WO2000069924A1 - Ziegler-natta polymerization of alpha-olefins in the presence of non-polymerizing olefins - Google Patents
Ziegler-natta polymerization of alpha-olefins in the presence of non-polymerizing olefins Download PDFInfo
- Publication number
- WO2000069924A1 WO2000069924A1 PCT/US1999/028471 US9928471W WO0069924A1 WO 2000069924 A1 WO2000069924 A1 WO 2000069924A1 US 9928471 W US9928471 W US 9928471W WO 0069924 A1 WO0069924 A1 WO 0069924A1
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- Prior art keywords
- olefin
- polymerizing
- olefins
- alpha
- mole percent
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
Definitions
- This invention relates to a method for increasing molecular weight and/or stereoregularity of poly(alpha-olef ⁇ ns) by polymerizing alpha-olefins in the presence of 1) a Ziegler-Natta catalyst system and 2) at least one non-polymerizing olefin which is not polymerizable under the polymerization conditions.
- Ziegler-Natta catalyst systems are commonly used for polymerization of alpha-olefins.
- US 3,732,198 (Whiteley) concerns a method of polymerizing ethylene, at high pressure and temperature, employing a Ziegler-Natta catalyst pretreated with an allylic compound.
- the reference teaches the use of the allylic compound to suppress free radical polymerization and thereby suppress branching in the resulting polymer.
- the present invention provides a method of increasing molecular weight and/or stereoregularity of poly(alpha-olefins) by polymerizing alpha-olefins having three or more carbon atoms in the presence of 1) a Ziegler-Natta catalyst system and 2) at least one non-polymerizing olefin which is not polymerizable under the polymerization conditions.
- the non-polymerizing olefin may then be volatilized or otherwise removed along with any unreacted monomer.
- the invention further provides a means to temper polymerization rates and reaction temperatures.
- cyclic internal olefin means a compound having a non-aromatic cyclic group wherein at least two carbon atoms of a ring are connected to each other by a double bond, e.g., cyclohexene, methyl cyclohexene, phenyl cyclohexene, and the like;
- alpha-olefin means a compound of the formula HaC ⁇ CHR wherein R is a substituted or unsubstituted alkyl group which may be straight-chain or may contain branches or cycles; and "substituted” means substituted by conventional substituents which do not substantially interfere with the characteristics of the desired processes or products, e.g., substituents may be alkyl, alkoxy, aryl, phenyl, halo (F, Cl, Br, I), cyano, nitro, etc.
- Figure 1 is a graph of the inherent viscosities of the polymers of Examples
- Race A 8C and 9-13 (Trace A) and Examples 14C and 15-19 (Trace B), charted as a function of the amount of non-polymerizing olefin added to the polymerization mixture.
- Figure 2 is a graph indicating the molecular weight populations of the polymers of Comparative Example 20 (Trace A) and Examples 21 and 22 of the invention (Traces B and C, respectively), based on size exclusion chromatography.
- Figure 3 is a graph of temperature vs. time demonstrating exotherm measurements performed during polymerization of Comparative Example 23 (Trace A) and Examples 24-26 of the invention (Traces B. C and D, respectively).
- Figure 4 is NMR spectra of the polymeric products of Comparative Example 29C (Trace A) and Examples 30-32 of the invention (Traces B, C and D, respectively).
- the present invention provides a method for increasing molecular weight and/or stereoregularity of poly(alpha-olefins) by polymerizing alpha-olefins in the presence of 1) a Ziegler-Natta catalyst system and 2) at least one non-polymerizing olefin which is not polymerizable under the polymerization conditions.
- Monomers for polymerization may include any suitable alpha-olefins or mixtures of alpha-olefins. Preferably, monomers contain between 3 and 30 carbon atoms and more preferably between 3 and 15 carbon atoms. Most preferably, monomers contain between 5 and 10 carbon atoms. Monomers may contain branch points or cycles but are preferably straight-chain. Monomers may be substituted but are preferably unsubstituted. A mixture of two or more monomers may be used to form copolymers.
- the non-polymerizing olefin is any suitable olefin that will not substantially polymerize under the polymerization conditions, including homopolymerization or incorporation into the product alpha-olefin polymer.
- non-polymerizing olefin does not include unreacted monomer molecules. Secondary, tertiary and quaternary olefins are preferred as the non-polymerizing olefin. Secondary and tertiary olefins are more preferred, with tertiary olefins being most preferred. Cyclic olefins are also preferred, and in particular cyclohexenes. Especially preferred are cyclohexenes where the olefin is tertiary.
- Preferred species include 1-methyl-cyclohexene, beta-pinene, alpha- pinene, 2-carene and 3-carene. Alpha-pinene, 2-carene and 3-carene are most preferred, and especially 3-carene. (See Examples 2-7 and Table I, below). Mixtures of two or more non-polymerizing olefins may be used.
- the non-polymerizing olefin is effective in relatively small amounts.
- the desired result is achieved with the use of 8 mole percent or less of the non-polymerizing olefin in the monomer; more preferably 6 mole percent or less, and most preferably 4 mole percent or less.
- the effectiveness of the non-polymerizing olefin may be characterized in a variety of ways.
- One measure of effectiveness compares the inherent viscosity of a polymer made from monomer only ('TVmo") with that of a polymer made under the same conditions but from a mixture of monomer and a given mole percentage of the non-polymerizing olefin ("IVnp").
- the IVnp/IVmo for 7.4 mole percent is preferably 1.7 or greater; more preferably 1.9 or greater, even more preferably 2.3 or greater, and most preferably 3.5 or greater.
- the IVnp/IVmo for 5.6 mole percent is preferably 2.0 or greater and more preferably 3.0 or greater.
- the IVnp/IVmo for 2.0 mole percent is preferably 1.5 or greater and more preferably 1.9 or greater.
- the IVnp/IVmo for 1.0 mole percent is preferably 1.3 or greater and more preferably 1.5 or greater.
- Mw average molecular weight measured by size exclusion chromatography (SEC) of a polymer made from monomer only (“Mw.mo”) with that of a polymer made under the same conditions but from a mixture of monomer and a given mole percentage of the non- p ' ymerizir '"fin ("Mw:np").
- Mw:np/Mw:mo for 1.0 mole percent is preferably ⁇ greater and more preferably 1.3 or greater.
- the Mw:np/Mw:mo for 6.0 mok t ..--cent is preferably 2.0 or greater and more preferably 2.5 or greater.
- characterization of the effectiveness of the non-polymerizing olefin is conducted using 1-octene monomer. Further means of characterization may be derived by reference to the Examples and other teachings herein.
- the non-polymerizing olefin species does not contain groups known to have activity as catalyst poisons. Such groups may include any of: amines, ethers, alcohols, ketones, esters, silyl ethers, and the like.
- the non-polymerizing olefin species does not contain groups that are strong Lewis acids and, more preferably, does not contain any groups that are Lewis acids.
- the non-polymerizing olefin species does not contain strong electron donor groups and, more preferably, does not contain any group that is a stronger electron donor than a double bond.
- the non-polymerizing olefin species binds reversibly to the catalyst and may associate and dissociate from the catalyst under polymerization conditions.
- the non-polymerizing olefin species does not bind irreversibly to the catalyst.
- Ziegler-Natta catalyst systems are described in Odian, G., "Principles of Polymerization", Ch. 8.4 (Second Edition, J. Wiley & Sons, New York, 1981). For a more detailed discussion, see Boor, J., “Ziegler-Natta Catalysts and Polymerizations", Ch. 19 (Academic Press, New York, 1979).
- Common Ziegler- Natta catalyst systems contain a transition metal compound or complex (e.g., TiCl 3 or TiCl 4 ) which may be supported (i.e., bound to an inorganic substrate such as MgCl 2 ) and an organometallic cocatalyst (e.g., a trialkylaluminum).
- Preferred catalyst systems are LynxTM 715 or LynxTM 1000 (Engelhard Corp.; Iselin, NJ) with triethylaluminum.
- the polymerization may be carried out by any suitable method.
- the polymerization may be carried out in a wide variety of reaction vessels and polymerization methods, including continuous stirred tank reactors (e.g., U.S. Pat. No. 3,074,922), loop reactors (e.g., Zacca et al. "Modeling of the Liquid Phase Polymerization of Olefins in Loop Reactors," Chem. Eng. Sc, 48, no. 22, 3743-65 (1993)), stirred tubular reactors (e.g., U.S. Pat. No.
- the reaction is carried out in the absence of solvent, excepting any solvent effect due to the presence of the non-polymerizing olefin or the monomer.
- the non-polymerizing olefin is added to the monomer prior to contact with the catalyst for ease of handling, processing simplicity and uniformity of results.
- the non-polymerizing olefin may be combined with the catalyst first or the three components may be combined simultaneously.
- the non-polymerizing olefin preferably comprises at least 0.5 mole percent of the combined amounts of alpha-olefin reactants plus non-polymerizing olefins, more preferably between 0.5 and 14 mole percent, and most preferably between 0.5 and 8 mole percent.
- the catalyst system should be present in an effective amount, typically between 0.0005 and 0.005 mole percent of active titanium relative to the reactant monomer and an aluminum/titanium molar ratio between 20 and 100.
- the non-polymerizing olefin is preferably removed from the polymeric product. Preferably the same means are used to simultaneously remove non- polymerizing olefin and unreacted monomer.
- Such means include volatilizing by exposure to heat, low pressure, or both. Such means also include washing with solvent.
- recovered non-polymerizing olefin is recycled to the beginning of the process and reused in subsequent polymerizations. More preferably, both non-polymerizing olefin and unreacted monomer are recycled together.
- recycled material is added to the reactant mixture before the catalyst. Recycling may be achieved by either batchwise or continuous means.
- product polymers of the present invention contain more high molecular weight polymer than comparable product polymers made without the non-polymerizing olefin.
- the molecular weight distribution displays a reduced main peak and a distinctive raised "shoulder" on the high molecular weight side of the main peak, which may rise to form a second peak. It is known in the art that higher molecular weight polymers can have many advantages, including increased strength and reduced need for crosslinking.
- product polymers of the present invention have greater stereoregularity.
- Polymers according to the present invention preferably contain 50% or more rnmmm pentad content, and more preferably 55% or more m-mmm pentad content, and most preferably 60% or more mmmm pentad content. It is known in the art that higher stereoregularity polymers can have many advantages, including increased crystallinity, strength and stiffness.
- non- polymerizing olefins of the present invention function to reversibly occupy fast- reacting catalytic sites that produce shorter and/or less stereoregular polymer chains, thereby allowing more polymerization to occur at slower-reacting catalytic sites which produce longer and/or more stereoregular polymer chains.
- This invention is useful in production of higher molecular weight alpha- olefin polymers by means that allow tempered polymerization rates and easier temperature control.
- polymerizations were carried out as follows. The polymerization was performed in a glass jar with an aluminum foil lined cap, made airtight by covering the threads of the jar with Teflon tape. In a nitrogen- purged glove box, the components of the polymerization were added in the following order: 40 mL of the specified alpha-olefin monomer, the specified amount of the specified non-polymerizing olefin, 5 mL of a vigorously-stirred heterogeneous catalyst solution containing LynxTM 715 catalyst (Engelhard Corp., Iselin, NJ) carried in the liquid alpha-olefin monomer at a concentration of 0.11 mg of active titanium per miUiliter, and 5 mL of a cocatalyst solution containing 0.63 M triethylaluminum in the liquid alpha-olefin monomer.
- LynxTM 715 catalyst Engelhard Corp., Iselin, NJ
- the jar was quickly capped, removed from the glove box, and placed in a cold water bath (15 °C) where it was shaken. After 3 hours, the jar was removed from the water bath. The lid was removed and the jar was placed in a vacuum oven (VWR Scientific. Model 1430, West Chester, PA) at 0.5 mm Hg and 60 °C for 15 hours to remove volatiles, including the non- polymerizing olefin and any unreacted monomer.
- VWR Scientific. Model 1430, West Chester, PA vacuum oven
- viscosity measurements were made on 10 mL of a 0.100 g/dL solution of the polymer in toluene, using a size 50 Cannon-Fenske viscometer (Ace Glass, Vineland, NJ) maintained at a temperature of 25.0 +/- 0.1 °C.
- the inherent viscosity values reported were calculated as the reciprocal of the solution concentration multiplied by the natural log of the ratio of the efflux times of the polymer solution and an equal volume of pure toluene (units of dL/g).
- SEC size exclusion chromatography
- exotherm measurements were made as follows. During poly ⁇ e ⁇ zation, the samples were left in the glove box instead of being capped and shaken in a cold water bath. A quartz-coated thermocouple (Aldrich, Cat. No. Z27751-7, Milwaukee, WI) was submerged into the solution. The temperature was noted every 15 seconds over the course of one hour.
- Examples designated with a “C” are comparative.
- Examples 2-7 demonstrate a variety of non-polymerizing olefins that are effective to increase the inherent viscosity of polyoctene according to the present invention.
- Comparison of Examples 20C, 21 and 22 indicates that very little of the higher molecular weight polymer is formed in the absence of the non-polymerizing polymer, and that addition of the non-polymerizing polymer increases the fraction of higher molecular weight polymer formed.
- Comparison of Examples 23C and 24-26 indicates that addition of the non- polymerizing polymer according to the present invention decreases the reaction rate and the intensity of the exotherm, diminishing the need to cool the solution during polymerization.
Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020017014484A KR20010113940A (en) | 1999-05-14 | 1999-12-02 | Ziegler-natta polymerization of alpha-olefins in the presence of non-polymerizing olefins |
AU31071/00A AU3107100A (en) | 1999-05-14 | 1999-12-02 | Ziegler-natta polymerization of alpha-olefins in the presence of non-polymerizing olefins |
JP2000618339A JP2002544340A (en) | 1999-05-14 | 1999-12-02 | Ziegler-Natta polymerization of α-olefins in the presence of non-polymerizable olefins |
EP99965082A EP1185564A1 (en) | 1999-05-14 | 1999-12-02 | Ziegler-natta polymerization of alpha-olefins in the presence of non-polymerizing olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/312,422 | 1999-05-14 | ||
US09/312,422 US6306983B1 (en) | 1999-05-14 | 1999-05-14 | Ziegler-Natta polymerization of alpha-olefins in the presence of non-polymerizing olefins |
Publications (1)
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WO2000069924A1 true WO2000069924A1 (en) | 2000-11-23 |
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PCT/US1999/028471 WO2000069924A1 (en) | 1999-05-14 | 1999-12-02 | Ziegler-natta polymerization of alpha-olefins in the presence of non-polymerizing olefins |
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US (2) | US6306983B1 (en) |
EP (1) | EP1185564A1 (en) |
JP (1) | JP2002544340A (en) |
KR (1) | KR20010113940A (en) |
AU (1) | AU3107100A (en) |
WO (1) | WO2000069924A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076479A1 (en) * | 2002-03-08 | 2003-09-18 | Basell Poliolefine Italia S.P.A. | Process for the polymerization of olefins |
WO2004076062A1 (en) * | 2003-02-24 | 2004-09-10 | Baker Hughes Incorporated | Process for preparing a polymer under predetermined temperature conditions, and apparatus therefor |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080230993A1 (en) * | 2007-03-19 | 2008-09-25 | Jay Chun | Paradise baccarat table |
US8969636B2 (en) * | 2009-07-29 | 2015-03-03 | The United States Of America As Represented By The Secretary Of The Navy | Homogeneous metallocene ziegler-natta catalysts for the oligomerization of olefins in aliphatic-hydrocarbon solvents |
Citations (2)
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US3732198A (en) * | 1969-01-20 | 1973-05-08 | Ici Ltd | Polymerisation of ethylene |
EP0557107A2 (en) * | 1992-02-21 | 1993-08-25 | Idemitsu Petrochemical Company Limited | Polyolefin resin and method for the preparation thereof |
Family Cites Families (12)
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US2894824A (en) | 1955-02-11 | 1959-07-14 | Phillips Petroleum Co | Polymerization apparatus |
US3074922A (en) | 1958-07-21 | 1963-01-22 | Phillips Petroleum Co | Polymerization process and apparatus |
DE2436259A1 (en) | 1974-07-27 | 1976-02-12 | Erdoelchemie Gmbh | METHOD FOR SUBSTANCE POLYMERIZATION OF ALPHA-OLEFINS |
DE2744559A1 (en) | 1976-10-07 | 1978-04-13 | Mitsubishi Petrochemical Co | PROCESS FOR MANUFACTURING CATALYST COMPONENTS FOR OLEFIN POLYMERIZATION |
US4124530A (en) | 1976-10-12 | 1978-11-07 | Stauffer Chemical Company | Olefin polymerization catalyst comprising a monoterpenic ketone and process employing same |
US4482687A (en) | 1979-10-26 | 1984-11-13 | Union Carbide Corporation | Preparation of low-density ethylene copolymers in fluid bed reactor |
EP0048627A1 (en) | 1980-09-24 | 1982-03-31 | BP Chemicals Limited | Catalyst system for cationic (co)polymerisation of 1-olefins |
US4792595A (en) | 1983-06-15 | 1988-12-20 | Exxon Research & Engineering Co. | Narrow MWD alpha-olefin copolymers |
US5407970A (en) | 1993-04-13 | 1995-04-18 | Minnesota Mining And Manufacturing Company | Radiation-curable poly(α-olefin) adhesives containing pendant olefinic funtionality |
US5536773A (en) | 1993-07-16 | 1996-07-16 | Mitsui Petrochemical Industries, Ltd. | Polypropylene resin composition and the use of the same |
US5869418A (en) | 1994-05-31 | 1999-02-09 | Borealis Holding A/S | Stereospecific catalyst system for polymerization of olefins |
US5644007A (en) | 1996-04-26 | 1997-07-01 | Minnesota Mining And Manufacturing Company | Continuous process for the production of poly(1-alkenes) |
-
1999
- 1999-05-14 US US09/312,422 patent/US6306983B1/en not_active Expired - Fee Related
- 1999-12-02 KR KR1020017014484A patent/KR20010113940A/en not_active Application Discontinuation
- 1999-12-02 WO PCT/US1999/028471 patent/WO2000069924A1/en not_active Application Discontinuation
- 1999-12-02 AU AU31071/00A patent/AU3107100A/en not_active Withdrawn
- 1999-12-02 JP JP2000618339A patent/JP2002544340A/en active Pending
- 1999-12-02 EP EP99965082A patent/EP1185564A1/en not_active Withdrawn
-
2001
- 2001-09-26 US US09/965,700 patent/US20020037978A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3732198A (en) * | 1969-01-20 | 1973-05-08 | Ici Ltd | Polymerisation of ethylene |
EP0557107A2 (en) * | 1992-02-21 | 1993-08-25 | Idemitsu Petrochemical Company Limited | Polyolefin resin and method for the preparation thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076479A1 (en) * | 2002-03-08 | 2003-09-18 | Basell Poliolefine Italia S.P.A. | Process for the polymerization of olefins |
US7098164B2 (en) | 2002-03-08 | 2006-08-29 | Basell Poliolefine Italia S.P.A. | Process for the polymerization of olefins |
WO2004076062A1 (en) * | 2003-02-24 | 2004-09-10 | Baker Hughes Incorporated | Process for preparing a polymer under predetermined temperature conditions, and apparatus therefor |
US7015290B2 (en) | 2003-02-24 | 2006-03-21 | Baker Hughes Incorporated | Method of preparing a polymer under predetermined temperature conditions, and apparatus therefor |
US7045101B2 (en) | 2003-02-24 | 2006-05-16 | Baker Hughes Incorporated | Method of preparing a polymer under predetermined temperature conditions, and apparatus therefor |
Also Published As
Publication number | Publication date |
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AU3107100A (en) | 2000-12-05 |
EP1185564A1 (en) | 2002-03-13 |
JP2002544340A (en) | 2002-12-24 |
US20020037978A1 (en) | 2002-03-28 |
KR20010113940A (en) | 2001-12-28 |
US6306983B1 (en) | 2001-10-23 |
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