WO2007002585A1 - Copolymeres d'alpha-olefines c10+ et d'autres alpha-olefines et procede de copolymerisation - Google Patents

Copolymeres d'alpha-olefines c10+ et d'autres alpha-olefines et procede de copolymerisation Download PDF

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Publication number
WO2007002585A1
WO2007002585A1 PCT/US2006/024804 US2006024804W WO2007002585A1 WO 2007002585 A1 WO2007002585 A1 WO 2007002585A1 US 2006024804 W US2006024804 W US 2006024804W WO 2007002585 A1 WO2007002585 A1 WO 2007002585A1
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WO
WIPO (PCT)
Prior art keywords
group
cyclopentadienyl
decene
alpha olefin
alkyl
Prior art date
Application number
PCT/US2006/024804
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English (en)
Inventor
Tze-Chiang Chung
Han Hong
Robert Wen Lee
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Shell Internationale Research Maatschappij B.V.
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Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2007002585A1 publication Critical patent/WO2007002585A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; 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
    • C08F4/60—Metals; 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the field of this invention is the copolymerization of alpha olefins and copolymers of Ci 0+ alpha olefins with lower carbon number alpha olefins.
  • LLDPE Linear low density polyethylene
  • the present invention provides a process for copolymerizing do + alpha olefins with lower carbon number alpha olefins to produce copolymers with high molecular weight.
  • the process can achieve high incorporation of the C 10+ monomer into the copolymer.
  • the present invention provides such a process which comprises copolymerizing a Ci 0+ alpha olefin with a lower carbon number, preferably C 2 -g, most preferably C 2 ⁇ 8, alpha olefin in the presence of a catalyst composition comprising a) a constrained geometry metallocene and b) a cocatalyst. It is preferred that the metallocene be a single-site constrained geometry metallocene.
  • the C1 0+ alpha olefin copolymers of this invention may have a viscosity molecular weight (M v ) of from 14,000 to 500,000, preferably from 14,000 to 100,000, most preferably from 14,000 to 60,000.
  • M v viscosity molecular weight
  • the amount of the C 10+ alpha olefin monomer in the copolymers may range from 0.5 % mol (mole percent) to less than 100% mol, preferably from 0.5 to 20, more preferably from 1 to 15, most preferably from 1.5 to 10.
  • Figure 1 is the DSC melting temperature curve for the copolymer described in Table 3 below.
  • Figure 2 illustrates the comparison of comonomer incorporation mole% (top) and weight% (bottom) among 1-decene (o) , 1-octene (*) , and 1-hexene ( ⁇ ) in the LLDPE copolymer by- varying monomer feed ratios.
  • C 10+ alpha olefins which may be used in the process herein include 1-decene, 1-dodecene, 1-tetradecene, 1- hexadecene, 1-octadecene, 1-eicosene, and Cn, 13 , ⁇ 5 ⁇ 17f 19 and C 21 - 24 alpha olefins, and the like.
  • the olefins may be linear or branched.
  • the preferred C3.0 + ⁇ -olefin is 1-decene.
  • C 2 - 9 alpha olefins which may be used herein as including ethylene, propylene, 1-butene, 4-methyl-l-pentene, 3-methyl-l-butene, 3-methyl-l-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene.
  • C 2 - S ⁇ -olefins are preferred.
  • the preferred C 2 -8 ⁇ -olefins for use herein are ethylene, propylene, 1- butene.
  • the olefins may be linear or branched. Ethylene is most preferred.
  • the metallocenes of this invention may have covalently- bridged ring ligands and a ligand-metal-ligand angle, ⁇ , formed at the metal center between the ligands of from 135° to 100°, preferably from 115° to 100°.
  • ⁇ ligand-metal-ligand angle
  • the angle ⁇ is measured from the centroid position of the five-membered ring (the point in a system of masses each of whose coordinates is a mean value of the coordinates for each dimension for all points in the system) .
  • the angle is measured by X-ray diffraction.
  • the amount of the metallocene employed may be from 20 ppm weight to 1 wt.%, based upon the total amount of comonomers .
  • the preferred amount may be from 0.001 to 0.2 wt.%, based upon the total amount of comonomers.
  • the constrained geometry metallocene be single site in order to obtain a copolymer with a desirably narrow molecular weight distribution.
  • the weight average molecular weight (M w ) is generally about twice that of the M n and the viscosity molecular weight (M v ) is generally in between the M w and the M n .
  • the M w /M n for the copolymers of this invention may be from 2 to 5, preferably closer to 2.
  • Preferred single-site constrained geometry metallocenes useful herein include metallocenes which may have the following formula:
  • M is a metal of Group 3 or Group 4 of the Periodic Table of the Elements. Preferred metals include titanium and zirconium.
  • L and L' are ligands independently selected from -NR-, -PR-, cyclopentadienyl, and substituted cyclopentadienyl groups . The cyclopentadienyl and/or substituted cyclopentadienyl groups may be bound in an ⁇ 5 bonding mode to the metal. At least one of L and L' is a cyclopentadienyl or substituted cyclopentadienyl group. Y is a bridging moiety.
  • Y may be selected from -SiR 2 -, -CR 2 -, and -CR 2 -CR 2 -.
  • R is independently selected from hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl and is defined in more detail below.
  • Hydrogen is most highly preferred as Y.
  • X is a metal substituent. X may be selected from hydrogen, halo, and alkyl, aryl, aryloxy, and alkoxy wherein the carbon atoms-containing groups may have from 1 to 20, preferably 1 to 15, more preferably 1 to 5 carbon atoms. Hydrogen is most highly preferred as X.
  • n may be 0, 1 or 2.
  • metallocenes which may have the following formula:
  • R may contain from 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.
  • specific examples of the hydrocarbon groups may include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, a butadienyl group, a triphenylcarbyl group or the like.
  • the substituted cyclopentadienyl ligands may have substituent hydrocarbon groups which may be monovalent groups bonded to the cyclopentadienyl group. These substituent groups may be those R groups described in the preceding paragraph. Furthermore, the two hydrocarbon substituent groups may be bonded with each other at end positions thereof to form a condensed ring. Typical examples of cyclopentadienyl groups having the condensed ring may include indene, fluorene, azulene or derivatives thereof.
  • R other than the aforementioned hydrocarbon groups
  • hydrocarbon groups containing silicon, oxygen, nitrogen, phosphorus, boron, sulfur or the like.
  • Typical examples of the hydrocarbon residues may include a methoxy group, an ethoxy group, a phenoxy group, a furyl group, a trimethylsilyl group, a diethylamino group, a diphenylamino group, a pyrazolyl group, an indolyl group, a carbazolyl group, a dimethylphosphino group, a diphenylphosphino group, a diphenylboron group, a dimethoxyboron group, a thienyl group or the like.
  • metallocenes useful herein include
  • Cocatalysts useful herein include those which activate the metallocene to form an active species for alpha-olefin polymerization. Cocatalysts are sometimes referred to as activators. Specific types of cocatalyst may include alumoxanes, borates, and acidic clay and clay minerals.
  • aluminoxane suitable for use as a cocatlayst can be used herein. Mixtures of two or more aluminoxane compounds may also be used herein. Suitable aluminoxane compounds for use herein include methylalur ⁇ inoxane (MAO) and modified methylaluminoxane (MMAO) . Modified methylaluminoxane is derived from methylaluminoxane with a portion of the methyl groups replaced with other alkyl groups, for example, isobutyl groups. The alkyl groups may contain from 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably from 1 to 5 carbon atoms.
  • hydrocarbon groups may include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, a butadienyl group, a triphenylcarbyl group or the like.
  • the cocatalyst is a modified methylaluminoxane, preferably herein about 25% of the methyl groups are replaced with isobutyl groups .
  • the cocatalyst may be a borate, preferably a borate.
  • Preferred borates include tetra (pentafluorophenyl) borate and methyltri (pentafluorophenyl) borate .
  • the cocatalyst may be acidic clay or a clay mineral.
  • Preferred acidic clays include allophane group clays or clay minerals such as allophane; kaolin group clays or clay minerals such as dickite, nacrite, kaolinite or anauxite, halloysite group clays or clay minerals such as meta- halloysite or halloysite; serpentine group clays or clay minerals such as chrysotile, lizardite or antigorite; smectite group clays or clay minerals such as montmorillonite, sauconite, beidellite, nontronite, saponite or hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite or glauconite; attapulgite; sepiolite; palygorskite; bentonite; gnarl clay; gairome clay hisingerite; pyrophyllite; and chlorite groups.
  • the catalyst may be prepared by any method known in the art. Generally, the preparation of the metallocene complex consists of forming and isolating the cyclopentadienyl or substituted cyclopentadienyl group ligands which are then reacted with a halogenated metal to form the complex. Other methods known in the art may also be employed.
  • the process for making the copolymers of Ci 0+ alpha olefins and other molecular size alpha olefins described herein may be carried out by any conventional means for copolymer!zation of other alpha olefins including solution, gas phase, and slurry polymerization.
  • the polymerization may be carried out at a temperature of 25°C to 200 0 C, preferably 12O 0 C to 180°C, and a pressure of 0.5 to 6 MPa, preferably from 2 to 6 MPa.
  • the cocatalyst may be mixed with the Cio + comonomer and then the ethylene (or other alpha olefin monomer) is added followed by the catalyst composition.
  • Other methods and sequences of steps known in the art may also be utilized.
  • the Cio + alpha olefin copolymers of this invention may have a viscosity molecular weight (M v ) of from 14,000 to 500,000, preferably from 14,000 to 100,000, most preferably from 14,000 to 60,000.
  • M v viscosity molecular weight
  • the amount of the C 10+ alpha olefin monomer in the copolymers may range from 0.5 mol% to less than 100 mol%, preferably from 0.5 to 20, most preferably from 1.5 to 10.
  • the ethylene/1-decene copolymers of this invention are generally homogeneous in terms of the incorporation of the 1- decene into the copolymer. One indication of this homogeneity is shown by the narrowness of the melting point.
  • the ethylene/1-decene copolymers of this invention are generally homogeneous in terms of the incorporation of the 1- decene into the copolymer. One indication of this homogeneity is shown by the narrowness of the melting point.
  • Differential scanning calorimetry (DSC) was used to measure the melting temperature of the some of the copolymers with a heating rate of 10°C/min. The DSC curve was recorded in the second heating cycle.
  • Figure 1 is the DSC melting temperature curve for the copolymer described in Table 3 below with 0.99%mol 1-decene. W is the power in watts. The melting peak completely disappears above 12 mole% of 1-decene content. The copolymer is amorphous at that point and there is only one melting point.
  • the half-width of the melting peak is a good way to gauge the narrowness of the melting point of the copolymers which have from 0.5 to 12 mole% 1-decene.
  • the half-width is determined by the peak width at half of the height of the melting peak measured from top of the peak to the baseline of the whole peak. This calculation is exemplified in Figure 1 wherein the height is from the peak of 128.25°C and the low point is 121.79°C (94.14 joules per second per gram).
  • the copolymers with 5 to 12 mole% of 1-decene content show a significant melting peak, the half-width of which may range from 5 0 C to 1O 0 C.
  • solution polymerization was carried out in an autoclave (300ml) equipped with a mechanical stirrer.
  • the comonomer i.e. 1-hexene, 1-octene, or 1-decene
  • heptane solvent and MAO in the autoclave.
  • the total volume of heptane and comonoraer was controlled at 100ml.
  • the sealed reactor was then saturated with 480-500 psi (3.4-3.6 MPa) ethylene pressure at 140 ⁇ 15Q°C before adding the metallocene solution (i.e. in toluene) to initiate the polymerization.
  • the viscosity molecular weights (M v ) of the copolymers were determined by intrinsic viscosity or/and Gel Permeation Chromatography (GPC) measurements.
  • the intrinsic viscosity ( ⁇ ) is measured in a dilute decalin solution with polymer concentration of 50 mg/50ml at 135°C.
  • GPC measurement is carried out in a Waters 150 C with a refractive index (RI) detector and a set of u-Styragel HT columns of 10 6 , 10 5 , 10 4 , and 10 3 pore size in series.
  • the measurements were taken at 140° C using 1,2, 4-trichlorobenzene (TCB) as solvent and a mobile phase of 0.7 ml/min flow rate.
  • TCB 1,2, 4-trichlorobenzene
  • Figure 2 illustrates the comparison of comonomer incorporation mole% (top) and weight% (bottom) among 1-decene (o) , 1-octene (*) , and 1-hexene ( ⁇ ) in the LLDPE copolymer by varying monomer feed ratios.
  • Figure 2 (E means ethylene) compares the comonomer incorporation (mole% and weight%) between 1-decene and two common comonomers (1- octene and 1-hexene) in the copolymer by varying monomer feed ratios.
  • the incorporation of 1-decene into the ethylene/1- decene copolymer is systematically higher than the incorporation of 1-hexene and 1-octene are incorporated into the ethylene/1-hexene and ethylene/1-octene copolymers.
  • Example 2 These experiments were carried out according to the procedure of Example 1 with the exceptions that the total liquid volume was 200 ml, the ethylene pressure was 600 psi (4.1 MPa), and the reaction time was 13 minutes.
  • Table 4 describes the copolymerization of 1-octene with ethylene and
  • Table 5 describes the copolymerization of 1-octene with ethylene and
  • Table 5 describes the copolymerization of 1- decene with ethylene.
  • the copolymers from each of the three runs for each comonomer were combined and tested according to ASTM D638. The results are shown in Table 6.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de copolymérisation d'alpha-oléfines C10+, qui consiste à copolymériser une alpha-oléfine C10+ avec une autre alpha-oléfine en présence d'un catalyseur métallocène à géométrie contrainte et d'un cocatalyseur. L'invention se rapporte également à des copolymères d'éthylène et de 1-décène.
PCT/US2006/024804 2005-06-28 2006-06-26 Copolymeres d'alpha-olefines c10+ et d'autres alpha-olefines et procede de copolymerisation WO2007002585A1 (fr)

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US60/694,812 2005-06-28

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WO2007002585A1 true WO2007002585A1 (fr) 2007-01-04

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999054369A1 (fr) * 1998-04-21 1999-10-28 Montell Technology Company B.V. Procede de preparation de copolymeres d'ethylene a l'aide d'alpha-olefines
US6124513A (en) * 1997-06-20 2000-09-26 Pennzoil-Quaker State Company Ethylene-alpha-olefin polymers, processes and uses
WO2002024769A2 (fr) * 2000-09-25 2002-03-28 Basell Technology Company B.V. Procede de preparation de polymeres d'ethylene
WO2004033510A2 (fr) * 2002-10-10 2004-04-22 Basell Polyolefine Gmbh Procede de copolymerisation d'ethylene
EP1416000A1 (fr) * 2002-10-30 2004-05-06 Mitsui Chemicals, Inc. Procédé de préparation de (co)polymères d'oléfine de bas poids moléculaire et catalyseur de polymérisation utilisé à cette fin
WO2005070976A1 (fr) * 2004-01-22 2005-08-04 Innovene Europe Limited Procede de polymerisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124513A (en) * 1997-06-20 2000-09-26 Pennzoil-Quaker State Company Ethylene-alpha-olefin polymers, processes and uses
WO1999054369A1 (fr) * 1998-04-21 1999-10-28 Montell Technology Company B.V. Procede de preparation de copolymeres d'ethylene a l'aide d'alpha-olefines
WO2002024769A2 (fr) * 2000-09-25 2002-03-28 Basell Technology Company B.V. Procede de preparation de polymeres d'ethylene
WO2004033510A2 (fr) * 2002-10-10 2004-04-22 Basell Polyolefine Gmbh Procede de copolymerisation d'ethylene
EP1416000A1 (fr) * 2002-10-30 2004-05-06 Mitsui Chemicals, Inc. Procédé de préparation de (co)polymères d'oléfine de bas poids moléculaire et catalyseur de polymérisation utilisé à cette fin
WO2005070976A1 (fr) * 2004-01-22 2005-08-04 Innovene Europe Limited Procede de polymerisation

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KIM I ET AL: "COPOLYMERIZATION OF ETHYLENE AND 1-DECENE BY METALLOCENES: DIRECT COMPARISON OF ME2C(CP)(FLU)ZRME2 WITH ET(CP)(FLU)ZRME2", POLYMER ENGINEERING & SCIENCE, WILEY, HOBOKEN, NJ, US, vol. 41, no. 6, June 2001 (2001-06-01), pages 899 - 907, XP001089090, ISSN: 0032-3888 *
RAZAVI A ET AL: "GEOMETRIC FLEXIBILITY, LIGAND AND TRANSITION METAL ELECTRONIC EFFECTS ON STEREOSELECTIVE POLYMERIZATION OF PROPYLENE IN HOMOGENEOUS CATALYSIS", JOURNAL OF MOLECULAR CATALYSIS. A, CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 115, no. 1, 1997, pages 129 - 154, XP008044622, ISSN: 1381-1169 *
RAZAVI A ET AL: "Preparation and crystal structures of the complexes (eta<5>-C5H3Me-CMe2-eta<5>-C13H8)MCl2 (M = Zr or Hf): mechanistic aspects of the catalytic formation of a syndiotactic-isotactic stereoblock-type polypropylene", JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 497, no. 1, 26 July 1995 (1995-07-26), pages 105 - 111, XP004023847, ISSN: 0022-328X *
RAZAVI A ET AL: "Preparation and crystal structures of the complexes (eta<5>-C5H3TMS-CMe2-eta<5>-C13H8)MCl2 and [3,6-di<t>ButC13H6-SiMe2-N <t>Bu]MCl2 (M=Hf, Zr or Ti): mechanistic aspects of the catalytic formation of a isotactic-syndiotactic stereoblock-type polypropylene", JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 621, no. 1-2, 1 March 2001 (2001-03-01), pages 267 - 276, XP004231263, ISSN: 0022-328X *

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