KR100490509B1 - Polyolefin composition with molecular weight maximum occuring in that part of the composition that has the highest comonomer content - Google Patents

Abstract

The present invention provides a method for polymerizing one α-olefin monomer with one or more olefin comonomers, produced by a catalyst having a metallocene complex in a single reactor and having 50% by weight of the composition having the highest comonomer content (% by weight). It relates to a polyolefin copolymer composition having a maximum molecular weight in the% portion. Preferably, the composition has a comonomer partition coefficient C _{pf of at} least 1.10 or a molecular weight partition coefficient M _{pf of} at least 1.15. In addition, preferred compositions have at least 0.01 long chain branches per 1000 carbon atoms along the polymer backbone. Such compositions by reverse molecular engineering have excellent properties due to the simultaneous presence of high molecular weight and long chain branches with high comonomer content and can be easily processed.

Description

POLYOLEFIN COMPOSITION WITH MOLECULAR WEIGHT MAXIMUM OCCURING IN THAT PART OF THE COMPOSITION THAT HAS THE HIGHEST COMONOMER CONTENT}

The present invention is produced by a single metallocene catalyst in a single reactor from one α-olefin monomer and one or more α-olefin comonomers, having the highest molecular weight at the highest monomer content and preferably having a long chain branching. Polyolefin copolymer compositions, and methods for preparing these materials and catalysts used therefor.

Recently, many advances have been made in the production of polyolefin copolymers by the introduction of metallocene catalysts. Metallocene catalysts have the advantage of being generally more active than traditional Ziegler catalysts and have been reported to exhibit single-site catalyst properties. Because of this single-site property, the polyolefin copolymers produced by metallocene catalysts exhibit a fairly uniform molecular structure. For example, compared to materials produced by traditional Ziegler catalysts, the single-site metallocene catalyst has a relatively narrow molecular weight distribution (MWD) and a narrow short chain branch distribution (SCBD). The narrow distribution of short chain branches means that the frequency of short chain branches formed when the comonomer is incorporated into the polyolefin chain is relatively independent of molecular weight. Although certain properties of metallocene products are enhanced by narrow molecular weight distributions, there are often difficulties in processing these materials into useful products and films compared to materials produced by Ziegler catalysts. In addition, the uniform nature of the short chain branching distribution of the material produced by the metallocene catalyst does not readily allow certain structures to be obtained.

One attempt to improve processability is to incorporate long chain branching (LCB), which is particularly desirable in terms of improving processability without compromising advantageous properties. U.S. Patent 5,272,236, U.S. Patent 5,278,272, U.S. Patent 5,380,810, EP 659,773, EP 676,421, and WO 94/07930 relate to a process for preparing polyolefins having long chain branches.

Another attempt is to add a polymer processing aid to the polymer before it is made into a film or product. This requires additional processing and is expensive.

Another approach to this problem is to prepare compositions that are blends or mixtures of individual polymeric materials with the goal of maximizing advantageous properties while minimizing processing problems. This requires special processing that increases the cost of the material produced. U.S. Patent 4,598,128, U.S. Patent 4,547,551, U.S. Patent 5,408,004, U.S. Patent 5,382,630, U.S. Patent 5,382,631 and U.S. Patent 5,326,602, and WO 94/22948 and WO 95/25141 relates to blends.

Another way to change the SCBD and provide a solution to the problem of processability has been the development of various stepwise processes, in which the material is prepared by a series of polymerizations under different reaction conditions, for example in a series of reactors. In essence, a material of a type similar to a blend is produced, which has one of the physical properties, such as a modality greater than the molecular weight distribution. Polyolefin compositions featuring excellent processability can be produced in this way, but these methods are expensive and complex compared to the use of a single reactor. Interesting methods are disclosed in US Pat. No. 5,442,018, WO 95/26990, WO 95/07942 and WO 95/10548.

Another potentially viable attempt to improve processability and change the SCBD is to use a multicomponent catalyst. In some cases, catalysts having a metallocene catalyst and a conventional Ziegler-Natta catalyst on the same support were used for the polyolefin polymerization, and in other cases two metallocene catalysts were used for the polyolefin polymerization to produce a polycrystalline material. . Components of different molecular weights and compositions are prepared in a single reactor operating under a set of polymerization conditions. Such attempts are difficult in terms of process control and catalyst preparation. Interesting catalyst systems are disclosed in WO 95/11264 and EP 676,418.

Summary of the Invention

It is desirable to be able to produce polyolefin copolymer compositions having the highest molecular weight and very easy processing in the portion of the composition with the highest number of short chain branches. In addition, using a single reactor operating under a set of reaction conditions semi-continuously or preferably continuously, preferably using a single metallocene catalyst, preferably a supported catalyst, in a gas phase polymerization process. It is desirable to be able to achieve it. In particular, it is desirable to be able to produce polyolefin copolymer compositions having the largest molecular weight and having significant long chain branches in the portion of the composition with the highest number of short chain branches.

The short chain branch distribution of the polyolefin composition due to incorporation of the α-olefin comonomers during the polymerization of the α-olefin monomers can be examined by several techniques, such as, for example, ATREF-DV and GPC-FTIR. If the material of the composition is divided into several parts starting at one end of the distribution or at the other end, the relationship between the high short chain branching content and the molecular weight due to the high comonomer content can be determined.

In one embodiment, the present invention is a polyolefin copolymer composition produced by a catalyst having a metallocene complex in a single reactor in a method of polymerizing one α-olefin monomer with one or more olefin comonomers, the composition comprising a polymer The molecular weight is maximum in the 50% by weight portion of the composition with the long chain branching along the backbone and the highest comonomer content (% by weight).

A preferred embodiment of the present invention is a polyolefin copolymer composition having 1.10 or more comonomer distribution factor C _pf or more 1.15 or more molecular weight distribution coefficient has a M _pf, or 1.10 the comonomer distribution factor C _pf and more than 1.15, a molecular weight distribution factor M _pf and Where the comonomer partition coefficient C _pf is calculated from Equation 1 and the molecular weight partition coefficient M _pf is calculated from Equation 2:

Where

c _i is the mole fraction of the comonomer content,

w _i is the normalized weight fraction measured by GPC / FTIR for n FTIR data points above the median molecular weight,

c _j is the mole fraction of the comonomer content,

w _j is the normalized weight fraction measured by GPC / FTIR for m FTIR data points below the median molecular weight, where only the weight fraction w _i or w _j associated with the mole fraction value of the comonomer content is used to calculate C _pf . Used,

n and m are three or more.

Where

M _i is the viscosity average molecular weight,

w _i is the normalized weight fraction measured by ATREF-DV for n data points at fractions below the intermediate elution temperature,

M _j is the viscosity average molecular weight,

w _j is the normalized weight fraction measured by ATREF-DV for m data points at fractions above the median elution temperature, where only the weight fraction w _i or w _j associated with a viscosity average molecular weight greater than zero calculates M _pf Used to

n and m are three or more.

In another embodiment, the present invention is a polyolefin copolymer composition produced in a single reactor by a catalyst having a metallocene complex in a continuous gas phase process in which one α-olefin monomer and one or more olefin comonomers are polymerized. The composition has a comonomer partition coefficient C _{pf of at} least 1.10 or a molecular weight partition coefficient M _{pf of} at least 1.15 or a comonomer partition coefficient C _{pf of at} least 1.10 and a molecular weight partition coefficient M _{pf of} at least 1.15, wherein the comonomer partition coefficient C _pf and Molecular weight partition coefficient M _pf is as defined above).

In another embodiment, the present invention provides a polyolefin copolymer composition produced in a single reactor by a catalyst having a bis-Cp metallocene complex in a method of polymerizing one α-olefin monomer and one or more olefin comonomers, the composition has a 1.10 or more comonomer distribution number C _pf or molecular weight distribution coefficient of more than M has a _pf or 1.10 or more to 1.15 the comonomer distribution factor C _pf and 1.15 or more molecular weight distribution factor M _pf (At this time, the comonomer distribution factor C _pf And the molecular weight partition coefficient M _pf is as defined above).

In a further embodiment, the present invention is a polyolefin copolymer composition produced in a single reactor by a catalyst having an organometallic compound in a method of polymerizing one α-olefin monomer and one or more olefin comonomers, the composition comprising a polymer The molecular weight is maximal in the 50% by weight portion of the composition with long chain branching along the backbone and the highest comonomer content (% by weight).

Polymerization methods for providing the aforementioned compositions are within the scope of the present invention, and one embodiment is a method of polymerizing one α-olefin monomer and one or more olefin comonomers using a metallocene catalyst in a single reactor, The resulting composition has a maximum molecular weight in the 50% by weight portion of the polymer having long chain branching along the polymer backbone and the highest comonomer content (% by weight). Preferred embodiment, a case where the polymer having 1.10 or more comonomer distribution factor C _pf or more 1.15 or more molecular weight distribution coefficient has a M _pf, or 1.10 the comonomer distribution factor C _pf and more than 1.15, a molecular weight distribution factor M _pf (wherein comonomer Partition coefficient C _pf and molecular weight partition coefficient M _pf are as defined above).

Another embodiment of the present invention is a continuous gas phase process for polymerizing one α-olefin monomer and one or more olefin comonomers using a catalyst having a metallocene complex in a single reactor, wherein the method has a comonomer distribution of at least 1.10. factor C _pf or more 1.15 or more molecular weight distribution coefficient has a M _pf, or 1.10 the comonomer distribution factor C _pf and more than 1.15, a molecular weight distribution factor M composition having a _pf (where the comonomer distribution factor C _pf and the molecular weight distribution factor M _pf is defined above As shown).

Another embodiment of the present invention is a method of polymerizing one α-olefin monomer and one or more olefin comonomers using a catalyst having a bis-C _p metallocene complex in a single reactor, wherein the method comprises at least 1.10 covalent monomer distribution factor C _pf or more 1.15 or more molecular weight distribution coefficient has a M _pf, or 1.10 the comonomer distribution factor C _pf and more than 1.15, a molecular weight distribution factor M composition having a _pf (where the comonomer distribution factor C _pf and the molecular weight distribution factor M _pf is As defined above).

A further embodiment of the invention is a method of polymerizing one α-olefin and one or more olefin comonomers in a single reactor using a catalyst having an organometallic compound, wherein the resulting composition is a long chain branching along the polymer backbone. Molecular weight is maximum in the 50% by weight portion of the composition having the highest comonomer content (% by weight).

Another embodiment of the present invention is a method of polymerizing one α-olefin and one or more olefin comonomers in a single reactor using a catalyst having an organometallic compound, wherein the resulting composition is long-chain branched along the polymer backbone. Molecular weight is maximum in the 50% by weight portion of the composition having the highest comonomer content (% by weight).

The compositions of the present invention have desirable properties and have a melt strength greater than 4 cN, a seal strength greater than 1.9 kg (4.2 lb), a hot tack greater than 0.23 kg (0.5 lb) or a dart output greater than 100 g. It can be easily processed into films or other products with strength.

Further embodiments of the invention

(A) a polyolefin copolymer composition produced in a single reactor by a catalyst having a metallocene complex in a process for polymerizing one α-olefin monomer and one or more olefin comonomers, the composition comprising a long chain branching Having a maximum molecular weight in the 50% by weight portion of the composition having the highest comonomer content (% by weight); And

(B) relates to a blend of two or more resin components, comprising from about 99% to about 1% by weight of one or more resins different from component (A).

Another embodiment of the invention

(A) a polyolefin copolymer composition produced in a single reactor by a catalyst having a metallocene complex in a continuous-phase process in which one α-olefin monomer and one or more olefin comonomers are polymerized, wherein the composition has a comonomer distribution of at least 1.10. _{Has a} coefficient C _pf or a molecular weight distribution coefficient M _{pf of} at least 1.15 or a comonomer distribution coefficient C _{pf of at} least 1.10 and a molecular weight distribution coefficient M _{pf of} at least 1.15, wherein the comonomer distribution coefficient C _pf and the molecular weight distribution coefficient M _pf are defined above About 1 to about 99 weight percent; And

(B) A blend of two or more resin components, comprising from about 99% to about 1% by weight of one or more resins different from component (A).

1 is an ATREF-DV plot for the composition of Example 1. FIG.

2 is an ATREF-DV plot for the composition of Example 2. FIG.

3 is an ATREF-DV plot for the composition of Example 3. FIG.

4 is an ATREF-DV plot for the composition of Example 4. FIG.

5 is an ATREF-DV plot for the composition of Example 5. FIG.

FIG. 6 is an ATREF-DV plot for the composition of Comparative Example D, Dowlex (commercially available polyethylene produced by Ziegler-Natta catalyst).

FIG. 7 is an ATREF-DV plot for the composition of Comparative Example A, BP Innovex (tradename) 7209.

FIG. 8 is an ATREF-DV plot for the composition of Comparative Example B, Exxon Exceed ™ 401. FIG.

FIG. 9 is an ATREF-DV plot for the AFFINITY produced by the composition of Comparative Example E, Solution Insight Metallocene.

10 is an ATREF-DV plot for the composition of Comparative Example C, Novacore (gas phase produced polyethylene).

11 is a plot of GPC-FTIR data for the composition of Example 1. FIG.

12 is a plot of GPC-FTIR data for the composition of Example 2. FIG.

FIG. 13 is a plot of GPC-FTIR data for the composition of Example 3.

14 is a plot of GPC-FTIR data for the composition of Example 5. FIG.

For elements or metals belonging to a particular group herein, see the Periodic Table of the Elements issued by CRC Press Inc. (CRC Press Inc., 1989). Also any group (s) referenced will be the group (s) as shown in the Periodic Table of the Elements using the IUPAC system for group numbering.

Suitable catalysts may be derivatives of any transition metal, including Group 3, Group 4 or lanthanide metals which exist in formal oxidation states of +2, +3 or +4. Preferred compounds include metal complexes containing 1 to 3 π-bonded anionic or neutral ligand groups, which may be cyclic or acyclic unlocalized π-bonded anionic ligand groups. Examples of such π-bonded anionic ligand groups are conjugated or unconjugated, cyclic or acyclic dienyl groups, allyl groups and arene groups. The term "π-bonded" means that the ligand group is bound to the transition metal by π-bonding.

Each atom in the unlocalized π-bonded group may be independently substituted by a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl and hydrocarbyl-substituted metalloid radicals, wherein the metalloid Is selected from Group 14 of the Periodic Table of the Elements, such hydrocarbyl- or hydrocarbyl-substituted metalloid radicals are further substituted with residues containing a group 15 or 16 hetero atom. The term "hydrocarbyl" includes C _1-20 linear, branched and cyclic alkyl radicals, C _6-20 aromatic radicals, C _7-20 aryl-substituted aromatic radicals and C _7-20 aryl-substituted alkyl radicals. do. In addition, two or more such radicals may form a fused ring system, a hydrogenated fused ring system, or a metallocycle with a metal. Suitable hydrocarbyl-substituted organometallic radicals include mono-, di- and trisubstituted organometallic radicals of Group 14 elements, wherein each hydrocarbyl group contains 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometallic radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgeryl and trimethylgeryl groups. Examples of residues containing Group 15 or Group 16 atoms include amine, phosphine, ether or thioether residues, or divalent derivatives thereof, such as transition metals or lanthanide metals, and hydrocarbyl groups or hydrocarbyl-substituted metals. Amide, phosphide, ether or thioether groups bound to the lloy containing group.

Examples of suitable anionic delocalized π-bonded groups are cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadiee Nil, dihydroanthracenyl, hexahydroanthracenyl and decahydroanthracenyl groups, as well as C _1-10 hydrocarbyl-substituted or C _1-10 hydrocarbyl-substituted silyl substituted derivatives thereof. Preferred anionic delocalized π-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, Fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl and tetrahydroindenyl.

Suitable classes of catalysts are transition metal complexes corresponding to the following formula or dimers thereof:

Where

L is an anionic unlocalized π-bonded group bonded to M, containing up to 50 non-hydrogen atoms, optionally two L groups can be linked together to form a crosslinked structure, and Optionally one L may be bonded to X;

M is a Group 4 metal of the Periodic Table of the Elements in a formal oxidation state of +2, +3 or +4;

X is any divalent substituent of up to 50 non-hydrogen atoms that together with L form a metallocycle with M;

X 'is any Lewis base having up to 20 non-hydrogen atoms;

Each X ″ is a monovalent anionic moiety having up to 40 non-hydrogen atoms, and optionally two X ″ groups can be covalently bonded together to form a bivalent anionic moiety having two valences bound to M or Optionally, the two X "groups can be covalently bonded together to form a neutral conjugated or non-conjugated diene π-bonded to M (if M is in the +2 oxidation state), or optionally optionally at least one X" and one Or more X's join together to form residues both covalently bonded to M and coordinated by a Lewis base functional group;

ℓ is 0, 1 or 2;

m is 0 or 1;

n is a number from 0 to 3;

p is an integer from 0 to 3;

The sum of l, m, and p is the same as the formal oxidation state of M, but in this case l and m except when two X ″ groups together form a neutral conjugated or nonconjugated diene that is π-bonded to M. The sum of is equal to the formal oxidation state of M.

Preferred complexes include complexes containing one or two L groups. The latter complex includes complexes containing a bridging group connecting two L groups. Preferred crosslinking groups correspond to the formula (ER ^* ₂ ) _x , wherein E is silicon, germanium, tin or carbon, and R ^* is each independently hydrogen or from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof Is a group selected, wherein R ^* has up to 30 carbon or silicon atoms and x is 1 to 8. Preferably, R ^* is each independently methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of complexes containing two L groups are compounds corresponding to formula I or formula II:

M is zirconium, zirconium or hafnium, preferably zirconium or hafnium in a formal oxidation state of +2 or +4;

Each R ³ is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germanyl, cyano, halo, and combinations thereof, wherein R ³ has up to 20 non-hydrogen atoms or is adjacent to R ³ The groups together form a divalent derivative (ie a hydrocarbodiyl, siladiyl or germanadiyl group), thereby forming a fused ring system;

X ″ is independently an anionic ligand group of up to 40 non-hydrogen atoms each, or two X ″ groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms, or together together 4 to 30 non-hydrogen groups A conjugated diene having an atom to form a π-complex having M, wherein M is in a formal oxidation state of +2;

R ^* , E and x are as defined above.

The metal complex is particularly suitable for the preparation of a polymerizer having a stereoregular molecular structure. For this performance, the complex preferably has a C _S symmetry or a chiral, stereorigid structure. Examples of the first type are compounds having different unlocalized π-bonded systems such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti (IV) or Zr (IV) are described in Ewen et al. Am. Chem. Soc. 110, 6255-6256 (1980), for the preparation of syndiotactic olefin polymers. Examples of chiral structures include racemic bisdenyl complexes. Similar systems based on Ti (IV) or Zr (IV) are described by Wild et al. Organomet. Chem. 232, 233-47 (1982), for the preparation of isotactic olefin polymers.

Examples of crosslinked ligands containing two π-bonded groups include (dimethylsilyl-bis (cyclopentadienyl)), (dimethylsilyl-bis (methylcyclopentadienyl)), (dimethylsilyl-bis ( Ethylcyclopentadienyl)), (dimethylsilyl-bis (tert-butylcyclopentadienyl)), (dimethylsilyl-bis (tetramethylcyclopentadienyl)), (dimethylsilyl-bis (indenyl)) , (Dimethylsilyl-bis (tetrahydroindenyl)), (dimethylsilyl-bis (fluorenyl)), (dimethylsilyl-bis (tetrahydrofluorenyl)), (dimethylsilyl-bis (2-methyl- 4-phenylindenyl)), (dimethylsilyl-bis (2-methylindenyl)), (dimethylsilyl-cyclopentadienyl-fluorenyl), (dimethylsilyl-cyclopentadienyl-octahydrofluorenyl ), (Dimethylsilyl-cyclopentadienyl-tetrahydrofluorenyl), (1,1,2,2-tetramethyl-1,2-dissilyl-bis-cyclopentadienyl), (1 , 2-bis (cyclotentadienyl) ethane) and (isopropylidene-cyclopentadienyl-fluorenyl).

Preferred X ″ groups are selected from the group of the hamidides, hydrocarbyl, silyl, germanyl, halohydrocamyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl, or two X ″ groups together form a divalent derivative of conjugated diene or are neutral together to form π-bonded conjugated dienes. Most preferred X ″ group is a C _1-20 hydrocarbyl group.

A further class of metal complexes used in the present invention corresponds to the above formula L _l MX _m X ' _n X " _p or dimers thereof, wherein X together with L form up to 50 or less metallocycles having M It is a divalent substituent of a non-hydrogen atom.

Preferred divalent X substituents include one or more atoms (ie, oxygen, sulfur, boron, or a Group 14 element of the periodic table directly bonded to an unlocalized π-bonded group), and nitrogen, phosphorus, oxygen, or sulfur (ie, covalently bonded to M). Group containing up to 30 non-hydrogen atoms, including different atoms selected from the group including the above.

A preferred class of such Group 4 metal coordination complexes used according to the invention corresponds to the formula:

Where

M is titanium or zirconium in a formal oxidation state of +2 or +4;

Each R ³ is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germanyl, cyano, halo, and combinations thereof, wherein R ³ has up to 20 non-hydrogen atoms, or adjacent R ³ groups Together form a divalent derivative (ie hydrocarbodiyl, siladiyl or germanadiyl group) and thereby form a fused ring system;

Each X "is a halo, hydrocarbyl, hydrocarbyloxy or silyl group and the group has up to 20 non-hydrogen atoms, or two X" groups together form a neutral C _5-30 conjugated diene or a divalent derivative thereof Forming;

Y is -O-, -S-, -NR ^* -and -PR ^* -;

Z is SiR ^* ₂ , CR ^* , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ , where R ^* is as defined above .

Particularly preferred groups of transition metal complexes for use in the catalysts of the present invention are those disclosed in U.S. Patent No. 5,470,993, which is incorporated herein by reference, corresponds to Formula 1:

Where

M is titanium or zirconium in a formal oxidation state of +2;

L is a group containing a cyclic unlocalized anionic π-system which is bonded to M and also to Z;

Z is a moiety of 60 or less non-hydrogen atoms which is bonded to M via σ-bond, which contains elements of group 14 of the boron or periodic table of the elements and contains an element selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen ego;

X, together with M, forms a π-complex and is a neutral conjugated or nonconjugated diene of up to 40 carbon atoms optionally substituted with one or more groups selected from hydrocarbyl or trimethylsilyl groups.

Examples of Group 4 metal complexes that may be used in the practice of the present invention include:

Cyclopentadienyl titanium trimethyl,

Cyclopentadienyl titanium triethyl,

Cyclopentadienyl titanium triisopropyl,

Cyclopentadienyl titanium triphenyl,

Cyclopentadienyl titanium tribenzyl,

Cyclopentadienyl titanium-2,4-dimethylpentadienyl,

Cyclopentadienyl titanium-2,4-dimethylpentadienyl triethylphosphine,

Cyclopentadienyl titanium-2,4-dimethylpentadienyl trimethylphosphine,

Cyclopentadienyl titanium dimethylmethoxide,

Cyclopentadienyl titanium dimethyl chloride,

Pentamethylcyclopentadienyltitaniumtrimethyl,

Indenyl titanium trimethyl,

Indenyl titanium triethyl,

Indenyl titanium tripropyl,

Indenyl titanium triphenyl,

Tetrahydroindenyl titanium tribenzyl,

Pentamethylcyclopentadienyl titanium triisopropyl,

Pentamethylcyclopentadienyltitaniumtribenzyl,

Pentamethylcyclopentadienyl titanium dimethylmethoxide,

Pentamethylcyclopentadienyl titanium dimethyl chloride,

Bis (η ⁵ -2,4-dimethylpentadienyl) titanium,

Bis (η ⁵ -2,4-dimethylpentadienyl) titanium trimethylphosphine,

Bis (η ⁵ -2,4-dimethylpentadienyl) titanium triethylphosphine,

Octahydrofluorenyl titanium trimethyl,

Tetrahydroindenyl titanium trimethyl,

Tetrahydrofluorenyl titanium trimethyl,

(Tert-butylamido) (1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl) dimethylsilanetitaniumdimethyl,

(Tert-butylamido) (1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl) Dimethylsilanetitanium dimethyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium dibenzyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium dimethyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dimethyl,

(Tert-butylamido) (tetramethyl-η ⁵ -indenyl) dimethylsilanetitanium dimethyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (III) 2- (dimethylamino) benzyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (III) allyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (III) 2,4-dimethylpentadienyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 1,3-pentadiene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 2,4-hexadiene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) isoprene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) 1,3-butadiene,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) isoprene,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) dimethyl,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) dibenzyl,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) 1,3-butadiene,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (II) 1,3-pentadiene,

(Tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 1,3-pentadiene,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dimethyl,

(Tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dibenzyl,

(Tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 1,3-pentadiene,

(Tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 2,4-hexadiene,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (IV) 1,3-butadiene,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (IV) isoprene,

(Tert-butylamido) (tepramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 1,4-dibenzyl-1,3-butadiene,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 2,4-hexadiene,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium (II) 3-methyl-1,3-pentadiene,

(Tert-butylamido) (2,4-dimethylpentadien-3-yl) dimethylsilanetitaniumdimethyl,

(Tert-butylamido) (6,6-dimethylcyclohexadienyl) dimethylsilanetitaniumdimethyl,

(Tert-butylamido) (1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilanetitanium dimethyl,

(Tert-butylamido) (1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalene-4- Dimethyl dimethyl titanium dimethyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) methylphenylsilanetitanium (IV) dimethyl,

(Tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) methylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

1- (tert-butylamido) -2- (tetramethyl-η ⁵ -cyclopentadienyl) ethanediyltitanium (IV) dimethyl, and

1- (tert-butylamido) -2- (tetramethyl-η ⁵ -cyclopentadienyl) ethanediyltitanium (II) 1,4-diphenyl-1,3-butadiene.

Complexes containing two L groups including crosslinked complexes suitable for use in the present invention include:

Bis (cyclopentadienyl) zirconium dimethyl,

Bis (cyclopentadienyl) zirconium dibenzyl,

Bis (cyclopentadienyl) zirconium methyl benzyl,

Bis (cyclopentadienyl) zirconium methyl phenyl,

Bis (cyclopentadienyl) zirconium diphenyl,

Bis (cyclopentadienyl) titanium-allyl,

Bis (cyclopentadienyl) zirconiummethylmethoxide,

Bis (cyclopentadienyl) zirconium methyl chloride,

Bis (pentamethylcyclopentadienyl) zirconium dimethyl,

Bis (pentamethylcyclopentadienyl) titanium dimethyl,

Bis (indenyl) zirconium dimethyl,

Indenyl fluorenyl zirconium dimethyl,

Bis (indenyl) zirconiummethyl (2- (dimethylamino) benzyl),

Bis (indenyl) zirconium methyltrimethylsilyl,

Bis (tetrahydroindenyl) zirconium methyltrimethylsilyl,

Bis (pentamethylcyclopentadienyl) zirconiummethylbenzyl,

Bis (pentamethylcyclopentadienyl) zirconiumdibenzyl,

Bis (pentamethylcyclopentadienyl) zirconiummethylmethoxide,

Bis (pentamethylcyclopentadienyl) zirconium methyl chloride,

Bis (methylethylcyclopentadienyl) zirconium dimethyl,

Bis (butylcyclopentadienyl) zirconium dibenzyl,

Bis (tert-butylcyclopentadienyl) zirconium dimethyl,

Bis (ethyltetramethylcyclopentadienyl) zirconium dimethyl,

Bis (methylpropylcyclopentadienyl) zirconium dibenzyl,

Bis (trimethylsilylcyclopentadienyl) zirconium dibenzyl,

Dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl,

Dimethylsilyl-bis (tetramethylcyclopentadienyl) zirconium (III) allyl,

Dimethylsilyl-bis (tert-butylcyclopentadienyl) zirconium dichloride,

Dimethylsilyl-bis (n-butylcyclopentadienyl) zirconium dichloride,

Methylene-bis (tetramethylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl,

Methylene-bis (n-butylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl,

Dimethylsilyl-bis (indenyl) zirconium benzyl chloride,

Dimethylsilyl-bis (2-methylindenyl) zirconium dimethyl,

Dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dimethyl,

Dimethylsilyl-bis (2-methylindenyl) zirconium-1,4-diphenyl-1,3-butadiene,

Dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium (II) 1,4-diphenyl-1,3-butadiene,

Dimethylsilyl-bis (tetrahydroindenyl) zirconium (II) 1,4-diphenyl-1,3-butadiene,

Dimethylsilyl-bis (fluorenyl) zirconium methyl chloride,

Dimethylsilyl-bis (tetrahydrofluorenyl) zirconium bis (trimethylsilyl),

(Isopropylidene) (cyclopentadienyl) (fluorenyl) zirconiumdibenzyl and

Dimethylsilyl (tetramethylcyclopentadienyl) (fluorenyl) zirconium dimethyl.

Particularly preferred bis-CP complexes for use in catalysts useful in the present invention are the crosslinked bis-Cp complexes of EP 676,421, which correspond to formula (2):

Where

Cp ¹ and Cp ² are independently substituted or unsubstituted indenyl or hydrogenated indenyl group;

Y is a monovalent anionic ligand or Y ₂ is a diene;

M is zirconium, titanium or hafnium;

Z is an alkylene group having 1 to 20 carbon atoms; Or dialkyl silyl groups or germanyl groups;

Or a bridging group comprising an alkyl phosphine or amine radical.

Other catalysts, especially those containing other Group 4 metals, will of course be apparent to those skilled in the art. A wide variety of organometallic compounds useful in the present invention and comprising nonmetallocenes are also apparent to those skilled in the art.

The complex is catalytically activated by combining with an activation promoter or using an activation technique. Suitable activating promoters for use herein are polymeric or oligomeric alumoxanes, in particular methylalumoxane, triisobutyl aluminum-modified methylalumoxane or diisobutylalumoxane: each hydrocarbyl group or halogenated hydrocarbyl C _1-30 hydrocarbyl substituted Group 13 compounds having 1 to 10 carbons in the group, in particular tri (hydrocarbyl aluminum- or tri (hydrocarbyl) boron-compounds and halogenated derivatives thereof, in particular tris (pentafluorophenyl Lewis strong acids, such as borane; and nonpolymeric, inert, compatible, non-coordinating, ion forming compounds (including use of such compounds under oxidative conditions) Suitable activation techniques are bulk electrolysis (hereafter The combination of the activating promoter and the technique can also be used if desired. Medium and active techniques have already been taught for different metal complexes in the following references cited herein: European Patent Application No. 277,003; US Patent No. 5,153,157; US Patent No. 5,064,802; European Patent Application No. 468,651 (Corresponding to US Patent Application No. 07 / 547,718); European Patent Application No. 520,732 (corresponding to US Patent Application No. 07 / 876,268); and International Patent Publication No. WO 93/23412 (5 1992). Corresponds to US patent application Ser. No. 07 / 884,966, filed May 1).

One exemplary useful Suitable nonpolymeric, inert, as a co-catalyst in the sun compatibility of the present invention, non-coordinating, ion forming compounds, probe capable of donating a proton roenseu ted acid cation and a compatible, non-coordination anion (A ^- ). Preferred anions are anions containing a single coordination complex comprising a charged metal or metalloid core, which can balance the charge of the active catalytic species (metal cations) formed when the two components are combined. The anions may also be replaced by olefinic, diolefinic and acetylenically unsaturated compounds, or other neutral Lewis bases such as ethers or nitriles. Suitable metals include but are not limited to aluminum, gold and platinum. Suitable metalloids are boron. Phosphorus and silicon, including but not limited to. Anion-containing compounds comprising coordination complexes containing single metal or metalloid atoms are well known, and in particular, many compounds containing a single boron atom in the anion moiety are commercially available.

Preferred cocatalysts can be represented by the general formula:

(L ^* -H) ⁺ dA ^d-

Where

L ^* is a neutral Lewis base;

(L ^* -H) ⁺ is a Bronsted acid;

A ^d- is a non-coordinating, compatible anion with a charge of d-;

d is an integer of 1 to 3.

More preferably, d is 1, ie A ^d- is A ⁻ .

Very preferably, A ^- is a formula [BO ₄ ] ^- (where B is boron in a formal oxidation state of +3, and Q is independently hydride, dialkylamido, halide, alkoxide, aryloxide, hydro Selected from carbyl, halocarbyl and halosubstituted-hydrocarbyl radicals, having up to 20 carbons, and only up to one case Q is a halide).

In a more highly preferred embodiment Q is a fluorinated C _1-20 hydrocarbyl group, most preferably a fluorinated aryl group, in particular pentafluorophenyl.

Non-limiting examples of ion forming compounds which can be used as activating promoters in the preparation of the catalyst of the invention and include proton donating cations are the trisubstituted ammonium salts as follows:

Trimethylammonium tetraphenylborate,

Triethylammonium tetraphenylborate,

Tripropylammonium tetraphenylborate,

Tri (n-butyl) ammonium tetraphenylborate,

Tri (tert-butyl) ammonium tetraphenylborate,

N, N-dimethylanilinium tetraphenylborate,

N, N-diethylanilinium tetraphenylborate,

N, N-dimethyl (2,4,6-trimethylanilinium) tetraphenylborate,

Trimethylammonium tetrakis (pentafluorophenyl) borate,

Triethylammonium tetrakis (pentafluorophenyl) borate,

Tripropylammonium tetrakis (pentafluorophenyl) borate,

Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,

Tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,

N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate,

Trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

Tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

Dimethyl (tert-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, and

N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate.

Examples of dialkyl ammonium salts are di (iso-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate.

Examples of trisubstituted phosphonium salts include triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (ortho-tolyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) force Phonium tetrakis (pentafluorophenyl) borate.

Preferred examples are N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and tributylammonium tetrakis (pentafluorophenyl) borate.

Other suitable ion forming, activating promoters include salts of non-coordinating, compatible anions with cationic oxidants represented by the formula:

(OX ^{e +} ) _d (A ^d- ) _e

Where

Ox ^{e +} is a cationic oxidant with a charge e +;

e is an integer from 1 to 3;

A ^d- and d are as defined above.

Examples of cationic oxidants include ferrocenium, hydrocarbyl-substituted ferrocenium, Ag ⁺ or Pb ⁺² . A preferred embodiment of A ^d- is an anion as defined above for Bronsted acid containing activating promoter, in particular tetrakis (pentafluorophenyl) borate.

Other suitable ion forming, activating promoters include compounds that are salts of non-coordinating, compatible anions with carbenium ions or silyllium ions, represented by the formula:

Where

Is C _1-20 carbenium ions or silyllium ions,

A ⁻ is as defined above.

Preferred carbenium ions are trityl cations, ie triphenylcarbenium. Preferred silyllium ions are triphenylsilyllium.

The active techniques and ion forming promoters also include tri (hydrocarbyl) aluminum compounds having 1 to 4 carbons in each hydrocarbyl group, oligomeric or polymeric alumoxane compounds, or 1 to 4 in each hydrocarbyl group Preference is given to using in combination with a mixture of tri (hydrocarbyl) aluminum compounds having two carbons and polymeric or oligomeric alumoxanes.

Particularly preferred activating promoters include combinations of trialkyl aluminum compounds having 1 to 4 carbons in each alkyl group with ammonium salts of tetrakis (pentafluorophenyl) borate (molar ratios of 0.1: 1 to 1: 0.1) And optionally up to 1000 mol% of alkylalumoxane relative to M.

Activation techniques for bulk electrolysis include the electrochemical oxidation of metal complexes under electrolysis conditions in the presence of a supporting electrolyte comprising uncoordinated inert anions. In the technique, solvents, supporting electrolytes, and electrolytic potentials for electrolysis are used so that electrolysis by-products that make the metal complex catalytically inert are substantially formed during the reaction. More specifically, suitable solvents are liquid and inert under the conditions of electrolysis (typically temperatures of 0 ° C. to 100 ° C.) capable of dissolving the supporting electrolyte. "Inert solvents" are not reduced or oxidized under the reaction conditions used for electrolysis. In general, in the desired electrolysis reaction, one can select a solvent and supporting electrolyte that are not affected by the electrical potential used for the desired electrolysis. Preferred solvents include difluorobenzene (all isomers), DMF and mixtures thereof.

Electrolysis can be carried out in a standard electrolysis cell (also referred to as each working electrode and counter electrode) containing a positive electrode and a negative electrode. Suitable materials for constructing the cell are glass, plastic, ceramic and metal coated with glass. The electrode is made from an inert conductive material, which means a conductive material in which the conductive material is not affected by the reaction mixture or reaction conditions. Platinum or palladium is the preferred inert conductive material. In general, ion permeable membranes, such as fine glass frits, separate cells into individual fractions, working electrode fractions, and counter electrode fractions. The working electrode is immersed in the reaction medium comprising the metal complex to be activated, the solvent, the supporting electrolyte, and any other material required to adjust the electrolysis or to stabilize the final complex. The counter electrode is immersed in a mixture of solvent and supporting electrolyte. The desired voltage can be theoretically calculated or experimentally determined by sweeping a cell using a reference electrode, such as a silver electrode immersed in the cell electrolyte. Background cell current, i.e., the current given in the absence of the desired electrolysis, is also determined. Electrolysis is completed when the current drops from the desired level to the background level. In this way, complete conversion of the initial metal complex can be easily detected.

Suitable supporting electrolytes are salts comprising cations and inert, compatible, uncoordinated anions (A ⁻ ). Preferred supporting electrolytes are salts corresponding to the formula:

G ⁺ A ^-

Where

G ⁺ is a cation that is unreactive to the starting and final complexes;

A ⁻ is a non ^- coordinating, compatible anion.

Examples of cations (G ⁺ ) include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 non-hydrogen atoms. Preferred cations are tetra-n-butylammonium cations.

While the complex of the present invention is activated by bulk electrolysis, the cations of the supporting electrolyte move to the counter electrode and A ⁻ moves to the working electrode to become the anion of the final oxidized product. Both cations of the solvent or supporting electrolyte are reduced at the counter electrode in the same molar amount as the amount of oxidized gold complex formed at the working electrode.

Preferred supported electrolytes are the tetrahydrocarbylammonium salts of tetrakis (perfluoroaryl) borates having 1 to 10 carbons in each hydrocarbyl group, in particular tetra-n-butylammonium tetrakis (pentafluorophenyl) borate.

The molar ratio of catalyst / cocatalyst used is preferably from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1 and most preferably from 1:10 to 10: 1.

Generally, the catalyst can be prepared by combining two components (metal complex and activator) in a suitable solvent at a temperature of about -100 ° C to about 300 ° C. The catalyst can be prepared separately before each combination of the components is used or , In combination in the presence of monomers to be polymerized.

It is contemplated that, with suitable functional groups on the catalyst or promoter, the catalyst system can be covalently or ionically bonded to the support material.

Preferred supports for use in the present invention include highly porous silica, alumina, aluminosilicates and mixtures thereof. The most preferred support material is silica. The support material may have granules, aggregates, pellets or any other physical form. Suitable materials include Grace Davison [Double U. R. under the trade names SD 3216.30, Davidson Syloid 245, Davison 948 and Darbyson 952. Department of W.R. Grace & Co., and Crossfield under the trade name ES70, and silica sold by Degussa AG under the trade name Aerosil 812; And alumina commercially available from Akzo Chemicals Inc. under the trade name Ketzen Grade B.

A support suitable for the present invention preferably be measured by the nitrogen captive Symmetry (porosimetry) using the BET method from 10 to about 1000m ² / g, preferably having a surface area of about 100 to 600m ² / g. Pore volume of the support is from 0.1 to 3cm ³ / g, preferably about 0.2 to 2cm ³ / g of glass was measured by nitrogen adsorption. The average particle diameter depends on the method of use, but is typically 0.5 to 500 μm, preferably 1 to 100 μm.

Both silica and alumina are inherently known to have small amounts of hydroxyl functionality. When used as a support herein, these materials are preferably heat treated and / or chemically to reduce their hydroxyl content. Typical heat treatments are carried out at 30 ° C. to 1000 ° C. (preferably 250 ° C. to 800 ° C. for at least 5 hours) under inert atmosphere or reduced pressure. Typical chemical treatments include contacting a Lewis acid alkylating agent, such as a trihydrocarbyl aluminum compound, a trihydrocarbylchlorosilane compound, a trihydrocarbyl alkoxysilane compound, or a similar agent. Thereafter, the remaining hydroxyl groups are removed through chemical treatment.

The support can be functionalized with a silane or chlorosilane functionalizing agent to attach to a pendant silane [-(Si-R) =] or chlorosilane [-(Si-Cl) =] functional group, where R is C _{1 -10} hydrocarbyl groups. Suitable functionalizing agents are compounds which react with the surface hydroxyl groups of the support or with silicon or aluminum of the matrix. Examples of suitable functionalizing agents include phenylsilane, hexamethyldisilazane diphenylsilane, methylphenylsilane, dimethylsilane, diethylsilane, dichlorosilane and dichlorodimethylsilane. Techniques for forming such functionalized silica or alumina compounds are already disclosed in US Pat. Nos. 3,687,920 and 3,879,368, the teachings of which are incorporated herein by reference.

The support is also of the formula AlR ¹ _{x '} R ² _y' wherein R ¹ is each independently hydride or R, R ² is hydride, R or OR, x 'is 2 or 3 and y' is 0 Or 1 and the sum of x 'and y' is 3]. Examples of suitable R ¹ and R ² groups are methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), butoxy (all isomers), phenyl, phenoxy Benzyl and benzyloxy. Preferably, the aluminum component is selected from the group consisting of aluminoxane and tri (C _1-4 hydrocarbyl) aluminum compounds. Most preferred aluminum components are aluminoxane, trimethylaluminum, triethylaluminum, tri-isobutyl aluminum and mixtures thereof.

Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric aluminumoxy compounds containing chains of alternating aluminum and oxygen atoms, where DMO solution aluminum has substituents, preferably alkyl groups. The structure of alumoxane is thought to represent cyclic alumoxane as general formula (-Al (R) -O) _{m '} and linear compound as R ₂ Al-O (-Al (R) -O) _m' -AlR ₂ . Wherein R is as defined above and m 'is an integer from 1 to about 50, preferably about 4 or more. Alumoxane is typically the reaction product of water and aluminum alkyl, which may contain halides or alkoxide groups in addition to alkyl groups. Some different aluminum alkyl compounds, such as trimethyl aluminum and tri-isobutyl aluminum, for example, react with water to produce the so-called modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxane and methylalumoxane modified with small amounts of C _2-4 alkyl groups, especially isobutyl. Alumoxanes generally contain less than the net mass of the starting aluminum alkyl compound.

A specific technique for preparing an alumoxane type compound by contacting an aluminum alkyl compound with an inorganic salt containing crystal water is disclosed in US Pat. No. 4,542,119. In a particularly preferred embodiment, the aluminum alkyl compound is contacted with a regenerative water-containing material such as hydrated alumina, silica or other material. This is disclosed in European Patent Application No. 338,044. Thus, alumoxane is subjected to the reaction of hydrated alumina or silica materials (optionally functionalized with silane, siloxane, hydrocarbyloxysilane or chlorosilane groups) and tri (C _1-10 alkyl) aluminum compounds according to known techniques. By incorporation into the support. In the teachings contained herein, these patents and publications or equivalent US patent applications are incorporated herein by reference.

In addition, treatment of the support materials to include the addition of an optional alumoxane or trialkylaluminum, prior to combining them with the alumoxane or trialkylaluminum compounds, in particular triethylaluminum or triisobutylaluminum, together with the complex or activated complex, Subsequent or simultaneous contacting. Optionally, the mixture may also be heated in a period of time and at a temperature sufficient to fix the alumoxane, trialkylaluminum compound, complex or catalyst system to the support under an inert atmosphere. Optionally, the treated support component containing the alumoxane or trialkylaluminum compound may perform one or more steps to remove alumoxane or trialkylaluminum that is not immobilized on the support.

In addition to contacting the support with alumoxane, alumoxane may be produced by contacting trialkyl aluminum compounds with silica or alumina or wet silica or alumina that has not been hydrolyzed, optionally in the presence of an inert diluent. Such methods are well known in the art and are described in European Patent Application No. 250,600; U.S. Patent 4,912,075; And US Pat. No. 5,008,228, the teachings of the US patent application or its corresponding patent application are incorporated herein by reference. Suitable aliphatic hydrocarbon diluents include pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane and combinations of two or more of these diluents. Suitable aromatic hydrocarbon diluents are benzene, toluene, xylene and other alkyl or halogen substituted aromatic compounds. Most preferably, the diluent is an aromatic hydrocarbon, in particular toluene. After prepared in this manner, its residual hydroxyl content is preferably reduced to a concentration of less than 1.0 meq of OH per gram of support by any of the techniques disclosed above.

The cocatalyst of the present invention is also according to the tri (hydrocarbyl) aluminum compound, oligomeric or polymeric alumoxane compound having 1 to 10 carbons in each hydrocarbyl group, in each hydrocarbyl or hydrocarbyloxy group. It may be used in combination with a di (harddrocarbyl) (hydrocarbyloxy) aluminum compound having 1 to 10 carbons, or a mixture of the above compounds. These aluminum compounds are usefully used for their beneficial ability to eliminate impurities such as oxygen, water and aldehydes from the polymerization mixture. Preferred aluminum compounds are C _2-6 trialkyl aluminum compounds, in particular alkyl groups of ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl, and methylalumoxane, modified methylalumoxane and di Isobutyl alumoxane. The molar ratio of aluminum compound to metal complex is preferably from 1: 10,000 to 1000: 1, more preferably from 1: 5000 to 100: 1 and most preferably from 1: 100 to 100: 1.

The molar ratio of catalyst / cocatalyst used is 1: 1000 to 1:10, preferably 1:10 to 10: 1, more preferably 1: 5 to 1: 1, most preferably 1: 1.2 to 1: 1 Mixtures of the activating cocatalysts of the present invention may also be used if desired. In most polymerization reactions, the catalyst used the molar ratio of polymerizable compound is 10 ^-12: 1 to 10 ^-1: 1, more preferably from 10 ^-12: 1: 1 to 10 ^-5.

Molecular weight modifiers can be used in combination with the promoters of the invention. Examples of such molecular weight modifiers include hydrogen, trialkyl aluminum compounds or other known chain transfer agents. It is contemplated that the present invention may be practiced in the absence of any component not specifically disclosed. The following examples are provided to further illustrate the invention and are not intended to be limiting. Unless otherwise indicated, all parts and percentages are expressed by weight.

Catalysts which may be used to polymerize addition polymerizable monomers and which are supported or unsupported by any of the methods of the present invention having a gas phase, solution, slurry or any other polymerization method, are ethylenically unsaturated monomers, acetylenic compounds, conjugated or Non-conjugated dienes, polyenes and mixtures thereof. Preferred monomers include olefins, for example α-olefins having 2 to 100,000, preferably 2 to 30, more preferably 2 to 8 carbon atoms and combinations of two or more such α-olefins.

Particularly suitable α-olefins are for example ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene Long chain vinyl terminated oligomeric or polymeric reaction products formed during polymerization, as well as 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene and C ₁₆ -C ₃₀ α-olefins or combinations thereof It includes. Preferably, the α-olefin is ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene, and combinations of ethylene and / or propene with one or more of the other α-olefins Water. Other preferred monomers include styrene, halo- or alkyl substituted styrenes, tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and 1,7-octadiene. Mixtures of the abovementioned monomers can also be used.

Preferred groups of olefin comonomers for polymerization in which ethylene is a monomer are propene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- Decene, 1,7-octadiene, 1,5-hexadiene, 1,4-pentadiene, 1,9-decadiene, ethylidenenorbornene, styrene or mixtures thereof. In polymerizations where propene is a monomer, preferred comonomers are the same comonomers as just mentioned, but include ethylene instead of propene.

The long chain macromolecular α-olefin may be a vinyl terminated polymeric residue formed in situ during the continuous solution polymerization reaction. Under suitable process conditions, such long chain macromolecular units can be polymerized with ethylene and other short chain olefin monomers into a polymer product to produce a small amount of long chain branched chain in the final polymer.

In general, the polymerization can be achieved at conditions well known in the art of Ziegler-Natta or Kaminsky-Sinn type polymerizations. Suspensions, solutions, slurries, vapor phases or high pressures used in batch or continuous form or in other process conditions may be used if desired. Examples of such well known polymerization methods are described in WO 88/02009, US Pat. No. 5,084,534; 5,405,922; No. 4,588,790; No. 5,032,652; No. 4,543,399; No. 4,564,647; 4,522,987 and the like, which is incorporated herein by reference. Preferred polymerization temperatures are from 0 to 250 ° C. Preferred polymerization pressures are atmospheric to 3000 atmospheres.

Preferably, the process of the present invention is carried out in a single reactor, which may have a single reaction vessel or two or more vessels which produce essentially the same polyolefin copolymer composition. Thus, the polymerization process of the present invention does not produce blends or, when one or more reaction vessels are used, does not require blending to produce an essentially uniform polyolefin copolymer composition.

In most polymerization reactions, the catalyst used the molar ratio of polymerizable compound is 10 ^-12: 1 to 10 ^-1: 1: 1, more preferably from ^10-2: 1 to ^10-5.

Suitable solvents for polymerization via the solution process are non-coordinated inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; Cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; Perfluorinated hydrocarbons such as perfluorinated C _4-10 alkanes and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene and xylene. Suitable solvents are also ethylene, propylene, 1-butene, butadiene, cyclopentane, 1-hexene, 1-heptene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1, 7-octadiene, 1,9-decadiene, 1-octene, 1-decene, styrene, divinylbenzene, ethylidenenorbornene, allylbenzene, vinyltoluene (including all isomers alone or mixed), Liquid olefins that can act as monomers or comonomers, including 4-vinylcyclohexene and vinylcyclohexane. Mixtures of such materials are also suitable.

Such polymerization methods include contacting the catalyst with one or more α-olefins in a solvent, optionally in one or more continuous stirred tanks or tubular reactors. U.S. Patents 5,272,236 and 5,278,272 relate to olefin polymerization reactions in solution and are incorporated herein by reference.

The process of the present invention can be advantageously used for gas phase copolymerization of olefins. Gas phase process for polymerization of olefins, in particular homopolymerization and copolymerization of ethylene and propylene, and copolymerization of ethylene with higher α-olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene Is well known in the art. This method is used on a large scale commercially for the production of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.

The gas phase method used may be of the type using, for example, a mechanical stirring bed or a gas fluidized bed as the polymerization reaction zone. It is preferred that the polymerization is carried out by the flow of fluidizing gas in a vertical cylindrical polymerization reactor containing a fluidized grid, fluidized bed of polymer particles supported on a perforated plate.

The gas used to fluidize the bed comprises the monomer or monomers to be polymerized and also acts as a heat exchange medium to remove heat of reaction from the bed. The hot gas is generally from the top of the reactor through a stabilization zone, which is larger in diameter than the fluidized bed and also known as the deceleration zone, where the fine particles entrained into the gas stream settle back into the bed. It is also advantageous to use cyclones to remove the ultrafine particles from the hot gas stream. Thereafter, the gas is generally recycled to the bed using a blower or compressor and one or more heat exchangers to remove the heat of polymerization from the gas.

In addition to the cooling method of providing a cooled gas as the recycle gas, a preferred method of cooling the bed is to supply a volatile liquid to the bed to provide an evaporative cooling effect. The volatile liquid used in this case may be a volatile inert liquid, such as a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6 carbon atoms. If the monomer or comonomer itself is a volatile liquid or can be condensed to provide such a liquid, it can be suitably fed into the layer to provide an evaporative cooling effect. Examples of olefin monomers that can be used in this way are olefins containing about 3 to about 8, preferably 3 to 6 carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form a gas that is mixed with the fluidizing gas. If the volatile liquid is a monomer or comonomer, some polymerization will occur in the bed. The vaporized liquid then exits the reactor as part of the hot recycle gas and enters the compression / heat exchange portion of the recycle loop. The recycle gas is cooled in a heat exchanger, and if the temperature of the cooled gas is below the dew point, the liquid will precipitate from the gas. This liquid is preferably continuously recycled to the fluidized bed. If the droplets move into the recycle gas stream, the precipitated liquid may be recycled. Methods of this type are described, for example, in European Patent No. 89691; U.S. Patent 4,543,399; International Patent Publication No. WO 94/25495 and US Pat. No. 5,352,749, which are incorporated herein by reference. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to re-inject the liquid directly into the bed using a method which preferably generates fine droplets of the liquid in the bed. Methods of this type are described in the document "BP Chemicals" and in WO 94/28032, which is incorporated herein by reference.

The polymerization reaction taking place in the gas fluidized bed is promoted by the addition of the catalyst continuously or semicontinuously. Such catalysts may be supported on inorganic or organic support materials as described above. The catalyst may also undergo a prepolymerization step, such as to polymerize a small amount of olefin monomer in a liquid inert diluent to provide a catalyst composite comprising catalyst particles embedded in the olefin polymer particles.

The polymer is produced directly in the fluidized bed by catalyzing the copolymerization reaction of one or more comonomers with the monomer on the fluidized particles of the catalyst, supported catalyst or prepolymer in the bed. Catalysts, monomers, preferably using layers of preformed polymer particles similar to the desired polyolefin, and having inert condensable gases, etc. when operating in a diluent gas, hydrogen chain transfer agent, or gas phase condensation mode in the recycle gas stream. And drying the inert gas or nitrogen prior to introducing any other nitrogen to adjust the state of the bed to initiate the polymerization reaction. The resulting polymer is optionally discharged continuously or discontinuously from the fluidized bed.

Gas phase methods suitable for the practice of the present invention are preferably continuous methods provided for continuously feeding the reactants into the reaction zone of the reactor and removing the product from the reaction zone of the reactor, whereby a steady state atmosphere is present within most of the reaction zone of the reactor. To provide.

Typically, the fluidized bed of the gas phase process is operated at 50 ° C. or higher, preferably from about 60 ° C. to bad 110 ° C., more preferably from about 70 ° C. to about 110 ° C.

Typically, the molar ratio of typical comonomer to monomers used in the polymerization reaction depends on the desired density of the resulting composition and is about 0.5 or less. Preferably, when preparing a material having a density from about 0.91 to about 0.93, the molar ratio of comonomer to monomer is less than 0.2, preferably 0.05, more preferably 0.02 and may be less than 0.01. Typically, the ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.02, and may be less than 0.01.

The range of method parameters described above is suitable for the gas phase method of the present invention and may be suitable for other methods that are acceptable for the practice of the present invention.

Many patents and patent applications include methods of the present invention, specifically US Pat. No. 4,588,790; No. 4,543,399; 5,352,749; 5,352,749; No. 5,436,304; 5,405,922; 5,462,999; 5,462,999; No. 5,461,123; No. 5,453,471; No. 5,032,562; 5,028,670; 5,028,670; No. 5,473,028; 5,106,804; 5,106,804; And European Patent Application No. 659,773; No. 692,500; And International Patent Publication No. WO 94/29032; WO 94/25497; WO 94/25495; WO 94/28032; WO 95/13305; WO 94/26793; And weather methods which are acceptable for use in WO 95/07942, all of which are incorporated herein by reference.

Preferably, the polyolefin copolymer composition of the present invention contains, as monomers, 0.01 to 99.99 mol% of ethylene and 99.99 to 0.01 mol% of at least one olefin comonomer in polymerized form. More preferably, the composition contains from 0.1 to 99.9 mol% of ethylene and from 99.9 to 0.1 mol% of at least one olefin comonomer in polymerized form as monomer. Preferably, the composition contains 50 to 99.9 mol% of ethylene and 50 to 0.1 mol% of at least one olefin comonomer in polymerized form as monomer. In a very preferred embodiment, the composition comprises 96 to 99.9 mol% of ethylene and 4 to 0.1 mol% of at least one olefin comonomer in polymerized form as monomer.

In general, the density of the composition is preferably about 0.87 to about 0.96, but may be higher or lower than the above range. More very preferably, the density is about 0.90 to about 0.94, preferably 0.910 to about 0.925. The composition preferably has a melt index (I ₂ ) of about 0.01 to about 150, and an I ₂₁ / I _{2 of at} least 24, and a Mw / Mn of about 2.0 to about 10.

Preferred polyolefin copolymer compositions have I ₂₁ / I _{2 of at} least 24 and Mw / Mn of from about 2.0 to about 3.5.

Preferred polyolefin copolymer compositions have a polycrystalline short chain branched distribution or a polycrystalline molecular weight distribution.

Other preferred polyolefin copolymer compositions have a composition having a density of about 0,910 to about 0.925, a comonomer to monomer molar ratio of less than 0.02, a hydrogen to monomer molar ratio of less than 0.02, and the composition having a reaction zone having a temperature of at least 70 ° C. It is a composition produced in the cabin.

The homogeneity of the polymer is typically described as the Short Chain Branching Distribution Index (SCBDI) or Composition Distribution Branch Index (CDBI), and the comonomer content within 50% of the molar content of the median total comonomer. It is defined as the weight percent of polymer molecules having. SCBDIs of polymers are known in the art, such as Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), US Pat. No. 4.798,081 to Hazlitt et al. Or US Pat. No. 5,089,321 to Chum et al., All of which are incorporated herein by reference. Easily calculated from data obtained by temperature rising elution fractionation (hereinafter abbreviated as "TREF"). The SCBDI or CDBI of the homogeneous linear ethylene / a-olefin polymer and the homogeneous substantially linear ethylene / a-olefin polymer used in the present invention is preferably greater than 50%.

In the polyolefin polymer composition of the present invention, the long chain branch is longer than the short chain branch produced by incorporation of one or more α-olefin comonomers into the polymer backbone. The experimental effect of the presence of long chain branches in the copolymers of the present invention is manifested as an improvement in rheological properties identified by higher I ₂₁ / I ₂ and higher flow activation energies than would be expected from other structural properties of the composition.

Determination of Comonomer Content vs. Log (Molecular Weight) by GPC / FTIR

Comonomer content as a molecular weight function was determined by combining a Fourier Transform Infrared Spectrometer (FTIR) with a Waters 150 ° C. Gel Permeation Chromatograph (GPC). The installation, measurement, operation and data processing of this system are as described above ("Characterization of Polyethylene Copolymers by Bound GPC / FTIR" in Raj Rose et al. "Characterization of Copolymers", Rapra Technology, Shawbury UK, 1995, ISBN 1-85957-048-86). To characterize the degree of comonomer concentration in the high molecular weight portion of the polymer, GPC / FTIR was used to calculate a variable called comonomer partition coefficient (C _pf ). M _n and M _w were also determined from GPC data using standard techniques.

Comonomer Distribution Factor (GPC-FTIR)

Comonomer partition coefficient (C _pf ) is calculated from GPC / FTIR data. The comonomer partition coefficient characterizes the ratio of the average comonomer content of the high molecular weight fraction to the average comonomer content of the low molecular weight fraction. High molecular weight and low molecular weight are each defined as greater or less than the median molecular weight. That is, the molecular weight distribution is divided into two parts of equal weight. C _pf is calculated from Equation 1:

Equation 1

Where

c _i is the mole fraction of the comonomer content,

w _i is the normalized weight fraction measured by GFC / FTIR for n FTIR data points of intermediate molecular weight or greater,

c _j is the mole fraction of the comonomer content,

w _j is the normalized weight fraction measured by GPC / FTIR for m FTIR data points below the median molecular weight.

Calculate C _pf using only the weight fraction w _i or w _j associated with the mole fraction value of the comonomer content. For valid calculations n and m must be at least 3. FTIR data corresponding to a molecular weight fraction of less than 5,000 are not included in the calculation because of inaccuracy.

In the polyolefin copolymer composition of the present invention, the C _pf is preferably 1.10 or more, more preferably 1.15 or more, even more preferably 1.20 or more, preferably 1.30 or more, more preferably 1.40 or more. And even more preferably 1.50 or more, even more preferably 1.60 or more.

ATREF-DV

ATREF-DV is described in US Pat. No. 4,798,081 and incorporated herein by reference, "Determination of Short Chain Branch Distribution of Ethylene Copolymers by Automated Assay Elevation Elution Fractionation (Auto-ATREF)," J. of Appl. Pol. Sci .: Applied Polymer Symposium 45, 25-37 (1990). ATREF-DV is a dual detector analysis system capable of fractionating semicrystalline polymers similar to linear low density polyethylene (LLDPE) as a function of crystallization temperature while determining the molecular weight of the fractions. In fractionation, ATREF-DV is similar to the Temperature Elevation Elution Fractionation (TREF) published in the public over the last 15 years. The main difference is that the Analyze-TREF (ATREF) technique is performed on a small scale and fractions are not actually isolated. Instead, a typical liquid chromatography (LC) mass detector, such as an infrared single frequency detector, is used to quantify the crystallinity distribution as a function of elution temperature. This distribution can be transformed into a number of other domains such as short chain branching frequency, comonomer distribution or possibly density. Thus, the converted distribution can be interpreted according to several structural variables, such as comonomer content, but routine use of ATREF for comparison of various LLDPE is often performed directly in the elution temperature domain.

To obtain ATREF-DV data, commercially available viscometers, particularly suited for LC analysis (e.g. Viskotek Combine)) with the IR mass detector. Using these two LC detectors together can calculate the intrinsic viscosity of the ATREF-DV eluent. The viscosity average molecular weight of a given fraction is then calculated using the appropriate Mark Houwink constant, the corresponding intrinsic viscosity, and the appropriate coefficients to calculate the fraction concentration (d / g) as the fraction passes through the detector. Can be. Thus, typical ATREF-DV results reveal the weight fraction polymer and viscosity average molecular weight as a function of elution temperature. Then M _pf is calculated using the given equation.

Molecular weight distribution coefficient

Molecular weight partition coefficient (M _pf ) is calculated from TREF-DV data. The molecular weight partition coefficient characterizes the ratio of the average molecular weight of the fraction with high comonomer content to the average molecular weight of the fraction with low comonomer content. High comonomer content and low comonomer content are defined as higher or lower than the median elution temperature of the TREF concentration plot, respectively. That is, the TREF data is divided into two parts of equal weight. M _pf is calculated from Equation 2:

Equation 2

Where

M _i is the viscosity average molecular weight,

w _i is the normalized weight fraction measured by ATREF-DV for n data points at fractions below the median elution temperature,

M _j is the viscosity average molecular weight,

w _j is the normalized weight fraction measured by ATREF-DV for m data points at fractions above the median elution temperature.

M _pf is calculated using only the weight fractions w _i or w _j associated with viscosity average molecular weights greater than zero. For valid calculations n and m must be at least 3.

In the polyolefin copolymer composition of the present invention, M _pf is preferably 1.15 or more, more preferably 1.30 or more. Even more preferably it is at least 1.40, preferably at least 1.50, more preferably at least 1.60, even more preferably at least 1.70.

Activation energy as an indicator of long chain branching

The importance and measurement of the activation energy of the flow, which indicates the temperature dependence of the viscosity, has been extensively described (JM Dealy and KF Wissbrun, "Melt Rheology and its Use in Plastic Processing", Van Nostrand Reinhold, New York (1990)). For polyolefins, because T> T _g +100 (ie, melting point (T) is greater than glass transition temperature (T _g ) +100; if this inequality is not true, Williams-Landell to describe the temperature dependence of viscosity) The Ferri (Williams-Landel-Ferry, WLF) equation is used, and the Arrhenius equation is generally used to describe the temperature dependence of viscosity. Long chain branched polymers have been found to have higher activation energies compared to comparable linear polymers. This comparison has been made in polyethylene homopolymers, where the activation energy of the long chain branched polymer produced by the high pressure free radical method is about 12-14 kcal / mol, whereas the activation energy of the linear homopolymer is about 6.5 kcal / mol. . When using the activation energy technique as an indicator of long chain branching, care should be taken to account for the causes of external influences such as crosslinking, comonomer content, or impurities (eg promoter residues).

For polyolefin copolymers, considering the effects described in the preceding paragraphs, activation energy values above about 8 kcal / mol with I ₂₁ / I ₂ greater than would be expected from other structural properties of the composition would be indicative of the presence of long chain branches. And an activation energy value of at least about 10 kcal / mol, especially with I ₂₁ / I ₂ greater than expected from other structural properties of the composition, clearly indicates the presence of long chain branches. Preferred polyolefin copolymers of one embodiment of the invention are preferably at least about 0.01 long chain branches, more preferably from about 0.01 to about 8, preferably from about 0.01 to about 3, per 1000 carbon atoms along the polymer backbone Dogs, more preferably about 0.01 to about 1, even more preferably about 0.02 to about 0.5. When the long chain branch is measured by some experimental technique such as NMR, it is believed that the units in the above range in the long chain branch number are based on a total of 1000 carbon atoms.

The temperature dependence of the density of polyethylene can be expressed by the Arrhenius equation, where the activation energy is related to the shift factor (a _T ) used to determine the principal curve of the material by time-temperature overlap. Can be. The coefficient of transfer (a _T ) values are independent of molecular weight and molecular weight distribution (WW Graessley, "Viscoelasticity and Flow in Polymer Melts and Concentrated Solutions". Edited by JE Mark et al. Among others, ACS, New York (1993): J. Wang and RS Porter et al., "Viscosity-Temperature Behavior of Polymer Melts", Rheol. Acta, 34, 496 (1995) Porter, Knox and JF Johnson (see "About the Flow and Activation Energy of Branched Polyethylene Melts", Trans. Soc. Rheol., 12, 409 (1968)), thus The activation energy is independent of the molecular weight and molecular weight distribution of the polymer following the Arrhenius relationship between the coefficient of motion and the inverse of the temperature. According to other documents, the high activation energy (10-18 kcal / mol) of long-chain branched polybutadiene is related to long-chain branching compared to the activation energy of linear polyethylene (6.4 kcal / mol) (VR Raju et al. See, “Characteristics of amorphous and crystalline hydrocarbon polymers IV. Melt rheology of linear and star-branched hydrogenated polybutadienes”, J. Polym. Sci., Polym. Phys. Ed., 17, 1223 (1979). ). It was concluded that the change in active energy between long chain branched samples was due to the change in average branch length.

Determination of Activation Energy

Stabilization of the Sample

If the sample was not stabilized, the sample was stabilized in the following stabilization package: 1250 ppm calcium stearate, 500 ppm Irganox 1076 and 800 ppm PEPQ. This stabilization package was dissolved in acetone and then carefully poured onto the sample. The sample was then placed in a vacuum oven and dried at 50-60 ° C. until the saple had dried (about 1 day).

Molding of samples

All samples were compression molded with a tetrahedron MTP-8 hot press before the rheology test. The tray was used to contain the sample and to enter and exit the sample into the press. The metal plate was placed on the tray and the Mylar sheet was placed on the brass plate. The sample shim used was approximately 2-3 mils thick and slightly larger than 1 inch in diameter in the form of discs / discs. These shims were filled with samples (up to 8 shims per molding). If much disk was needed for a given sample, a 3 inch diameter shim was used. Then, another Miller fragment was placed on top of the sample and a metal plate was placed on it. The tray with the sample was then placed between 350 ° F tetrahedron plates. The tetrahedron plates were then combined for 5 minutes at 1500 pounds of force. Then, the tray was removed from the press and cooled. The sample for the rheology test was then cut using an arc punch with a diameter of 25 mm.

Rheology test

Rheology tests were performed on Rheometrics RMS-800 with parallel plates 25 mm in diameter in dynamic mode. Before performing the flow activation energy experiment, two strain sweep experiments were performed to measure the strain for performing the activation energy experiment, so the test is performed in the linear viscoelastic region and the torque signal is important. One strain sweep experiment was performed at the highest test temperature (210 ° C.) at low frequency (0.1 rad / sec) to determine the minimum strain required to generate a significant torque signal. Another strain sweep experiment was performed at the lowest temperature (170 ° C.) at the highest frequency (100 rad / sec) to determine the maximum strain that could remain in the linear viscoelastic region. In general, the strain was 10-30% depending on the molecular weight / stiffness of the sample.

The activation energy was measured by performing a frequency sweep from 100 rad / sec to 0.01 rad / sec using the strains described above for 5 points per 10 at 210, 190 and 170 ° C. Each experiment used a separate 25 mm disc or plaque material. Rheological data was analyzed using Leometrics RHIOS 4.4 software. According to the Arrhenius equation where the time-temperature overlap (tT) and the coefficient of motion (a _T ) are related to E [a _T = exp (E _a / RT), where R is the gas constant and T is the absolute temperature] The following conditions were selected for the determination of the flow activation energy (E _a ): transfer method: 2D, transfer accuracy: high, insertion: spline, all reference temperatures of 190 ° C.

The polyolefin copolymer composition of a preferred embodiment of the invention preferably has a flow activation energy of at least about 8 kcal / mol, more preferably at least about 10 kcal / mol, preferably at least about 12 kcal / mol, more preferably about 15 kcal More than a mole.

The polyolefin copolymer composition of the present invention may be blended with a variety of other resins to achieve desirable balanced properties or for economic reasons. In general, the physical properties of the blend are expected from the weight insertion of the physical properties of the individual components and appear to deviate most significantly from the straight line when one of the blend components is small compared to the other components.

Preferably, the blend of the present invention comprises at least two resin components (A) and (B), wherein the blend comprises from about 1 to about 99 weight percent of component (A) and at least one resin (B) other than component (A) ) About 99 to about 1 weight percent. Component (A) may be the polyolefin copolymer composition of the present invention, but component (B) may be any other resin that is not incompatible with component (A). Preferred component (B) is various polyolefins.

In one embodiment, where component (B) is preferred, the blend comprises from about 1 to about 30 weight percent of component (A) and from about 99 to about 70 weight percent of at least one resin (B) other than component (A) do. If it is desired that the amounts of the components differ greatly, the blend comprises about 1 to about 15 weight percent of component (A) and about 99 to about 85 weight percent of one or more resins (B) other than component (A).

In another embodiment, where it is desired to have more component (A), the blend may contain from about 99 to about 70 weight percent of component (A) and from about 1 to about 30 weight percent of at least one resin (B) other than component (A). Include. If it is desired that the amounts of components differ greatly, the blend comprises from about 99 to about 85 weight percent of component (A) and from about 1 to about 15 weight percent of one or more resins (B) other than component (A).

Examples 1-3 are three samples taken three consecutive days during a single polymerization experiment. The same catalyst was used throughout the experiment and basically maintained the same polymerization conditions throughout the experiment.

Preparation of Catalysts for Examples 1-3

(i) Treatment of Silica:

110 liters of hexane were placed in a 240 liters container under a nitrogen atmosphere and 0.75 g of Stadis ) 425 (diluted to 1% by weight in hexane) was added. Stadith 425 is a hydrocarbon-based antistatic agent available from DuPont Chemicals. Next, 5 kg of Sylopol ) 948 silica was added. 150 ml of water were then added at ambient temperature for 1 hour. Then 16.67 moles of TEA were added at 30 ° C. for 1 hour. After leaving for 30 minutes, the silica was washed six times with 130 L of hexane.

(ii) catalyst preparation:

The silica treated as above was dried and then 25 L toluene was added. Next, 59.59 L of a tris (pentafluorophenyl) boron solution (3.1 wt.%) In hexane was added at ambient temperature for 30 minutes. Then, 3.38 L of a solution of C ₅ Me ₄ SiMe ₂ NCMe ₃ TiMe ₂ ((t-butylamino) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitaniumdimethyl) in hexane (12.25% by weight) was added for 15 minutes. Was added at ambient temperature. The catalyst was then left at 25 ° C. for 1 hour and additionally 0.125 g Stadiz 425 was added (diluted to 1% by weight in hexane). The catalyst was then dried under vacuum (20 mmHg) at 40 ° C. to give a brown / ocher free flowing powder.

(iii) Polymerization Using Continuous Fluidized Bed Reactors in Examples 1-3

Ethylene, n-hexene, hydrogen and nitrogen were fed to a continuous fluidized bed reactor 45 cm in diameter. The polymer product was collected continuously from the reactor. The operating conditions and the properties of the composition are shown in Table 1 below.

Example 4

(i) Treatment of Silica:

A suspension of ES70 silica (7 kg, precalcined at 500 ° C. for 5 hours) in 110 liters of hexane was configured in a 240 L vessel under a nitrogen atmosphere. A solution of TEA in hexanes (9.1 mol, 0.976 M solution) was added slowly to the stirred suspension over 30 minutes, during which the temperature of the suspension was kept at 30 ° C. The suspension was further stirred for 2 hours. The hexanes were filtered off and the silica was washed four times with hexanes so that the aluminum content in the final wash was less than 1 mmol Al / L. Finally, the suspension was dried at 40 ° C. under vacuum to give free flowing treated silica powder.

(ii) catalyst preparation:

Na-dry distilled toluene (55 ml) was added to 13 g of the treated silica powder in a 250 ml round bottom flask in anhydrous nitrogen glove box. To the suspension was added a solution of tris (pentafluorophenyl) boron in toluene (7.6 mL, 7.85 wt%, d = 0.88 g / mL) with a syringe. Then, a solution of (t-butylamino) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium η ⁴ -1,3-pentadiene in toluene (2.6 ml, 10.7 wt.%, D = 0.88 g / Ml) was added by syringe. The suspension was mixed well for 5 minutes and then dried under vacuum at 20 ° C. to obtain a free flowing pale green powder.

(iii) polymerization using semicontinuous fluidized bed reactor:

Ethylene, n-hexene, hydrogen and nitrogen were fed to a batch 15 cm diameter fluidized bed reactor. Starting with a seed layer of LLDPE powder (˜1 kg), catalyst was injected and polymerization was carried out to increase the mass of the layer to about 3.5 kg. The product was then withdrawn to leave about 1 kg of powder in the reactor. The polymerization and product withdrawal steps were carried out a total of five times to give only 0.3% by weight of the product contained in the region of the starting layer. The product was a white free flowing powder with a bulk density of 0.36 g / cm 3. The average productivity of the catalyst was about 1000 g powder / g catalyst. The operating conditions and the properties of the composition are described in Table 1: Total pressure 9 bar, temperature 70 ° C., C ₂ pressure 8 bar, H ₂ / C ₂ pressure 0.0018, C ₆ / C ₂ pressure 0.0033.

Example 4A

(i) Treatment of Silica:

A suspension of ES70 silica (7 kg, precalcined at 500 ° C. for 5 hours) in 110 liters of hexane was configured in a 240 L vessel under a nitrogen atmosphere. A solution of TEA in hexanes (9.1 mol, 0.976 M solution) was added slowly to the stirring suspension over 30 minutes, during which the temperature of the suspension was kept at 30 ° C. The suspension was further stirred for 2 hours. The hexanes were filtered off and the silica was washed four times with hexanes so that the aluminum content in the final wash was less than 1 mmol Al / L. Finally, the suspension was dried at 40 ° C. under vacuum to give free flowing treated silica powder.

(ii) catalyst preparation:

Na-dry distilled toluene (55 ml) was added to 13 g of the treated silica powder in a 250 ml round bottom flask in anhydrous nitrogen glove box. To the suspension was added a solution of tris (pentafluorophenyl) boron in toluene (7.6 mL 1, 7.85 wt%, d = 0.88 g / mL) with a syringe. Then, in toluene (t- butylamino) - > (tetramethyl -η ⁵ cyclopentadienyl) dimethylsilane titanium -η ⁴ -3- methyl-1,3-pentadiene (2.6㎖, 10.7% by weight, d = 0.88 g / ml) was added by syringe. The suspension was shaken well for 5 minutes and then dried under vacuum at 20 ° C. to obtain a free flowing pale green powder.

(iii) polymerization using semicontinuous fluidized bed reactor:

Ethylene, n-hexene, hydrogen and nitrogen were fed to a batch 15 cm diameter fluidized bed reactor. Starting with a seed layer of LLDPE powder (˜1 kg), catalyst was injected and polymerization was carried out to increase the mass of the layer to about 3.5 kg. The product was then withdrawn to leave about 1 kg of powder in the reactor. The polymerization and product withdrawal steps were carried out a total of five times giving only 0.3% by weight of product contained in the region of the starting phase. The product was a white free flowing powder with a bulk density of 0.36 g / cm 3. The average productivity of the catalyst was about 1000 g powder / g catalyst. The operating conditions and the properties of the composition are described in Table 1: Total pressure 9 bar, temperature 70 ° C., C ₂ pressure 8 bar, H ₂ / C ₂ pressure 0.0018, C ₆ / C ₂ pressure 0.0033.

Example 5

(i) Preparation of Catalysts:

The catalyst was prepared in a 110 L container maintained in an inert atmosphere. Mixing was performed throughout the experiment using a paddle stirrer operating at 20 revolutions / minute. 7.5 moles of MAO (1.6 moles / liter in toluene) was added at ambient temperature. Additional 3.88 L of toluene was added to rinse the addition system. Next, 100 mM ethylene-crosslinked bis (indenyl) zirconium dichloride diluted in 2.3 L of toluene was added, and 1 L of toluene was further added for washing. The temperature was raised to 80 ° C. and maintained at this temperature for 1 hour. Cool to 50 ° C. and add 2 kg ES70 silica (dried at 800 ° C. for 5 hours). The temperature was raised to 80 ° C., maintained for 2 hours, then 0.5 g of Stadith 425 antistatic agent in 0.5 g of toluene was added and the catalyst was dried at 70 ° C. under vacuum (700 Torr).

(ii) Polymerization Using a Continuous Fluidized Bed Reactor in Example 5:

Ethylene, n-hexene, hydrogen and nitrogen were fed to a fluidized bed reactor 45 cm in diameter. The polymer product was collected continuously from the reactor through a valve. The operating conditions are as follows: total pressure 20.2 bar, temperature 80 ° C., C ₂ pressure 11 bar, H ₂ / C ₂ pressure 0.0011, C ₆ / C ₂ pressure 0.012.

The properties of the composition are described in Table 1. The value of activation energy found by flow activation analysis was 19.2 kcal / mol, indicating significant long chain branching.

Example 6

(i) Preparation of Catalysts:

The catalyst was prepared in a 110 L container maintained in an inert atmosphere. Mixing was performed throughout the experiment using a paddle stirrer operating at 20 revolutions / minute. 48.8 mol of MAO (1.85 mol / l in toluene) was added at ambient temperature. Additional 3.88 L of toluene was added to rinse the addition system. Then, 650 mM ethylene-crosslinked bis (indenyl) zirconium dichloride diluted in 5 L of toluene was added, and 1.2 L of toluene was further added for washing. The temperature was raised to 80 ° C., held at this temperature for 1 hour, then cooled to 50 ° C. and 13 kg of ES70 silica (dried at 800 ° C. for 5 hours) was added. The temperature was raised to 80 ° C., maintained for 2 hours, then 0.5 g of Stadith 425 antistatic agent in 0.11 g of toluene was added and the catalyst was dried at 70 ° C. under vacuum (700 mmHg).

(ii) Polymerization Using a Continuous Fluidized Bed Reactor in Example 6:

Ethylene, n-hexene, hydrogen and nitrogen were fed to a fluidized bed reactor with a diameter of 74 cm. The polymer product was collected continuously from the reactor through a valve. The operating conditions are as follows: total pressure 20.2 bar, temperature 65 ° C., C ₂ pressure 12 bar, H ₂ / C ₂ pressure 0.005, C ₆ / C ₂ pressure 0.009.

The properties of the composition are described in Table 1.

Examples 100-104

To prepare the catalysts of these examples, the same catalyst formulations and preparation methods as in Examples 1 to 3 were used. However, only 3.5 kg of silica was used and the amount of all other components was thus reduced. The polymerization was carried out in the same continuous fluidized bed reactor 45 cm in diameter. Operating conditions and properties of the compositions are shown in Table 1A below.

In Table 1A below, I ₂ and I ₂₁ were measured by ASTM D-1238, and the density was measured by ASTM D-1505.

Catalyst Preparation for Example 105

(i) Treatment of Silica:

110 L of hexane was placed in a 240 L container under a nitrogen atmosphere, and 0.75 g of Stadith 425 diluted to 1% by weight in hexane was added. Then, 2.9 kg of Crossfield ES70 silica was added which was pre-dried at 500 ° C. for 5 hours and containing 1.1 mM of 0H / g. 3.75 moles of TEA were then added at 30 ° C. for 1 hour. After leaving for 30 minutes, the silica was washed with hexane to remove excess TEA and the desired aluminum in the supernatant was 1 mM per liter of hexane.

(ii) catalyst preparation:

The silica treated as above was dried and then 10.4 L of toluene was added. Next, 0.2 moles of tris (pentafluorophenyl) boron solution (7.85 wt.%) In toluene was added at ambient temperature for 30 minutes. 0.15 mole of (t-butylamino) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitaniumdimethyl) -η ⁴ -1,3-pentadiene (10.17% by weight) in toluene was then added for 15 minutes. Add at ambient temperature. The catalyst was then dried under vacuum (20 mmHg) at 40 ° C. to give a green free flowing powder.

(iii) Polymerization Using a Continuous Fluidized Bed Reactor in Example 105:

Ethylene, n-hexene, hydrogen and nitrogen were fed to a continuous 45 cm diameter fluidized bed reactor. The polymer product was collected continuously from the reactor. Operating conditions are described in Table 1A.

Example 106

To prepare the catalyst of Example 106, the same catalyst formulation and preparation method as in Examples 1-3 were used. However, 10 kg of silica was used, thus reducing the amount of all other components. The polymerization was carried out in the same continuous fluidized bed reactor 74 cm in diameter. Operating conditions and properties of the compositions are shown in Table 1A below.

Example 107

To prepare the catalyst of Example 107, the same catalyst formulation and preparation method as in Example 105 was used. However, 17 kg of silica was used, thus reducing the amount of all other components. The polymerization was carried out in the same continuous fluidized bed reactor 74 cm in diameter. Operating conditions and properties of the compositions are shown in Table 1A below.

Comparative Examples A to F:

Comparative Examples A-F are commercially available materials, tested under the same conditions and compared with the compositions of Examples 1-6. Data for comparison is shown in Table 2 below.

Comparative Example A is Inovex 7209, a commercially available gas phase produced polyethylene produced by BP Chemicals using a conventional Ziegler-Natta catalyst.

Comparative Example B is Exon EXID 401, a commercially available gas phase produced polyethylene produced by Exxon Chemical using a metallocene catalyst. (Note: when evaluating another sample of this material, the E _a value was determined to be 7.53 kcal / mol, I ₂₁ was 77.92 dg / min, I ₁₀ was 27.02 dg / min, and therefore I ₂₁ / I ₂ was 17.3 And I ₁₀ / I ₂ was 6.0.The critical shear rate at the start of surface melt fracture was 294 sec ⁻¹ at a shear stress of 2.15 × 10 ⁶ dynes / cm 2, and at the onset of total melt break. The critical shear rate was 795 sec ⁻¹ at a shear stress of 3.45 × 10 ⁶ dynes / cm 2, which indicates no long chain branching.)

Comparative Example C is Novapol TD902, using a conventional Ziegler-Natta catalyst (Novascor Commercially available gas-producing polyethylene manufactured by

Comparative Example D is Dowrex 2056A, a commercially available solution method polyethylene manufactured by The Dow Chemical Company using a conventional Ziegler-Natta catalyst.

Comparative Example E is Affinity FM 1570, a commercially available solution method polyethylene manufactured by The Dow Chemical Company using a limited geometry metallocene catalyst.

Comparative Example F is an improved polyethylene XU-59900.00, a commercially available solution method polyethylene from The Dow Chemical Company.

Improved processability was observed for the compositions of Example 2a (see note 5 in Table 3 below) and Example 3 due to the presence of long chain branches in the polymer. The Dowrex 2056A produced by the solution method using a Ziegler-Natta catalyst does not contain long chain branches. The melt strength measured by the Getettfert Rheotens instrument is greater due to the presence of long chain branches. The data is reported in Table 3 below.

The polyolefin copolymer compositions of the present invention have excellent mechanical properties such as dart impact strength, optical properties and heat sealability compared to comparable densities of compositions prepared by conventional Ziegler. They also have processing properties, as measured by good melt strength and melt flow ratio, for example compared to conventional metallocene products of comparable density and melt index and in particular preferred embodiments compared to conventional Ziegler materials. Polyolefin copolymer compositions also have the advantage that they can be prepared using a single catalyst in a single reactor process. In a preferred embodiment, the materials of the present invention can be extruded through conventional polyethylene extruders with lower power requirements, lower extruder pressures and lower melting points than conventional Ziegler-Natta products and conventional metallocene products.

Films and other products made from the polyolefin copolymer compositions of the present invention preferably have a melt strength greater than 4 CNN, preferably greater than 7 CNN, more preferably greater than 9 CNN. The sealing strength is preferably greater than 4.2 lb, preferably at least 4.6 lb, more preferably at least 4.8 lb. The high temperature adhesion force is preferably greater than 0.5 lb, preferably at least 1.0 lb, more preferably at least 2.0 lb. The dart impact strength is preferably greater than 100 g, more preferably greater than 200 g, preferably at least 500 g, more preferably at least 700 g, even more preferably at least 850 g.

Blend of Polyolefin Copolymer Composition with Ethylene Homopolymer

Blends of the polyolefin copolymer compositions of the present invention with ethylene homopolymers prepared by high pressure tube processes were prepared and tested. The polyolefin copolymer compositions designated L022 of Example 100 and L023 of Example 101 were individually blended with ethylene homopolymer resin (LDPE 5011) in an amount of 0-100%. These resins did not contain slip agents or blockers except LDPE 5011 which was stabilized with 500 ppm of Aganox 1076, a phenolic antioxidant. The properties of the resins used in the blends are shown in Table 4 below.

Data on the composition of these blends and unblended materials are shown in Samples A through G in Table 5 below.

By blending LDPE into the substantially linear low density polymer of the present invention, the increase in the amount of long chain branching increased the processability compared to the unblended polyolefin copolymer composition of the present invention, as shown by the decrease in extruder current and pressure. . The data on the workability are shown in Table 6. The blend also has a significant improvement in optical properties, as can be seen by the reduced cloudiness and increased transparency and gloss compared to the unblended polyolefin copolymer compositions of the present invention. This is evident from the data in Table 7 below.

For films made from blends, the heat seal initiation temperature, as seen by the decrease in temperature and the final seal strength (lbs) required to obtain a two pound heat seal over the unblended polyolefin copolymer composition of the present invention. Increased significantly. The data related to such heat sealing and sealing strength is shown in Table 8 below.

As the amount of homopolymer LDPE resin increased, it was observed that the film strength or mechanical properties decreased as the linear properties of the blend decreased compared to the unblended polyolefin copolymer compositions of the present invention. The reduction in mechanical properties is shown in Table 10 below.

Blending the polyolefin copolymer composition of the present invention into an LDPE homopolymer improved the properties of the resulting film, such as ultimate tensile strength, dart impact resistance, Elmendorf tear strength, and high temperature adhesive strength compared to unblended LDPE. .

High temperature adhesive strength is the strength (N) required to separate the two films in a partially dissolved state. This test is used to simulate the ability of the package to maintain the seal without distracting the contents, during which the heat seal has not yet cooled. When the polyolefin copolymer composition of the present invention was blended into LDPE, the hot tack strength increased as in the temperature range where hot tack was observed. The data is shown in Table 9 below.

For the polyolefin copolymer compositions of the present invention, the relatively low machine direction (MD) Elmendorf tearing is relatively unaffected by the addition of LDPE. The stretching effect changed the transmembrane (CD) tearing degree. The dart impact of the polyolefin copolymer composition of the present invention is very high and slightly affected when blended moderately with LDPE. Data on these film properties are shown in Table 10 below.

Thus, while the high strength of the polyolefin copolymer compositions of the present invention is slightly damaged by blending with LDPE homopolymers, it is evident that other properties can be advantageously affected. Similarly, some properties of the unblended LDPE homopolymer may be adversely affected by blending with the polyolefin copolymer composition of the present invention, but the strength of the blend is superior to the unblended LDPE.

Claims (20)

In a polyolefin copolymer composition prepared by a polymerization process of one α-olefin monomer and one or more olefin comonomers using a catalyst having a metallocene complex in a single reactor, 50 weight of the composition having the highest comonomer content (% by weight) exhibited by having a comonomer partition coefficient C _pf defined by Equation 1 above 1.10 and / or a molecular weight partition coefficient M _pf defined by Equation 2 above 1.15. Polyolefin copolymer composition having a maximum molecular weight in% portion: Equation 1 Where c _i is the mole fraction of the comonomer content, w _i is the normalized weight fraction measured by GPC / FRIR for n FTIR data points of at least median molecular weight, c _j is the mole fraction of the comonomer content, w _j is the normalized weight fraction measured by GPC / FTIR for m FTIR data points below the median molecular weight, where only the weight fraction w _i or w _j associated with the mole fraction value of the comonomer content is used to calculate C _pf . Used, n and m are 3 or more. Equation 2 Where M _i is the viscosity average molecular weight, w _i is the normalized weight fraction measured by ATREF-DV for n data points at fractions below the median elution temperature, M _j is the viscosity average molecular weight, w _j is the normalized weight fraction measured by ATREF-DV for m data points at fractions above the median elution temperature, where only the weight fraction w _i or w _j associated with a viscosity average molecular weight greater than zero calculates M _pf Used to n and m are three or more. The method of claim 1, A polyolefin copolymer composition having a density of 0.87 to 0.96 g / cm 3. The method of claim 1, Polyolefin copolymer composition having a melt index I _{2 of} from 0.01 to 150. The method of claim 1, A polyolefin copolymer composition having I ₂₁ / I ₂ of 24 or more. The method of claim 1, The polyolefin copolymer composition having M _w / M _n of 2.0 to 10. The method of claim 1, A polyolefin copolymer composition having at least 0.01 long chain branches per 1000 carbon atoms along the polymer backbone. The method of claim 1, Olefin comonomers include propene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1,7-octadiene, A polyolefin copolymer composition which is 1,5-hexadiene, 1,4-pentadiene, 1,9-decadiene, ethylidene norbornene, styrene or a mixture thereof. The method of claim 1, A polyolefin copolymer composition containing 0.01 to 99.99 mol% of ethylene and 99.99 to 0.01 mol% of at least one olefin comonomer as a monomer. The method of claim 1, A polyolefin copolymer composition containing from 0.01 to 99.99% by weight of propylene and from 99.99 to 0.01% by weight of at least one olefin comonomer as a monomer. The method of claim 1, A polyolefin copolymer composition prepared using a catalyst having a metallocene complex of Formula 1 Formula 1 Where M is titanium or zirconium in a formal oxidation state of +2; L is a group containing a cyclic, unlocalized anionic π-system that binds M and also Z; Z is a moiety of 60 or less non-hydrogen atoms which is bonded to M via σ-bond, which contains elements of group 14 of the boron or periodic table of the elements and contains an element selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen ego; X forms a π-complex with M and is a conjugated or nonconjugated diene having 40 or less carbon atoms optionally substituted with one or more groups selected from hydrocarbyl or trimethylsilyl groups. The method of claim 1, A polyolefin copolymer composition prepared by a catalyst having a metallocene complex of formula Formula 2 Where Cp ¹ and Cp ² are independently substituted or unsubstituted indenyl or hydrogenated indenyl groups; Y is a monovalent anionic ligand or Y ₂ is a diene; M is zirconium, titanium or hafnium; Z is an alkylene group having 1 to 20 carbon atoms; Dialkyl silyl groups or germanyl groups; Or a bridging group comprising an alkyl phosphine or amine radical. The method of claim 1, A polyolefin copolymer composition wherein the catalyst is a single metallocene complex. The method of claim 1, Copolymer composition prepared in a continuous process in a single gas phase reactor. The method of claim 1, Polyolefin copolymer composition prepared in a reactor having a reaction zone of 60 ℃ or more. The method of claim 1, Polyolefin copolymer composition prepared in a reactor having a reaction zone of 70 ℃ or more. The method of claim 1, A polyolefin copolymer composition having a polycrystalline short chain branching distribution or a polycrystalline molecular weight distribution. The method of claim 1, A polyolefin copolymer composition prepared in a reactor having a reaction zone of at least 70 ° C., with a density of 0.910 to 0.925, a molar ratio of comonomer to monomer less than 0.02, and a ratio of hydrogen to monomer less than 0.02. Copolymers of 1-hexene and ethylene at molar ratios of 0.02 or less at a temperature of 70 ° C. and ethylene pressure of 8 bar have a long chain branching along the polymer backbone or 50% of the highest comonomer content (% by weight) in a continuous gas phase polymerization process. The polyolefin copolymer according to claim 1, wherein the molecular weight is maximum and the density is 0.918 in the 50% by weight part of the composition having the highest molecular weight in the weight part or the long chain branching along the polymer backbone and the highest comonomer content (% by weight). Organometallic polymerization catalysts suitable for preparing the composition. Melt strength greater than 4 cN, sealing strength greater than 1.9 kg (4.2 lb), hot tack greater than 0.53 kg (0.5 lb) or dart impact greater than 100 g prepared from the polyolefin copolymer composition according to claim 1 (dart impact) Films or other products having strength. (A) 1 to 99% by weight of the polyolefin copolymer composition according to claim 1; And (B) A blend of two or more resin components, comprising 99% to 1% by weight of one or more resins different from component (A).