 and 6.

Another unique attribute of the polymer produced according to the present invention is the fact that the crystallinity, expressed as a percentage, of the above-mentioned different fractions does not differ significantly from each other. In a preferred embodiment of the present invention, the crystallinity, expressed as a percentage, of fractions 1, 4 and 6 does not relatively differ by more than 6 percent, preferably does not differ by more than 5 percent, preferably does not differ by more than 4 percent, preferably does not differ by more than 3 percent, preferably does not differ by more than 2 percent. By relative is meant relative to the mean crystallinity, expressed as a percentage, of fractions 1, 4 and 6.

Another unique attribute of the polymer produced according to the present invention is the fact that the molecular weight distribution (M _w / M _n ) of the above-mentioned different fractions does not differ significantly from each other. In a preferred embodiment of the present invention, the molecular weight distribution (M _w / M _n ), fractions 1, 4, 5 and 6 does not differ relatively by more than 20 percent, preferably does not differ by more than 10 percent, preferably does not differ by more more than 8 percent, preferably does not differ by more than 6 percent, preferably does not differ by more than 4 percent, preferably does not differ by more than 2 percent. By the expression • ·· 9 · ·· 9 99

9 9 9 9 9 9 9 9 9 9 9 9 9

9 9 9 9 9 9 9 9 999 9 relative to the mean molecular weight distribution (M _w / M _n ) of fractions 1, 4 and 6. Numerically average molecular weight (Mn) and weight average molecular weight (M _w ) were determined by gel permeation chromatography (GPC) on a Waters 150 ° C GPC instrument equipped with differential detectors based on refractive index measurements. Gel permeation chromatography (GPC) columns were calibrated using a series of narrow molecular weight polystyrene standards, and the molecular weights were calculated using the wide molecular weight polyethylene standards of the National Bureau of Standards 1496, which were selected according to the polymer. .

In another embodiment, the polymer of the present invention has a molecular weight distribution (M _w / M _n ) of 8 or more, preferably 10 or more, preferably 12 or more.

In another embodiment, a characteristic of the polymer produced according to the present invention is that the crystalline morphology of the particles of said polymer varies with their size. The fraction 1 particles preferably have an aspect ratio in the range of 0.5 to 1.5, the fraction 4 particles have an aspect ratio in the range of 1.2 to 4, the fraction 6 particles have an aspect ratio in the range of about 1.75 to 5, provided according to claim 1, characterized in that the individual particle aspect ratios of said fractions differ by at least 0.3, preferably by at least 0.5, more preferably by at least 1.0. In one embodiment of the present invention, the fraction 1 aspect ratio is <fraction 4 aspect ratio <fraction 6 aspect ratio. The value of said particle aspect ratio is in the range of [<110> / <011>] as discussed in the example below 13.

· ♦ e e e s * e e e e e e e e e e e e e e e e e

- · · * »» »»

In another preferred embodiment, the polymer produced according to the present invention comprises 10 weight percent to 90 weight percent, preferably 20 weight percent to 80 weight percent, more preferably 40 weight percent to 60 weight percent of a low molecular weight polymer (meaning a molecular weight of 50,000 or less) %, preferably 40,000 or less) based on the total weight of the polymer.

In another embodiment of the present invention, it has been found that the polymer produced comprises at least two components of different molecular weight, the amount of which in the polymer is more than 20% by weight, based on the weight of the polymer.

In another embodiment of the present invention, the produced polymer can be labeled bi- or multimodal due to the shape of the graph obtained by chromatographic separation (SEC). By bi- or multimodal is meant that the graph obtained by chromatographic separation based on the molecular size (SEC) of said polymer comprises two or more ascending curves, two or more descending curves and three or more inflection points (where the inflection point is a point on the curve) in which the value of the second curve derivative changes to negative), or said graph comprises at least one of

a rising curve, one falling curve, one inflection point, and a change in the rising and / or falling curve that is greater than 20 percent of said curve before the change. In another embodiment of the present invention, the SEC-size chart of a given polymer comprises one ascending curve, one ascending curve, one ascending curve. Decreasing curve, one inflection point, wherein the ratio of the weight-average molecular weight to the number-average molecular weight (M _w / M _n ) is 10 or more, preferably 15 or more, more preferably 20 or more. The above-mentioned graph obtained by molecular size chromatographic separation (SEC) was generated by gel permeation chromatography on a Waters 15 ° C GPC equipped with differential detectors operating on refractive index measurements. Gel permeation chromatography (GPC) columns were calibrated using a series of narrow molecular weight polystyrene standards and the molecular weights were calculated using Mark Houwink coefficients for the polymer.

The polyolefins of the present invention can be formulated into films, shaped articles, plates, tubes and the like. Said films can be produced by conventional methods known in the art, the group of which comprises extrusion, co-extrusion, lamination, blow molding and casting. The film may be obtained in the form of a flat film or by a process to produce a film in the form of a sleeve, followed by orientation of the film in the direction of one axis or two mutually perpendicular directions in the plane of the film. A group of particularly preferred processes for processing the polymers of the present invention to form films include extruding or co-extruding to a blown or extruded plant.

of cast foils.

The films made in accordance with the present invention may further comprise additives such as glidants, anti-blocking agents, antioxidants, pigments, fillers, anti-fouling agents, anti-damage stabilizing agents. Ultraviolet radiation, antistatic agents, agents for better polymer processing, neutralizing agents, lubricants, surfactants, pigments, dyes and nucleation agents. reagents. Preferred additives include silica, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal atom stearates, calcium stearate, zinc stearate, clay, barium sulfate, diatomaceous earth, wax, carbon black, flame retardants, low molecular weight polymers, glass beads and the like. Said additives are usually used in an amount sufficient for their effective action, which amounts are well known in the art and can be, for example, from 0.001% by weight to 10% by weight.

Films made from the polymers of the present invention have extremely good appearance properties. Said films contain a small amount of gel and / or have a good haze and shine. In a preferred embodiment of the present invention, the film has a thickness of 0.25 microns (i.e. 1 mil) of gloss at 45 ° 7 or more, preferably 8 or more, measured according to ASTM D 2475. In a preferred embodiment, the film has a thickness of 0, 25 micrometers (i.e. 1 mil) turbidity degree of 75 or less, preferably 70 or less, measured according to ASTM D 1003, Condition A.

Brief Description of the Drawings

Figures 1 to 5 show graphs of dwt / d (log M) versus the logarithm of the weight-average molecular weight, which serves as a measure of the molecular weight distribution. in polymers whose properties are summarized in Table 1.

Figures 6 and 7 show chromatograms obtained by chromatographic separation of polymers according to Examples 11 and 12 based on molecular sizes (SEC).

Figure 8 shows a chromatogram obtained by chromatographic separation of the polymer of Example 14 based on molecular sizes (SEC).

Figure 9 shows the chromatogram obtained by chromatographic separation of the polymer of Example 14, which was disclosed in United States Patent Application Serial No. 09 / 103,620 of June 23, 1998 (which was published as published international application no.

WO 99/01460), based on molecular sizes (SEC).

DETAILED DESCRIPTION OF THE INVENTION

The melt indexes I ₂ and I ₂₂ were measured in accordance with ASTM standard 1238, conditions E and F.

The melt index (MFR) ratio was measured in accordance with ASTM standard 1238.

BBF index (which is the butyl branching frequency index of

polymer chain for every 1000 carbon atoms) was measured by infrared spectroscopy as described in U.S. Patent No. 5,227,752.

The polydispersity index (PDI) is the same as the ratio of the weight-average molecular weight to the number-average molecular weight (M _w / M _n ). and was measured by chromatographic separation based on molecular sizes.

The weight-average molecular weight (M _w ) and the number-average molecular weight (M _n ) were measured by gel permeation chromatography on a Waters 15 ° C GPC, equipped with differential detectors working on refractive index measurements. Gel permeation chromatography (GPC) columns were calibrated using a series of narrow molecular weight polystyrene standards and the molecular weights were calculated using Mark Houwink coefficients for the polymer.

The melt index (MI) was measured in accordance with ASTM standard 1238, Condition E.

The melt index ratio (MIR) is the ratio of the melt index I ₂ i and the melt index I ₂ , which were measured in accordance with ASTM standard 1238.

The density was measured in accordance with ASTM D 1505.

Example 1

Preparation of [1- (2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropylphenyl] amine

22.45 millimoles (6.34 grams) of 2-acetylpyridine (2,6-diisopropylphenylimine) was added to a 250-ml round-bottom flask in a dry cabinet equipped with a 250 mL round-bottomed flask. · · ··· · ····· · ····· · · ···· · stirrer and whisper. The flask was tightly capped, removed from the dry cabinet, and placed under a stream of nitrogen. 50 mL dry toluene was added to the flask and the mixture was stirred until the above ligand was completely dissolved. The vessel was then cooled in an ice bath to 0 ° C and a 2 molar solution of trimethyl aluminum in toluene (obtained from Aldrich) was added dropwise over 10 minutes. The temperature of the reaction mixture was kept below 10 ° C. After all the trimethyl aluminum solution was added dropwise, the mixture was allowed to warm slowly to room temperature and placed in an oil bath where it was heated to 40 ° C for 25 minutes. The reaction vessel was removed from the oil bath and placed on ice, a dropping funnel containing 100 ml of a 5% potassium hydroxide solution was added, and the solution was added dropwise slowly to the reaction mixture over 1 hour. The mixture was transferred to a separatory funnel, the aqueous layer was separated, and the solvent-containing layer was washed successively with 100 mL of water and 100 mL of brine. The obtained reddish brown liquid was dried over anhydrous sodium sulfate, evaporated in vacuo and dried under vacuum overnight.

ml of the reddish brown liquid was transferred to a 200 ml Schlenk flask equipped with a stirrer. A distillation head with a dry ice cooler was attached to the flask. The mixture was distilled under vacuum to give approximately 70 grams of the desired product as a dark yellow viscous liquid.

• • • • • • •

Example 2

Preparation of [1- (2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropylphenylamido] zirconium tribenzyl

5.0 millimoles (1.45 g) of the ligand prepared in Example 1 was added to a 100 ml Schlenk flask equipped with a stirrer in a dark room and dark dry cabinet. The ligand was dissolved in 5 ml of toluene. To a second vessel equipped with a stirrer was added 5.5 millimoles (2.5 grams) of tetrabenzyl zirconium and 10 milliliters of toluene.

The ligand solution was transferred to a tetrabenzyl zirconium solution. The vessel was covered with foil and allowed to stir in a dry cabinet at room temperature. After stirring at room temperature for 6 hours, z was added to the reaction mixture

ml of dry hexane and the resulting mixture was allowed to stir overnight. Then, the reaction mixture was filtered through a medium porosity frit and approximately 2 grams of a light yellow solid was obtained.

«»

· 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 44 444

Example 3

Preparation of [[1- (2-pyridyl) N-1-methylethyl] [1 -N-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl

0.10 ml of dry acetone was added to the GC vial which had been previously dried in the oven, cooled, rinsed and tightly sealed. The GC vial was tightly sealed into another vial that served as its sheath and the assembly was placed in a dry cabinet. 2.0 millimoles (1.3 grams) of the substance prepared in Example 2 and 9 milliliters of toluene were added to a 100 milliliters Schlenk flask equipped with a stirrer in a dark room and dark dry cabinet. 2.0 millimoles (146 microliters) of acetone and 1.0 milliliters of toluene were added to the second GC vial. The acetone / toluene mixture thus prepared was added dropwise to the stirred ✓ syringe

of a solution of [1- (2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropylphenylamido] zirconium tribenzyl. The vessel was covered with foil and allowed to stir overnight in a dry cabinet at room temperature. The reaction mixture was evaporated in vacuo to give an orange sticky residue, to which 20 ml of dry hexane was added and the mixture was first vigorously intensified. Stir and then re-evaporate in vacuo to give a yellow-orange color. glassy fabric. Hexane was again added to this residue and the mixture was again vigorously stirred.

The reaction vessel was placed in a -24 ° C freezer for approximately 2 hours, filtered through a medium porosity frit to yield approximately 0.8 g of a pale yellow solid. Slow intentional addition of acetone combined with good mixing of the mixture appears to be the best procedure.

Example 4

A series of bimodal ethylene / hexene copolymers were prepared on a laboratory scale. In preparation of these copolymers, a slurry polymerization reactor containing mixed catalyst compositions formed from the complexes described in Example 2 and Example 3 and a cocatalyst of modified methylalumoxane (MMAO) type 3A (commercially available from Akzo) was used. Chemicals, Inc., under the tradename Modified Methylalumoxane type 3A and which is protected by US Patent No. 5,041,584).

In all cases, the catalyst composition was prepared by first preparing mixtures of the complexes of Examples 2 and 3 in toluene and then contacting them with a solution of modified methylalumoxane (MMAO) (which contained 7.0 weight percent aluminum) in heptane in the presence of 0.1 ml of 1-hexene. The polymerization was carried out at 85 ° C, ethylene pressure of 586 kilopascals (85 psi), in the presence of 43 milliliters of 1-hexene, 0.5 micromole of zirconium, the MMAO / Zr ratio being

000: 1. The ratios of the individual complexes are expressed as the molar ratios of the complex described in Example 3 to the complex described in Example 2. The results obtained are summarized in Table 1 below.

Table 1

The ratio of complexes Activity* I ₂ grams / 10 minutes MFR ** BBF ** per 1000 atoms carbon PDI ** 100: 0 139765 162.2 1.82 6.28 11.18 90:10 291765 13.49 61, 66 10,08 25.84 80:20 175529 0.05 1 027 7.54 23.74 60:40 235765 0.0085 317.4 9, 92 28.24 50:50 189647 0.012 173, 1 11.01 30.25

Explanation of the table * Activity is given as gram of PE / millimol catalyst / at ethylene pressure of 690 kilopascals (100 psi) / hour * ★ The meaning of each abbreviation has been explained in the introduction to this section.

The polymers listed in Table 1 were subjected to chromatographic separation on the basis of molecular sizes, the results of which clearly showed that, with increasing concentration of the complex of Example 2, the proportion of high molecular weight component in the polymerization product increased. The relative proportions of the two complexes of Example 3 and Example 2, respectively, reflect the proportion of low and high molecular weight components in the above-mentioned bimodal polymers. This fact demonstrates that the two catalysts are highly compatible.

Example 5

An ethylene / hexene copolymer was prepared in a 35.6 centimeter (14 inch) gas phase polymerization reactor operating at 85 ° C, 1517 kilopascals (220 psi) and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 25 kilograms / hour (i.e. about 55 Ib / hour), hexene was fed to the reactor at a rate of 0.64 kilograms / hour (i.e. 1.4 Ib / hour), and hydrogen was fed to the reactor. at a rate of 0.01 kilogram / hour (i.e. 0.021 lb / hour), which was sufficient to produce approximately

15.9 kilograms / hour (i.e., about 35 lbs / hour) of the polymer. The total reactor pressure was 2413 kilopascals (i.e., 350 psi). Further, nitrogen was fed to the reactor at a rate of about 1.4 to 1.5

3.2 kilograms / hour (i.e., approximately 3 to 7 lb / hour). The reactor was equipped with a pressurized device set to power

818.2 kilograms / hour (ie 1800 lb / hour), with single-hole injector with conical nozzle of inside diameter

0.14 centimeter (i.e., 0.055 inch) (said pressurizing device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone. More information on the use of this type of device can be found in U.S. Pat. US 5,693,727).

The procedure was repeated several times, changing one or more of the following parameters: reaction temperature, aluminum / zirconium ratio, reaction temperature, injection temperature! or the type of hydrocarbon feed carrier used. Changes made to the reaction conditions are listed in Table 2 below.

Table 2

Example Reaction temperature Weight percent of low molecular weight fraction * Catalyst Mw / Mn Ratio Al: Zr AND 85 60 3 14 350: 1 (B) 90 57 3 16 360: 1 C 95 51 3 12 350: 1 D 105 35 3 11 350: 1 E 85 22nd 2: 3 450: 1 F 85 70 3 72: 1

Explanatory notes to the table:

* The weight percent of the low molecular weight fraction refers to the proportion of the lower molecular weight components produced, which were determined by processing the results of the chromatographic separation according to the size of the molecules using the logarithmic normal Gaussian distribution.

Example 6

The above example was repeated using the catalysts of Examples 2 and 3 except that the following conditions were used in the polymerization: temperature 85 ° C, ethylene pressure 1517 kilopascals (220 psi), 500: 1 Al / Zr ratio Catalyst addition rate of 10 cm ³ / hour, Modified methylalumoxane (MMAO) addition rate of 300 cm ³ / hour (as a solution in hexane concentration 2) , 3 weight percent aluminum). The ratio of the two catalysts was varied.

Table 3

Catalyst ratio 2/3 Activity* I ₂ grams / 10 minutes MFR ** Density gram / cm ³ 60/40 15 651 0.196 51.47 0.9455 40/60 17 929 0.150 59.89 0.9475 20/80 16 905 0.165 63.45 0.9498 0/100 16 061 0.167 76, 27 0,951 80/20 40 048 0.150 52.08 0.9422

Explanation of table ★ Activity is given as gram PE / millimol zirconium / hour ** The meaning of each abbreviation has been explained in the introduction to this section.

Example 7

In a gas-phase polymerization reactor with a diameter

Two ethylene / hexene copolymers were prepared 2.4 meters (8 ft) (approximately 56.6 m ³ (2000 ft ³ )). The ethylene feed rate was about 3636-4090 kilograms / hour (i.e., about 8000-9000 lbs / hour). The hexene feed rate was about 90.0 to 104.5 kilograms / hour (i.e., about 200 to 230 lbs / hour). He was in the reactor

further adding hydrogen at a rate of about 2.2 to 4.4 kilograms / hour (i.e., about 1 to 2 lbs / hour). The copolymer was formed at a rate of 3636-4090 kilograms / hour (i.e., 8000-9000 lbs / hour). Further, nitrogen was fed to the reactor at a rate of 13.6 to 27.3 kilograms / hour (i.e., about 30 to 1b / hour). The reactor was equipped with a pressurized device set at a power of 22,727 kilograms / hour (50,000 lb / hour) and a three-hole nozzle having an internal diameter of 0.32 centimeters (0.125 inch), with the diameter of the center hole narrowing to a diameter 0.13 centimeter (i.e. 0.05 inch) and the diameter of the other two orifices positioned perpendicular to the direction of gas flow was 0.76 centimeter (i.e. 0.30 inch) and the nozzle width was 0.20 centimeter (5 / 64 inch). The orbiting gas velocity was approximately 60 to 67 centimeters / second (i.e., 2-2.2 ft / second). The injection temperature was 22 ° C in the first cycle and increased to 80 ° C in the second cycle. The catalyst produced in Example 3 was used together with 2% by weight of modified methylalumoxane 3A, with an Al: Zr ratio of 150: 1. In the first cycle, a polymer containing a lower molecular weight fraction was produced, and in a second cycle, a polymer containing a lower molecular weight fraction was produced.

Example 8 of

Five 0.02 molar solutions of the compounds of Examples 2 and 3 in toluene were prepared, each containing 80/20, 60/40, 40/60, 20/80 and 0/100. These solutions were used in the polymerization process described in Example 5 using modified methylalumoxane 3A as the cocatalyst. The fluidized bed temperature was maintained at 85 ° C, the ethylene partial pressure was 1537 kilopascals (220 psi), and the Al: Zr ratio was 500: 1. The properties of the polymers obtained are summarized in Table 4.

Table 4

80/20 60/40 40/60 20/80 0/100 Hexene / ethylene ratio (x 10 ~ ³ ) 8.1-9.1 6.6-7.7 6, 1-6, 7 5.4-5.6 5.4-5.7 Hydrogen / ethylene ratio (x 10 ~ ³ ) 23,7- 25.5 17,5- 18.6 14.0 12,3- 12, 6 12,1- 12.2 Production speed (kilogram / hour) (lb / h) 12.7 (28) 11.8 Italy (26) 11.8 Italy (26) 11.8 Italy (26) 12.2 Italy (27) Activity* 19000 17500 15000 16100 17500 Flow index melt (gram / 10 minutes) 0,15- 0.26 0,17- 0.26 0,13- 0.34 0, 12- 0.17 0,16- 0.21 Flow index melt (gram / 10 minutes) 8,07- 12.3 0, 95- 12.88 8,81- 14.07 9, 68- 10, 95 12,53- 14.50 MFR ** 39,87- 55.63 46,37- 64.39 32,96- 65.75 61,24- 81.87 70,73- 77.83 Density gram / cm ³ 0,942- 0,944 0,945- 0,947 0,947- 0, 950 0,950- 0,951 0,951- 0, 952

Explanation of the table * Activity is given as gram PE / millimol zirconium / hour ** The meaning of each abbreviation was explained in the introduction to this section.

Example 9

Synthesis of [[1- (2-pyridyl) N1-methylethyl] [1N-2,6-diisopropylphenylamido]] [3-benzyl-3-pentoxy] zirconium dibenzyl millimoles (4.0 mL) of diethyl ketone (available from Aldrich as 99.5 % 3-pentanone, [86,13]) was dissolved in 96 ml dry toluene. The resulting diethyl ketone solution was slowly transferred to

400 ml of stirred 0.125 molar toluene solution of the complex of Example 2. The resulting solution was allowed to stir overnight.

Example 10

Synthesis of [[1- (2-pyridyl) N1-methylethyl] [1N-2,6-diisopropylphenylamido]] [2-benzyl-2-butoxy] zirconium dibenzyl millimoles (3.6 mL) of methyl ethyl ketone (available from Aldrich as 99.5 % 2-butanone) was dissolved in 100 mL dry toluene. The resulting methyl ethyl ketone solution was slowly transferred to 400 mL of a stirred 0.125 molar toluene solution of the complex of Example 2. The resulting solution was allowed to stir overnight.

✓

Example 11

0.1 milliliters of 1-hexene dried over alumina was added to a 14.2 milliliters (4 drama) glass vial in a dry cabinet, which was previously dried in an oven. 0.25 micromol (2.0 microlitres) of the complex of Example 2 as a 0.125 molar solution in toluene and 0.25 micromol (3.7 microliters) of the complex of Example 9 as

A 0.067 molar solution in deuterated benzene was added to the indicated volume of 1-hexene to give a pale yellow solution. To the vial containing the mixture was added 0.25 millimoles of modified methylalumoxane (MMAO) type 3A to give a light yellow reaction mixture. The reaction mixture was added to a reactor containing 600 milliliters of hexane, 43 milliliters of 1-hexene and 0.13 milliliters (0.25 millimoles) of methylalumoxane (MMAO) type 3Ά, and allowed to react at 70 ° C, ethylene pressure for 30 minutes. 586.5 kilopascals (i.e., 85 psi) and 69 kPa (i.e., 10 psi) hydrogen pressure. The reaction was obtained

26.3 grams of product (corresponding to 123765 grams of polyethylene (millimole Zr / hour) at ethylene pressure)

690 kilopascal (i.e. 100 psi), the polymer having the following melt index properties

I ₂ = 28.49 grams / 10 minutes, I ₂ = 838 grams / 10 minutes, MFR = 29.4 and BBF 7.63). Molecular Size Chromatography (SEC) showed the following molecular weight results: number average molecular weight M _n = 12611, weight average molecular weight M _w = 50585, PDI = 4.01. The chromatogram obtained by SEC-size chromatographic separation is shown in the attached Figure 6.

Example 12

0.1 milliliters of 1-hexene dried over alumina was added to a 14.2 milliliters (4 drama) glass vial in a dry cabinet, which was previously dried in an oven. 0.25 micromoles of the complex of Example 2 in the form

A 0.125 molar solution in toluene and 0.25 micromole of the complex of Example 10 as a 0.080 molar solution in toluene was added to the indicated volume of 1-hexene to give a light yellow solution. To the vial containing the mixture was added

0.25 millimoles of modified methylalumoxane (MMAO) type 3A to give a pale yellow reaction mixture. The reaction mixture was added to the slurry polymerization reactor it contained

600 milliliters of n-hexane, 43 milliliters of 1-hexene and 0.13 milliliters (0.25 millimoles) of methylalumoxane (MMAO) type 3A, and were allowed to react at 70 ° C, ethylene pressure of 586.5 kilopascals (i.e. psi) and a hydrogen pressure of 69 kilopascals (i.e., 10 psi). The reaction yielded 30.7 grams of product (corresponding to an activity of 144471 millimoles Zr / hour) at ethylene pressure (i.e. 100 psi), the polymer having: melt index I ₂ =

690 had grams of polyethylene / kilopascals following

11.47 grams / 10 minutes, minutes, MFR = 40.8 and BBF 7.53). At

I21 = 468 grams / 10 chromatographic results showed the following results regarding the molecular weight of the product obtained: number average molecular weight M _n = 12794, weight average molecular weight

M _w = 62,404, PDI = 4.88. The chromatogram obtained with SEC-size chromatographic separation is shown in the attached Figure 7.

of

Example 13

An ethylene / hexene copolymer (referred to as A) was produced having a density of about 0.946 grams / cm ³ , and the polymer was prepared according to the procedure of Example 5 except that the catalyst of Example 3 was added.

9 ml / hour and the catalyst of Example 2 was injected at 1 ml / hour (i.e. the ratio of the catalysts was 90:10). Hexene was fed to the reactor at a rate of about 0.36 to 0.41 kg / hour (i.e., about 0.8 to 0.9 lb / hour), and ethylene was fed to the reactor at a rate of about 18.5 to 19.4 kg / hour (i.e. about 41 to 43 lb / hour), hydrogen was fed to the reactor at a rate of 7.7 to 9.1 grams / hour (i.e. 0.017 to 0.02 lb / hour) and a hexane carrier was fed to the reactor at a rate of about 100 milliliters / hour. The ethylene partial pressure in the reactor was 827 kilopascals (i.e. 120 psi) and the reactor temperature was 75 ° C. The ratio of aluminum to zirconium Al: Zr was 300: 1.

Another ethylene / hexene copolymer (referred to as B) was prepared by the same procedure except that only the catalyst of Example 3 was injected into the reactor at a rate of 10 ml / h, the reactor temperature was 95 ° C, the hydrogen was fed at 5.4 up to 6.4 grams / hour (i.e. 0.012 to 0.014 lbs / hour), ethylene was fed to the reactor at a rate of about 18.5 to 20.3 kilograms / hour (i.e. about 41 to 45 lbs / hour) and ethylene partial pressure there were 827 kilopascals (ie 220 psi) in the reactor. The density of the resulting copolymer was 0.951 g / cm ³ .

Another ethylene / hexene copolymer (referred to as C) was prepared by the same procedure except that only the catalyst of Example 3 was injected into the reactor at 12 milliliters / hour, the reactor temperature was 95 ° C, the hydrogen was fed at 5.4 up to 5.9 grams / hour (i.e. 0.012 to 0.013 lb / hour), ethylene was charged to the reactor

at a rate of about 19.9 to 21.2 kilograms / hour (i.e. about 44 to 47 lbs / hour), the ethylene partial pressure in the reactor was 827 kilopascals (i.e. 220 psi), and the hexane carrier was injected into the reactor at a rate of 70 ml. hour. The density of the resulting copolymer was 0.951 g / cm ³ .

The polymers were separated into fractions by particle size using the following sieves:

Sieve size Collected faction Fraction designation 10 mesh > 2000 micrometers Fraction 1 18 mesh 2000 to 1000 micrometers Fraction 2 35 mesh <1000 to 500 micrometers Fraction 3 60 mesh <500 to 250 micrometers Fraction 4 120 mesh <250 to 125 micrometers Fraction 5 pan <125 micrometers Fraction 6

The fractions obtained were characterized and the results are summarized in Tables A, B, C and D.

Summary of experimental procedures used to collect data in X-ray diffraction and methods used to determine crystallinity percentage and crystal morphology analysis

X-ray diffraction data collection

The Siemens GADDS X-ray Diffraction (XRD) unit equipped with a copper tube lamp was used to collect all data.

irradiated at a wavelength of λ = 1.54056 A and operating at a voltage of 40 kilovolts and a current of 40 milliamps, a graphite monochromator, a 0.3 millimeter collimator placed in front of the sample and a full-area diffraction generator (GADD) whose distance from the sample was 15 centimeters. The individual large particles were adhered to a thin glass rod which allowed the particle to suspend and rotate in the beam without causing undesirable interactions with the glass rod or glue. The fine particles were placed in a thin silicon capillary during analysis. All data collection was in transmission mode with the beam stopped 3 centimeters behind the sample. Spectra were recorded at three different diffractometer settings, said detector covering the following 2Θ regions: 4 ° -34 °, 32 ° -58 ° and 56 ° 76 °, and data acquisition for each region typically took 600 seconds. The data obtained for the three regions were devoid of distortions (distortion correction) and then combined together to form a single spectrum covering the region 2-4 ° to 76 °. The GADDS system, in which the detector was 15 centimeters from the sample, provided a view of the 120 ° arc of Deby's ring. In these measurements, uniform intensity was observed along the entire circle, indicating an perfectly homogeneous structure not showing the presence of a preferred polymer chain orientation or texture. ,

Creating a curve

To create a spectrum profile, a full profile curve fitting program was used, which was part of the system. 9 9 Ί> 9 9

9 * 9> 9 · 1 · 1 ·

GADDS. For large particles, the airborne scattering signals measured under the same conditions were subtracted from the measured values before the curve, whereas for the small particles, the silicon capillary and airborne scattering signals measured under the same conditions were subtracted from the measured values. conditions. Four components were used to compile the curves from the measured data; (i) the diffraction signals were assembled into a pseudoVoigt profile function with mixing parameter 1; (ii) the amorphous signals were assembled into a Lorentzian profile function with the maximum signal width at half maximum intensity (FWHM) and signal positions determined based on simulations (iii) the paracrystalline component was assembled into a Pearson VII shape function in which the exponent was 50 and (iv) the values corresponding to Compton scattering were linearized.

After subtracting the values corresponding to Compton scattering from the data obtained, the total scattered intensity was composed of three components, (1) amorphous intensity I _am , (2) paracrystalline component I _para and (3) diffraction signals of crystals I _x and i served the following formula:

Percentage of crystallinity = I _x and i / (Iam + Ipara + I _xa i) ^x 100.

of

Size of crystals

The crystal size was measured by the signal width at half the maximum reflection intensity {110} and {011} contained in the X-ray diffraction curves of the granular polyethylene polymer. These two values allow calculating the size of a given crystal in a given crystallographic direction using the Scherrer equation:

Crystal size (t) = 0.9a / B'cos6 _b

B ^- Measured instrumental extension where λ is the wavelength of incident X-rays,

B 'is the corrected signal width at half maximum intensity, expressed in radians (instrumental broadening the beam was measured in accordance with SRM 660, which was established by the National Bureau of Standards, wherein in the measurement, a sample of lanthanum hexaboride) _θ Β position is signal t and t is the crystal size to a given crystallographic direction, which was determined by the respective reflection.

Reflection <110> provides information on crystal size in the <110> direction that lies in the ab plane of the polyethylene (PE) diamond, similarly reflection {011} provides information on a crystal size in direction <011> that lies in the bc plane of the diamond crystal polyethylene (PE), which contains the c-axis component, therefore it is possible to obtain information about the thickness of said crystal from this data.

Therefore, the value of crystal size in the two directions can provide information about the morphology of said crystal, using a so-called shape factor, which is defined as the ratio <110> / <011>. If the value of this ratio is large, they are

-τ λ ··· · · ···.

/ 4 .. ···· ♦ ····

........ ·,

... the crystals are large in the ab plane, but thin in the bc plane, so that they resemble "slices, whereas if the ratio is close to one, both dimensions are similar and the crystal morphology more resembles a cubic or spherical face.

Table A summarizes the X-ray diffraction data of all three samples studied. It was found that the degree of crystallinity did not change with varying particle size, with small particles having the same percent crystallinity as particles that were much larger.

It has been observed that the crystal size in the ab plane decreases monotonically as the particle size increases. On the contrary, it was observed that the crystal size in the plane bc (which serves as an estimate of the size of the c-axis component) monotonically increases with increasing particle size.

These results led to the conclusion that the shape of the crystal is dependent on the particle size. The crystal shape of small particles is more reminiscent of “slices with aspect ratio [<110> / <011>] = 2.23.5; as the particle size increases, the aspect ratio shifts toward a 1-1.5, which makes the crystal shape more resembling a cube or sphere. Thus, the shape of the crystal domains that are embedded in the granular polymer structure of the present invention varies from a slice-like shape to a cubic / spherical shape with increasing particle size away from the fraction trapped in a ladle screen analysis

(i.e. away from particles smaller than 125 microns) to particles trapped on a 10 mesh screen (i.e. particles larger than 2000 microns). The particles can be viewed as stepped microstructure particles.

The observed properties of the catalyst system described above are just one example of a stepped microstructure. An opposite structure may also be formed with cubic / spherical crystals located in the center of the particle that change towards a particle surface more like a "petal morphology". Another possible crystal morphology is "rod-like morphology, in which the value of said shape factor is less than 1. The distribution of the different crystal morphologies can give rise to a wide range of possible microstructures, the formation of which can be controlled by appropriate choice of catalyst type.

Table A - X-ray diffraction data of the samples of Example 13

+ J w 0 * rl H (1)> (011) 143.4 WHAT and- 143.4 126.9 O o o ! —1 00 Γ i — 1 i — 1 143.4 O O 114.7 13, 6 H (ti X P ω 0 44 WHAT LO CM CM CM LO • r | TO TO Γ X LO r — 1 Φ> O r- ' LQ O- θ ' O O X O X cn O cn CM WHAT what O what what and- CM and- CM CM OJ CN CM H (ti N 0 WHAT 00 what θ ' what O WHAT O WHAT kD with X *. WHAT what 00 what σι what O CM i — 1 □ 3 r-1 WHAT what what kO 1 ------ what O OA 2 H m LO LO LO 00 θ ' LiO O O EL O X X X X X X X X X X x-z O O O O O O O O O O 0 LO kO 1 ------ O O what kO > <* X what CM ΟΊ LO and- 10 0Λ O LO & O O cn O LO LO O LO O E rd rd what what 00 what O 00 O x ** O O O O O O O O O O tí σ> and- kO 00 CM kO ΟΊ what 5 X χ X X X X X X <; dP cn 0Á what r- CM WHAT what cn CM what what what WHAT 'xT WHAT 00 what <ti M WHAT r- 00 LO ΟΊ LO WHAT 50 00 what flj X X X X X X X X X cu LO kO what 10 tr O LiO , —1 dP H what CM i — 1 kO Γ 1—1 O CM what O X X X X X χ · »· X x LO LO LO LO what LD LO O ’ΧΓ dP LiO LO LO LO LO 10 LO LO O i — 1 fÚ X-X 44 (ti 44 > No x: i — 1 CM WHAT 1 — 1 O deviations 'Π5 O 44 (1) 1 1 x: 1 XI 1 x: i — 1 1 CM 1 and-! 04 \ from P (D m ω ω m > > O n 0 N> Φ Φ Φ Φ Φ Φ k <D '(those £ £ £ £ C C > φ C 1 o 1 o 1 o 1 o Bye '(those CLi £ -os '(those X> (0 o LO rH t — 1 i — 1 LO S-1 -O o Ό > Φ Ό CLi £ 0 ěr ěrc Qj Sm £ ω <

• 99 • • • • •

Table A - X-ray diffraction data of the samples of Example 13 - continued

+> 0) 0 44 rl H Φ> (011) 180.3 180.3 179, 6 159, 9 154.0 LO 00 1 H 180.1 'xT o 152.5 8.3 H <e +> <n o 44 • rl CH LO X. and- * » r- O CM Xk 03 / LO rH Φ!> O WHAT t — 1 CM CM 0 ϊ— O Xk O [ WHAT r- Τ ' O 00 CM r- CM CM CM CM CM 00 what WHAT CM WHAT rH flj N O WHAT what LO • xT Γ 10 O CM what 5] O- O- cn O- 0- Γ- what i — 1 O rH LO what CM what what O LiO what § rd ’ΖΓ LT) 10 LD O ld O gí O X. X. Xk Xk Xk X. Xk Xk Xk X— ' O O O O O O O O O O 0 what LiO O CM 00 r- 1 — 1 CX1 r- O 5] CM Γ- r- r- cr> C- ΟΊ what CM O O ΟΛ cn LO 00 10 σ \ O LO t — 1 § r1 what CM CM CM CM OJ CM O CM O ttJ i — 1 Xk TO. Xk X » Xk Xk Xk Xk Xk Xk * O O O O O O O O O O tí O Ϊ— r- CM σ CM what 'tr *to X. X. Xk Xk Xk Xk Xk <X> lo lo what LO what m CM what what what what what what what what 5— ! - 00 what what σ m LiO what LO <β X. X » Xk Xk Xk X. Xk X. Xk *to incl what 00 10 00 kO 00 O LO 1 — I dP al ΟΊ what O uo what σ> 92 O CM ΐ — l X. X. * » Xk Xk *to *to X AND- O O t— ΟΛ σ> O dP LO lo LO LO LiO LiO LO LO O ř — 1 rd 4 ^ Lka > l -------- 1 CD (7 47 i — 1 C \ J what i — 1 O > 1 47 U Ό 0 '05 AT > OJ 44 Φ 1 4 =: 1 47 1 47 1 47 t — 1 1 CM 1 i — i 0, after O ω WHAT WHAT > > O 'fd Qm 0 N> O <1) and; Φ Φ Φ WHAT '05 6 £ £ £ í7 S7 > φ í7 1 o 1 o 1 o 1 o '(Ό P-i '(Ό 04 / £ »5 -P 05 / about what i — 1 1 — 1 rH what M Ur > <r> Ό Cli ňrodat E 0 r ěr Cl, Srn £ ω O

• • •

Table A - X-ray diffraction data of the samples of Example 13 - completion

Xal size 1 (011) 229.2 229.2 143.3 131.0 131.0 131.0 200.6 9 '6t 131.0 O O +> ω 0 TO H Gů O Ol he *> Ϊ— G> O rH <D> O LO LO and- Gů r- <- Γ- ΟΊ WHAT LO TO rH r- * 10 OJ 10 LO 1— LO LO CXj what what what rH rt N 0 what WHAT LO C- and- t— CM LO rH O 5] WHAT what Gů LO LO LO NO. 1 r- LO O with rH lo kD WHAT * xT OJ O § rH what what LO LO LO LO rH LO O Eu O «Κ *. * » << • w > K «Κ in** O O O O O O O O O O 0 1— WHAT what O what * XT LO O 5J what r- t— O LO LO O what r- Ol with O σ> OJ LO what r * Γ- LO 00 Γ- O with rH Ol Ol Ol C- 1— rH Ol O rH O bi rH TO. in * » O O O O O O O O O O tí kD O O- OJ kD Ol what what WHAT kD 5 with. * » TO 0. << ο'Ρ what what ΟΊ C- what what what Gů Ol Oů Ol what Ol OJ Ol Ol rt Μ Gů WHAT what and- Γ Gů Ol O- LO rt TO < O. »» *> Λ LO LO lo LO LO r- O LO O dP al · < Ol kD r- Gů τ — 1 00 no. 1 Ol N WHAT LO 00 Ol LO in TO 'kT dP kD kD kO kD kD kD kD τ — 1 kD O no. 1 rt -, rt oz > I — 1 No x: rH WHOSE what rH O deviations 'rt O AND! Φ 1 x: 1 x: 1 Λ 1 x: T — 1 1 Ol 1 , —1 0, from φ ω what w cn > > O 'rt Ců 0 N> Φ Φ Φ Φ Φ Φ LJ LO 'rt £ £ £ £ C C > φ C 1 o 1 o 1 o 1 o 'rt di 'rt Qj £ -rt '05 Ol x> rt o LO rH rH 1—1 lo 01 ěrodatr > Φ Ό Cu rum Íro Cl, Sm £ ω OQ

• · ·· ·· ··. ·. · · · · · · ··· ·. · * * .....

. ···· ·· ·· ··

In Tables B, C and D below, abbreviations are used, the meaning of which will be clarified in the following paragraphs.

The abbreviation CHMS refers to the proportion of high molecular weight components (i.e., those whose molecular weight is greater than 500,000), the abbreviation CLMS refers to the proportion of low molecular weight components (i.e., those whose molecular weight is less than 3000), abbreviation VLD is used to denote very low density, LD denotes low density, HD denotes high density. The abbreviation CCLDI refers to the crystalline chain length distribution index, the definition of which is described in U.S. Patent No. 5,698,427. The abbreviation CDI (50) denotes the mixture distribution index, which indicates the proportion of polymer that differs from the median distribution of components in a given polymer by a maximum of ± 25 percent. The abbreviation CDI (100) denotes the distribution index of a blend that indicates what proportion of the polymer differs by a maximum of ± 50 percent from the median distribution of the components in a given polymer. Both of the above-mentioned mixture distribution indices are measured using a stepwise increasing temperature elution fractionation (TREF) as described, for example, in the Journal of Polymer Science, Poles. Phys. Ed. 1982, 20, 441 (Wild et al.). A dilute solution of the polymer in a solvent such as 1,2,4-trichlorobenzene is applied to the packed column at high temperature. The column is allowed to cool slowly at 0.1 ° C / minute to room temperature. During the slow cooling process, the ethylene polymer crystallizes on the surface of the packed bed with decreasing temperature in the order of increasing branching (i.e., decreasing crystallinity). After cooling down the column

reheat at a rate of 0.7 ° C / minute, the solvent flowing through the column at a constant rate and the eluent exiting the column is monitored by an infrared concentration detector.

Both the CDI (100) and CDI (50) are similar to the so-called branch distribution index (CDBI), which is defined as the weight percent of copolymer chains in which the comonomer content does not differ by ± 25 percent from the average total molar content of the states. US distribution of branches of comonomer (for details see U.S. Patent No. 5,470,811). The difference between the mixture index (CDBI) and the mixture distribution index in that the average of the branching frequency of the polymer chain (or comonomer content) is used instead of the median comonomer content in the calculation of the CDI index (50). The CDI (50) is calculated from the TREF data by converting the respective elution temperature to the polymer chain branching frequency as described below.

The branching frequency of the polymer chain can be expressed as the average distance (in units of CH ₂ ) between the branches along the polymer main chain or as the length of the crystallizable chain (L), where z

L = 100 / BF and lim L-> 2260

BF-> 0

Using distribution moments that are analogous to molecular weight distribution, it is possible to define numerically mean (L _n ) and mass mean (L _w ) moments for Li, • ·

where:

L _n = 1 / L (L 1) and L _w = L (L 1) where

Wi is the mass fraction of the polymer component i, in which the distance between two adjacent points of the chain branching is equal to Li.

The mixture distribution index or crystalline chain length distribution index (CCLDI) is then defined by:

CCLDI = L _w / L _n

The mean value of the branching frequency is calculated according to the formula:

BF = ^ Wibi i = i where

W i and b i are the mass fraction, respectively, the branching frequency corresponding to the individual bands 1 in the TREF chromatogram.

The CDI (50) is calculated by determining the cumulative mass fraction of the polymer contained within ± 25 percent BF. While the CDI (100) is defined as the cumulative weight fraction of a polymer comprised within ± 50 percent BF.

• · • ·

Table B - Data obtained from polymer characterization

Fractions 1 4 5 6 M _n 10 604 8 320 8 815 8 831 M _w 230 395 227 935 234 524 247 901 M _w / M _n 19.2 27.4 26, 6 28.1 CHMS (percentage) 11.3 13, 1 13.7 14.5 CLMS (percentage) 1.3 2.2 2,0 2,0 VLD (percentage) 3.5 5.7 3, 6 7 LD (percentage) 5.8 7.6 4.9 8.8 HD (percentage) 66.1 62 67.7 64.1 CCLDI 10, 9 12.4 10.6 13, 9 CDI (50) (percentage) 9.8 10.2 8.7 10 CDI (100) (percentage) 19.5 20.2 17.1 19, 7

Table C - Characteristics of Polymer B Characterization

Fractions 1 3 4 5 6 M _n 12 335 11 486 10 957 10 408 10 400 M _w 285 402 236 008 249 496 244 990 248 000 M _w / M _n 23.1 22.9 22.8 23.5 23.8 CHMS (percentage) 17.1 15, 9 15.3 15.0 15.2 CLMS (percentage) 05 / 0, 6 0.7 0.7 0.73 VLD (percentage) 4.2 5.9 2.5 3.8 2.3 LD (percentage) 5.7 7.6 3.8 5.5 co ¹ HD (percentage) 65.5 60, 9 63.8 58 62, 6 CCLDI 11 11.7 9.7 10.5 9.7 CDI (50) (percentage) 11 13, 9 12.5 15.5 14.1 CDI (100) (percentage) 20, 6 26, 5 23.5 28.8 25.3

Table D - Characteristics of Polymer C Characterization

Fractions 1 4 5 6 M _n 13 114 13 081 11 451 11 328 M _w 243 241 236 908 219 370 217 120 M _w / M _n 18.5 18.2 19.2 19.2 CHMS (percentage) 13.7 13, 6 12.6 12.5 CLMS (percentage) 0.7 0.6 0.9 1.0 VLD (percentage) 1.5 2.5 1,8 3.9 LD (percentage) 1.9 3.3 2.9 4,5 HD (percentage) 84.3 77 78, 6 75.4 CCLDI 6, 6 8.4 CO I— ¹ 9.2 CDI (50) (percentage) 4.1 9.2 8.3 11.8 CDI (100) (percentage) 9.3 17.7 16, 11 21.5

Example 14

A bimodal ethylene / hexene copolymer was produced in a laboratory slurry polymerization reactor. In the manufacture of this polymer was used complex prepared in Example 3 of this invention together with a modified methyl alumoxane (MMAO) type 3A, which served as a cocatalyst (this compound is commercially available from Akzo Chemicals, Inc. Under bu _from dním name Modified Methylalumoxane type 3A and is protected by U.S. Patent No. 5,041,584). In this experiment, the modified methylalumoxane (MMAO) type 3A was allowed to react in toluene with the complex prepared in Example 3 for 4 hours prior to the actual polymerization.

0.4 ml of toluene dried over alumina was added to a glass vial of volume

14.2 milliliters (4 drams) which have been previously dried in an oven. 2.0 micromoles (0.067 ml) of the complex of Example 3 as a 0.030 molar solution in deuterated benzene was added to the indicated volume of toluene to give a pale yellow solution. To this solution was added 1.0 millimol (0.52 milliliters) of modified methylalumoxane (MMAO) type 3A in the form of a 1.89 molar solution in heptane, or as a 7 wt. pale yellow reaction solution. The vial was wrapped with aluminum foil and after 4 hours was

0.25 milliliters of said reaction solution (corresponding to 0.5 micromole of zirconium and 0.25 millimolar of MMAO) was added to a reactor containing 600 milliliters of n-hexane, milliliters of 1-hexene and 0.13 milliliters (0.25 millimoles). modified methylalumoxane (MMAO type 3A) (in the form of

1.89 molar solution, or as a weight percent solution, in a heptane solvent). The reaction was carried out at 85 ° C and ethylene pressure for 30 minutes

600 kilopascals (ie 85 psi). The reaction was obtained

44.3 grams of polyethylene polymer (corresponding to an activity of 208471 grams of polyethylene (millimole Zr / hour) at an ethylene pressure of 690 kilopascals (i.e. 100 psi), the polymer having the following characteristics: melt index from

I ₂ ~ 20.9 grams / 10 minutes, I21 = 824.1 grams / 10 minutes,

BBF 9.5 butyl branching / 1000 CH ₂ groups). Molecular Size Chromatography (SEC) yields the following results regarding the molecular weight of the product obtained: number average molecular weight M _n = 9123, weight average molecular weight

M _w = 104,852, M _w / M _n = 11.49. The chromatogram obtained by SEC-size chromatographic separation is shown in the attached Figure 8.

Example 15

5.8 milliliters (10 millimoles) of modified methylalumoxane (MMAO) type 3A (as a 1.74 molar solution in heptane, or as a 6.42 weight percent solution) was added to a 14-liter glass vial in a dry cabinet. 2 milliliters (i.e. 4 drams) which had been previously dried in an oven. To the modified methylalumoxane (MMAO) was added dropwise, with stirring, 15.5 microliters (0.1 millimole) of 2-methyl-1-phenyl-2-propanol to form a clear solution.

0.1 ml of toluene dried over alumina was added to a glass vial in a dry cabinet

14.2 ml (4 drams) which had been previously dried in an oven. 0.5 micromole (6.3 microliter) of the complex of Example 2 as a 0.080 molar solution in toluene was added to the indicated volume of 1-hexene to give a pale yellow solution. To the vial containing the mixture was added 0.25 millimoles (0.13 milliliters) of the modified methylalumoxane (MMAO) / 2-methyl-1-phenyl-2-propanol mixture prepared above from

pale yellow reaction mixture. The vial was heated in an oil bath at 50 ° C for 5 minutes to give a red-brown reaction mixture.

This reaction mixture was added to a 1 liter slurry polymerization reactor containing 600 milliliters.

of n-hexane, 43 mL of 1-hexene and 0.13 mL (0.25 mmol) of the modified methylalumoxane (MMAO) / 2-methyl-1-phenyl-2-propanol mixture, and allowed to react at 85 ° C for 30 minutes and an ethylene pressure of 600 kilopascals (i.e., 85 psi). The reaction yielded 16.3 grams of polyethylene polymer (corresponding to activity)

706 grams of polyethylene (millimole Zr / hour) at an ethylene pressure of 700 kilopascals (100 psi), the polymer having the following properties: melt index

I ₂ = 0.069 grams / 10 minutes, ₁₂ i = 2.15 grams / 10 minutes, MFR = 31.1 and BBF 7.71). Molecular Size Chromatography (SEC) showed the following molecular weight results: number average molecular weight M _n = 54,637, weight average molecular weight M _w = 292,411, PDI = 5.35.

Example 16

5.8 milliliters (10 millimoles) of modified methylalumoxane (MMAO) type 3A (as a 1.74 molar solution in heptane, or as a 6.42 weight percent solution) was added to a 14-liter glass vial in a dry cabinet. 2 milliliters (i.e. 4 drams) which had been previously dried in an oven. To the modified methylalumoxane (MMAO) was added dropwise, with stirring, 15.5 microliters (0.1 millimole) of 2-methyl-1-phenyl-2-propanol to form a clear solution.

0.1 ml of toluene dried over alumina was added to a glass vial in a dry cabinet

14.2 milliliters (4 drams) which had been previously dried in an oven. 0.5 micromoles (6.3 microliters) of the complex of Example 2 as a 0.080 molar solution in toluene was added to said volume of toluene to give a pale yellow solution. To the vial containing the mixture was added 0.25 millimoles (0.13 milliliters) of the modified methylalumoxane (MMAO) / 2-methyl-1-phenyl-2-propanol mixture prepared above to give a light yellow reaction mixture. The vial was heated in an oil bath at 50 ° C for 15 minutes to give a red-brown reaction mixture.

The reaction mixture was added to a 1 liter slurry polymerization reactor containing 600 ml of n-hexane, 43 ml of 1-hexene and 0.13 ml (0.25 mmol) of modified methylalumoxane (MMAO) / 2-methyl -1-phenyl-2-propanol, and was allowed to react at 85 ° C and ethylene pressure of 600 kilopascals (i.e. 85 psi) for 30 minutes. The reaction yielded 13.2 grams of polyethylene polymer (corresponding to activity)

118 grams of polyethylene (millimole Zr / hour) at an ethylene pressure of 700 kilopascals (i.e., 100 psi), the polymer having the following properties: melt index

I ₂ = 0.248 grams / 10 minutes, I ₂ i = 7.85 grams / 10 minutes,

MFR = 31.6 and BBF 6.30). Chromatographic separation (SEC) showed the following results with respect to the molecular weight of the product obtained:

z number average molecular weight M _n = 42,411, weight average molecular weight M _w = 205,990, PDI = 4.86.

All documents cited above, including all priority documents and / or test procedures, are incorporated herein by reference. As will be apparent from the foregoing general description and the description of specific embodiments of the present invention, various changes may be made to the above-described procedures without departing from the scope of the present invention.

Accordingly, the scope of the present invention is not limited in any way by the above examples.

Claims (35)

PATENT CLAIMS An olefin polymerization catalyst composition comprising the product of mixing at least one activating agent and one of a component selected from the group consisting of: a) at least two different transition metal compounds of general formula (I) ((Z) XAt (YJ)) qMQ _n (I) wherein M is a metal selected from Group 3 to Group 13 or from the group of lanthanides or actinoids of the Periodic Table of the Elements; Q is a group bound to M and each Q is a monovalent, divalent or trivalent anion; X and Y are groups bound to M and independently represent a carbon atom or a heteroatom, wherein at least one of X and Y is a heteroatom and Y is part of the heterocyclic ring J; J is a heterocyclic ring containing from 2 to 50 atoms, which are not hydrogen; • · ·· • · Z is a group bound to X, wherein Z contains from 1 to 50 non-hydrogen atoms; is 0 or 1, wherein when t is 1, the bridging group is bonded to at least one of X, Y or J; q is 1 or 2; is the oxidation state of the group M - q 1, if the group Q is a monovalent anion; is (oxidation state of group M - q) / 2, Q is a divalent anion; or is (oxidation state of group M Q is a trivalent anion; or if a group q) / 3 if group b) mixing the transition metal compound of the above formula (I) and an additive; or c) a compound of general formula ((Z) XA _t (YJ)) _q MQ _m T _s M is a metal selected from Groups 3 to 13 of the Periodic Table or from the group of lanthanides and actinoids; T is a group bound to M and represents an element of Group 13-16, wherein T may also be bound to one or more groups containing 1 to 50 carbon atoms optionally containing one or more heteroatoms; Q are groups bound to M and each Q is a monovalent, divalent or trivalent anion; X and Y are groups bound to M and independently represent a carbon atom or a heteroatom, wherein at least one of X and Y is a heteroatom and Y is part of the heterocyclic ring J; J is a heterocyclic ring containing from 2 to 50 carbon atoms which are not hydrogen atoms; Z is a group containing from 1 to 50 non-hydrogen atoms; t is the number 0 or 1, and when t is 1 A is a bridging group bonded to at least one of X, Y or J, preferably to X and J; ✓ q is the number 1 or 2; m is the oxidation state of the group M - q - s, if the group Q is a monovalent anion; · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · m is (oxidation state of group M - q - s) / 2 when group Q is a divalent anion; or m is (oxidation state of group M - q - s) / 3 when group Q is a trivalent anion; with is 1, 2, or 3, which have been allowed to react for at least Fifteen minutes. 2. The composition of claim 1 wherein: t is 1; OF is bonded to one or more R 'groups independently selected from hydrogen or linear, branched alkyl or cyclic alkyl, alkenyl, alkynyl or aryl groups; wherein two or more R 'groups may be joined to form a cyclic group, optionally the R' group may be linked to a group A; and J is substituted with two or more R '' groups, which are independently selected from the group consisting of of a hydrogen atom or a linear, branched, cyclic alkyl or alkenyl group, alkynyl group, alkoxy group, aryl group or aryloxy group, wherein two or more R '' groups may be joined to form a cyclic group or the R '' group may be bonded to Group A. The composition of claim 1, wherein t is 1; Z is bonded to one or more R 'groups independently selected from the group consisting of hydrogen or linear, branched alkyl or cyclic alkyl groups, alkenyl groups, alkynyl groups or aryl groups; wherein two or more R 'groups may be joined to form a cyclic group, optionally the R' group may be linked to a group A; and J is substituted with two or more R '' groups independently selected from hydrogen or linear, branched, cyclic alkyl or alkenyl, alkynyl, alkoxy, aryl or aryloxy groups, wherein two or more groups R '' may be joined to form a cyclic group, or the group R '' may be attached to group A. A composition according to claim 1, characterized in that T is a hydrocarbyl group, a boronate group, an amide group or a cyclopentadiene group. of 5. The composition of claim 1, wherein: T is an alkoxide group, an acetylacetonate group, a carboxylate group, a phenoxide group, or a combination thereof. 6. The composition of claim 1 wherein n is 2 or 3 and the second catalyst is the same as the first catalyst except that one Q is a hydrocarbyl, boronate, or amide group. 7. The composition of claim 1 wherein n is 2 or 3 and the second catalyst is the same as the first catalyst except that one Q is alkoxide, phenoxide, acetylacetonate, carboxylate, cyclopentadienyl, fluorenyl or indenyl. 8. The composition of claim 1 wherein n is 2 or 3 and the second catalyst is the same as the first catalyst except that one group Q in said second catalyst is a hydrocarbon adduct of an analogous group Q contained in the structure of the first catalyst. 9. A composition according to claim 8 wherein said hydrocarbon adduct is an alkoxide adduct, boronate adduct or amide adduct, phenoxide adduct, acetylacetonate adduct or carboxylate adduct. 10. The composition of claim 1 wherein said additive is an alkoxy compound of the formula 11. 12. 13. · · • • • · · R = 0 where R is a group containing from 1 to 100 carbon atoms, wherein the oxygen atom may be bonded at any point along the entire chain of the R group, and the R group may contain heteroatoms in addition to 1 to 100 carbon atoms. The composition of claim 1, wherein said additive is one or more compounds selected from acetone, benzophenone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tert. butyl ketone, acetophenone, cyclohexanone, cyclopentanone, benzaldehyde, pivaldehyde, ethyl-n-propylketone and ethylisopropylketone. The composition of claim 1 wherein the M group in all said transition metal compounds is titanium, zirconium or hafnium. A composition according to claim 1 wherein all Q groups are independently selected from the group consisting of boronates, halogen atoms, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarbyl, or phenoxy having 1 to 20 carbon atoms, amides, phosphides, sulfides, silylalkyl groups, diketones and carboxylates and / or X and Y independently represent a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom and / or 14. 15 Dec 16. 17. 18. Z is an aryl group and / or J is pyridine. 14. The composition of claim 1, wherein the two different transition metal compounds are [1- (2-pyridyl) N1-methylethyl] [1H-2,6-diisopropylphenylamido] zirconium tribenzyl and [[1- (2-pyridyl) N1]. methylethyl] [1'-2,6-diisopropylphenylamido]) [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl. The composition of claim 1 wherein said activating agent is an alumoxane, a non-coordinating anion or a modified methylalumoxane. An olefin polymerization process comprising contacting an olefin with a catalyst composition according to any one of claims 1 to 15. The process of claim 26 wherein said olefin comprises one or more monomers having 2 to 30 carbon atoms. The process of claim 26 wherein said olefin comprises ethylene or ethylene alone in admixture with one or more hydrocarbons selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- octene, 1-decene, 3-methyl-1-pentene. Process according to claim 16, 17 or 18, characterized in that the temperature in the reactor is varied in order to change it 19 Dec • · · · · · 20 May 21. 22nd 23. the value of the ratio M _w / M _n of the polymer produced compared to the ratio M _w / M _{n of the} polymer produced before said temperature change. The method of claim 16, 17 or 18, wherein the temperature of said catalyst system before the catalyst system is injected into the reactor is varied to change the M _w / M _n ratio of the polymer produced compared to the M _w / M _n ratio of the polymer produced. before the temperature change. The method of claim 16, 17 or 18, wherein the ratio of the amount of activating agent to the amount of catalyst is varied to change the value of the ratio M _w / M _r . the polymer produced compared to the ratio M _w / M _{n of the} polymer produced prior to changing said ratio. The method of claim 16, 17 or 18 wherein the ratio of said first catalyst to said second catalyst is from 5:95 to 95: 5. The method of claim 16, 17 or 18, further comprising a method for controlling the molecular weight distribution (M _w / M _n ), melt index and / or density, which comprises making changes directly to the a gas phase polymerization reactor of 42.5 m ³ or more (i.e., 1500 ft ³ or more), the changes including a change in the reaction temperature and / or a change in the amount of catalyst of the present invention in a well mixed catalyst solution and / or change concentration 24. 25. · · · · · · · · · · · · * <<<<<<<<<<<<<<<<< And / or changing the ratio of the amount of said activating agent to the amount of transition metal. A polymer which is produced by a process according to any one of claims 16 to 23. A polyolefin having an M _w / M _n ratio of 10 or more, wherein the melt indexes of fractions 1, 4 and 6 of said polyolefin do not differ by more than 20 percent relative to the mean melt index of fractions 1, 4, and 6, fractions 1, 4 and 6 are obtained using the following sieves: Sieve size Collected faction Faction designation 10 mesh > 2000 micrometers Fraction 1 18 mesh 2000 to 1000 micrometers Fraction 2 35 mesh <1000 to 500 micrometers Fraction 3 60 mesh <500 to 250 micrometers Fraction 4 120 mesh <250 to 125 micrometers Fraction 5 pan <125 micrometers Fraction 6 26. The polyolefin of claim 25 wherein said polyolefin is an ethylene homopolymer or a copolymer of ethylene and a linear, branched, or cyclic olefin containing from 3 to 20 carbon atoms. The polyolefin of claim 25, wherein said polyolefin is a copolymer of ethylene and one or more hydrocarbons selected from the group consisting of: 27 Mar: 28. 29. 30. propylene, butene, hexene, pentene, heptene, octene, nonene, decene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene and dodecene. Polyolefin according to claim 25, 26 or 27, characterized in that: (a) the percent crystallinity of fractions 1, 4 and 6 of said polyolefin does not differ by more than 6 percent relative to the mean crystallinity of fractions 1, 4 and 6; and / or (b) the ratio M _w / M _{n of} fractions 1, 4 and 6 of said polyolefin does not differ by more than 20 percent relative to the mean value of the ratio M _w / M _{n of} fractions 1, 4 and 6 and / or c) Fraction 1 crystal aspect ratio is 0.5 to 1.5, Fraction 4 crystal aspect ratio is 1.2 to 4, and Fraction 6 crystal aspect ratio is approximately 1.75 to 5, provided that the crystal aspect ratios of the individual fractions differs by at least 0.3. Polyolefin according to claim 28, characterized in that the crystal aspect ratios of said fractions differ by at least 0.5, preferably by at least 1.0. The polyolefin of claim 28 wherein the M _w / M _n ratio is 20 or more. A film, characterized in that it is produced by blowing, extruding or casting a polyolefin produced according to any one of claims 24 to 30. 31. 100 ALIGN! 32. 33. 34. 35. Molded article, characterized in that it is produced by blow molding or extrusion molding of a polyolefin produced according to any of claims 24 to 30. Polyolefin according to any one of claims 24 to 30, characterized in that the graph obtained by chromatographic separation based on the molecular size (SEC) of said polymer comprises one rising curve, one falling curve, one inflection point and the ratio M _w / M _n of the polymer is 20 or more. Polyolefin according to any one of claims 24 to 30, characterized in that the graph obtained by chromatographic separation based on the molecular size (SEC) of said polymer comprises two or more rising curves, two or more falling curves, three or more inflection points and a ratio M _w / M _n of this polymer is 10 or more. Polyethylene according to any one of claims 24 to 30, characterized in that the graph obtained by chromatographic separation based on the molecular size (SEC) of said polymer comprises one or more rising curves, one or more falling curves, one or more inflection points, M _w ratio The µ _{m of} this polymer is 10 or more, and the curve change on any of the curves is 20 percent or more compared to the curve before this change.