WO1991002012A1 - Very high molecular weight polyethylene - Google Patents

Very high molecular weight polyethylene

Info

Publication number
WO1991002012A1
WO1991002012A1 PCT/US1990/004366 US9004366W WO1991002012A1 WO 1991002012 A1 WO1991002012 A1 WO 1991002012A1 US 9004366 W US9004366 W US 9004366W WO 1991002012 A1 WO1991002012 A1 WO 1991002012A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
weight
molecular
polyethylene
distribution
high
Prior art date
Application number
PCT/US1990/004366
Other languages
French (fr)
Inventor
Gregory George Hlatky
Howard William Turner
Original Assignee
Exxon Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Abstract

A very high molecular weight distribution can be prepared from a two component catalyst system. The polymer has a molecular weight range of from 1 x 106 to 25 x 106 and a molecular weight distribution range of 1.0 to 3.0

Description

VERY HIGH MOLECULAR WEIGHT POLYETHYLENE

Specification This is a continuation-in-part of U.S. patent application Serial No. 133,480, filed December 22, 1987, which was a continuation-in-part of U.S. patent application Serial No 008,800, filed January 3, 1987. Field of the Invention:

This invention relates to polymers produced by (co)polymerizing ethylene in the presence of certain catalyst systems described herein. More particularly, this invention relates to (co)polyethylene having a very high molecular weight and a narrow molecular weight distribution.

A method of preparing polymers, which includes the catalyst compositions and methods of preparing these catalysts, is set forth in full detail in copending U.S. patent application Serial No. 133,480 (also European patent application Serial No. 277,004, published August 3, 1988) and will not be repeated herein except to the extent necessary for clarity. However, the entire disclosure of U.S. patent application Serial No. 133,480 is expressly incorporated herein by reference. The disclosure does not exemplify polyethylenes having molecular weights 1n excess of about 1,000,000. Molecular weights in excess of 2,000,000 are not mentioned. Background of the Invention

The production of polyethylene and Its uses are well known in the prior art. It is also known that the physical properties of polyethylene (Indeed any polymer) vary with Its molecular weight. For example, very high molecular weight polyethylene—I.e., polyethylene with a weight-average molecular weight in excess of 1,000,000—has a low coefficient of friction and high abrasion resistance, Impact toughness and tensile strength. Very high molecular weight polyethylene 1s used In rolling stock, materials handling, and fiber spinning from polymer gels.

Another characteristic which affects the physical properties of a polymer is its molecular weight distribution, defined by the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). A polymeric product which has a broad molecular weight distribution, i.e., greater than about 5, will have certain undesirable characteristics. For Instance, it is now realized when used in fiber spinning, polyethylene having both a broad molecular weight distribution and a very high molecular weight causes Instabilities in the fiber spinning process. The use of Ziegler-Natta type catalysts for the polymerization of ethylene to polyethylene is well known 1n the prior art. The traditional Ziegler-Natta type systems comprise a transition metal halide activated to a catalyst species by reaction with a metal alkyl cocatalyst, particularly an aluminum alkyl cocatalyst. The activation of these traditional Ziegler-Natta catalysts generates a variety of different active sites, each of which has Its own rate of Initiation, propagation, and termination. As a consequence of this non-uniformity of active sites, the catalysts linear polyethylene having a broad molecular weight distribution. Recently, it has been found that active polymerization catalysts are formed when bis(cyclopentadienyl) compounds of the Group I\ B metals are used with methylalumoxane. As is well known, these systems offer several distinct advantages, in particular the production of polymers with narrower molecular weight distributions (Mw/Mn<3) than those from conventional Ziegler-Natta type catalysts. These recently discovered catalyst systems, however, yield polymeric products having relatively moderate weight-average molecular weights, i.e., less than 500,000.

The need for a very high molecular weight polyethylene and preferably Tinear polyethylene having narrow molecular weight distribution is apparent. Summary ofthe Invention:

In accordance with the present invention, very high molecular weight polyethylene, preferably high density, linear polyethylene having a narrow molecular weight distribution is produced. One method involves using a catalyst prepared by combining at least two components. The first component is a bis(cyclopentadienyl) derivative of a Group IV-B metal compound containing at least one ligand which will combine with the second component or at least a portion thereof, such as a cation portion. The second component is an ion-exchange compound comprising a cation which will irreversibly react with the first component and an anion which is a single coordination complex capable of stabilizing the Group IV-B metal cation complex and sufficiently labile to permit displacement by ethylene during polymerization.

In the synthesis of the polymers of this invention, bis(cyclopentadienyl) hafnium-based catalysts are preferred and tr1alkyl- and/or -arylammonium salts of tetrakis(pentafluoro- phenyDboron are the most preferred activators. These catalyst systems can produce polyethylenes having molecular weights in the range of about 5 x 10 and greater. In accordance with this Invention it has been discovered that through pressure and temperature controls one can obtain polyethylene having molecular weight in excess of 1,000,000 and typically from 1 x 10 to about 25 x 10 with molecular weight distributions less than about 3. Typically the molecular weight distributions will be in the range of about 1.3 to about 3.0. These polymers are unique in that they combine a very high molecular weight with a very narrow molecular weight distribution. The preferred polymer has a molecular weight range from about 2 x 10 to 6 x 10 with a molecular weight distribution of about 2.0 or less. Detailed Description of the Invention:

It has been discovered that very high molecular weight polyethylene having a narrow molecular weight distribution can be produced. The hafnium-based catalyst system used to produce the polymers of this Invention are detailed in U.S. patent application Serial No. 133,480 which is expressly incorporated herein by reference.

The present invention relates to polyethylenes having both a very high molecular weight and a narrow molecular weight distribution. The term "very high molecular weight" is Intended to encompass polymers having a molecular weight of about 1 x 10 and above. Preferably the polymers will have a molecular weight of 2 x 10 and above. In accordance with this Invention, polymers having molecular weight up to about 25 x 10 and greater can be produced while maintaining the molecular weight distribution at about less than 3.

A surprising feature of this invention 1s that such very high molecular weight polyethylene polymers can be produced with a narrow molecular weight distribution. The molecular weight distribution Is defined as the ratio of weight-average molecular weight to number-average molecular weight. For the purpose of this invention, a "narrow" molecular weight distribution means In the range of about 1.0 to about 3.0. Generally, the molecular weight distribution is about 1.3 to about 3 or less.

A catalyst useful for preparing such very high molecular weight polyethylene polymers is prepared by combining at least one first compound which is a bis(cyclopentadienyl) derivative of a metal of Group IV-B containing at least one ligand which will combine with a cation of the second compound which first compound 1s capable of forming a cation formally having a coordination number of 3 and a valence of +4 and at least one second compound which is a salt comprising a cation capable of donating a proton which will irreversibly combine with said at least one Ugand (substituent) liberated by said Group IV-B metal compound and an ion which"is a single coordination complex comprising a charge-bearing metal or metalloid core, which anion 1s both bulky and labile, compatible with and non-coordinating toward the Group IV-B metal cation formed from the first component, and capable of stabilizing the Group IV-B metal cation without Interfering with said Group IV-B metal cations or its decomposition product's ability to polymerize ethylene. T e Group IV-B metal compounds, I.e., titanium, zirconium and hafnium compounds, useful as first compounds in the preparation of the catalyst capable of producing the polymer of this invention are bis(cyclopentadienyl) derivatives of titanium, zirconium and hafnium. The preferred Group IV-B metal compound is hafnium. Compounds useful as a second component 1n the preparation of the catalyst used to make the very high molecular weight polyethylene of this invention will comprise a cation, which is a Bronsted add capable of donating a proton, and a compatible non-coordinating anion containing a single coordination complex comprising a charge-bearing metal or metalloid core, which anion is relatively large (bulky), capable of stabilizing the active catalyst species (the Group IV-B cation) which 1s formed when the two compounds are combined and said anion will be sufficiently labile to be displaced by ethylene. The preferred second component is trlalkyl- and/or -arylammonium salts of tetrak1s(pentaf1uoro- phenyDboron. Especially preferred second components are tri(n-butyl)ammonium tetrakls(pentafluorophenyl)boron and N,N-d1methylanil1n1um tetrakis(pentafluorophenyl)boron.

The following examples are illustrative of the types of polymers that can be produced and are not Intended to limit the scope of this invention: EXAMPLE 1

In this example, ethylene was polymerized to linear polyethylene by adding to a 1 liter stainless-steel autoclave, previously purged with nitrogen and containing 400 ml of dry, deoxygenated hexane, first a solution containing 15 mg of b1s(eyelopentadienyl)hafnium dimethyl in 30 ml of toluene, then, after 5 minutes, a solution of bis(cyclopentadienyl)hafnium dimethyl (12 mg) and tri(n-butyl)ammonium tetrakis(pentafluoro- phenyl)boron (30 mg) in toluene (50 ml). The autoclave was pressured with 90 psig of ethylene and stirred for 1 hour at 60*C. The autoclave was then vented and opened, and the polymer product Isolated. The yield of polyethylene was 73.8 g. This material had a weight-average molecular weight of 1,123,000, a peak-maximum molecular weight of 1,097,000 and a molecular weight distribution of 1.78. EXAMPLE 2

In this example, ethylene was polymerized by adding to an autoclave as described In Example 1 a solution of b1s(eyelopenta¬ dienyl)hafn1urn dimethyl (9 mg) and N,N-d1methy1an1l1n1um tetrak1s(pentafluorophenyl)boron (3 mg) 1n toluene (10 ml). The autoclave was pressured to 400 psig and stirred at 30'C for 30 minutes. The autoclave was vented and opened, and the polymer product isolated. The yield of linear polyethylene was 42.4 g. This material had a calculated weight-average molecular weight of 2,487,000, a peak-maximum molecular weight of 3,204,000 and a calculated molecular weight distribution of 1.49. In accordance with the Invention, polymerizations carried out at lower temperatures will lead to polymers with higher molecular weights and polymerizations carried out at higher pressures will obtain polymers of higher molecular weight.

These very high molecular weight polyethylenes having narrow molecular weight distributions have been found to be highly deslreable fn high tensile strength applications, such as in the production of oriented polyethylene fibers by gel-spinning.

The principle of the invention and the best mode contemplated for applying that principle have been described. It is to be understood that the foregoing Is illustrative only and that other means and techniques can be employed without departing from the true scope of the invention defined 1n the following claims.

Claims

1. Polyethylenes having a weight-average molecular weight greater thhaann aabboouutt 11 x 10 and a molecular weight distribution less than about 3.0.
2. The polymer of claim 1 wherein the molecular weight distribution ranges from about 1.3 to about 2.0.
3. The polymer of claim 2 having a weight-average molecular weight ranging from about 2 x 10 to about 25 x 10 .
4. The polymer of claim 3 wherein the weight-average molecular weight ranges from about 2 x 10 to about 6 x 10 .
PCT/US1990/004366 1989-08-03 1990-08-03 Very high molecular weight polyethylene WO1991002012A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US38909989 true 1989-08-03 1989-08-03
US389,099 1989-08-03

Publications (1)

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US5296433A (en) * 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
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