WO1995002630A1 - Films polymeres a faibles vitesses de transmission de vapeur d'eau - Google Patents
Films polymeres a faibles vitesses de transmission de vapeur d'eau Download PDFInfo
- Publication number
- WO1995002630A1 WO1995002630A1 PCT/US1994/007553 US9407553W WO9502630A1 WO 1995002630 A1 WO1995002630 A1 WO 1995002630A1 US 9407553 W US9407553 W US 9407553W WO 9502630 A1 WO9502630 A1 WO 9502630A1
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- WO
- WIPO (PCT)
- Prior art keywords
- film
- less
- wvtr
- mil
- density
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0616—VLDPE, i.e. very low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0065—Permeability to gases
- B29K2995/0067—Permeability to gases non-permeable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
Definitions
- This invention relates generally to films. More specifically this invention is directed toward films having iow vapor transmission rates, specifically a low water vapor transmission rate.
- barrier polymers Polymers exhibiting low permeability are generally referred to as barrier polymers.
- the major use of these barrier polymers is in the packaging industry, especially in packaging applications for foods and beverages.
- the driving force behind the increased market penetration by barrier plastics are that they are light weight, strong, easily disposed of by incineration, and of low costs.
- the functional requirement of a package is to protect its contents from the environment over the normal shelf life of the product contained therein.
- the package may be a rigid container, a flexible container like a pouch or a non-barrier article with a barrier coating. In most food packaging applications protection from oxygen can be of great importance as can protection from the entry of moisture.
- the polymer In order to provide a useful packaging material the polymer must also have other attributes including: sufficient strength to form a durable package, with good impact and tear strength; resistance to puncture; good clarity when desirable; packaging processability; ability to withstand heat processing such as hot filling and pasteurization; anti-static properties; general chemical resistance including resistance to environmental stress cracking, sealability and organoleptic properties.
- a good barrier polymer must have some of the more important of these properties such as tensile strength, toughness or impact resistance and optical properties as well as have low permeability.
- the process of permeation through a polymeric barrier generally involves four steps: absorption of the permeating species into the polymer wall; solubility in the polymer matrix; diffusion through the wall along a concentration gradient; and desorption from the outer wall.
- a practical problem is that the property might result in a good gas barrier but a poor water barrier or a good water barrier but poor strength and optical properties.
- highly polar polymers those having many hydroxyl groups for example, poly(vinyl alcohol) or cellophane are excellent gas barriers but are amongst the poorest water barriers.
- very non-polar hydrocarbon polymers such as polyethylene have good water barrier properties but are poor gas barriers.
- the barrier polymers of this invention are those non-polar hydrocarbon polymers.
- Moisture transmission rates (MTR) or water vapor transmission rates (WVTR) depend generally on the crystallinity or density of the polymer.
- High density polyethylene (HDPE) usually has a density in the range of 0.945 g/cn to 0.960 g/cir HDPE is generally linear without any side chain branching and is substantially crystalline. HDPE because of its highly crystalline structure has a low water transmission rate but poor optical, tear strength and seal strength properties.
- At the other end of the density or crystallinity spectrum are those polymers generally known as very low density polyethylene (VLDPE).
- VLDPE's generally have a density below to 0.915 g/cn VLDPE's at the low end of the spectrum are substantially amorphous and thus lack the desired stiffness property necessary for making films. However, VLDPE's have high water vapor transmission rates.
- metallocene catalyst systems can be used to produce polymers having not only excellent strength, sealing and optical properties but having superior water vapor transmission rates. These polymers or barrier polymers of the invention are particularly well suited for use in the packaging industry, specifically in those applications in which low water vapor transmission rates are desirable.
- the invention is directed toward a polymer film comprising at least one resin layer.
- This layer has a density less than 0.935 g/crn 3 , a M w M n less than 3, a composition distribution breadth index greater than 80%; and said resin characterized in that at a density of 0.90 g/cm 3 said film has a water vapor transmission rate less than 2.25 g/mil/100 in 2 day.
- the film is either a single layer or multilayer film and can be coextruded, laminated or blended with other materials.
- FIG. 1 illustrates water vapor transmission rates as a function of density comparing films of this invention made with metallocene catalysts with those films made from resins produced by Ziegler-Natta catalysts.
- Figure 2 is a DSC curve for the polymers of this invention and shows a single melting peak.
- Figure 3 is a DSC curve for a prior art material showing multiple melting peaks.
- This invention concerns certain classes of non-polar hydrocarbon polymers specifically polyethylene resins, their production into film and applications in which films having a low water vapor transmission rates are desirable. These resins have unique properties particularly well suited for use in producing certain classes of polymeric films. Principally, these resins are used primarily in packaging applications, specifically those applications requiring good water vapor transmission rates, for example, food and chemical packaging. The resulting films have combinations of properties rendering them superior to resins previously available. Some of these resins have been placed into commerce under the trade names EXACT 3001, 3025, 3024, 3026, 3027, 3028, 4011, 2009, 2010, 3006 and 3016 all available from Exxon Chemical Company, Houston, Texas.
- the polymer resins of this invention are produced using metallocene catalyst systems in a polymerization or copolymerization process in gas, slurry solution or high pressure phase.
- the process for polymerizing or copolymerizing involves the polymerization of one more of the alpha-olefin monomers having from 2 to 20 carbon atoms, preferably 2-15 carbon atoms.
- the invention is particularly well suited to the copolymerization reactions involving the polymerization of one or more of the monomers, for example alpha-olefin monomers of ethylene, propylene, butene-1, pentene-1, 4-methylpentene-l, hexene-1, octene-1, decene-1 and cyclic olefins such as styrene.
- Other monomers can include polar vinyl, dienes, norbornene, acetylene and aldehyde monomers.
- a copolymer of ethylene is produced such that the amount of ethylene and comonomer is adjusted to produce a desired polymer product.
- the comonomer is an alpha- olefin having from 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and most preferably 4 to 10 carbon atoms.
- ethylene is polymerized with at least two comonomers to form a te ⁇ olymer and the like.
- the monomer is generally polymerized in a proportion of 70.0-99.99, preferably 70-90 and more preferably 80-95 or 90-95 mole percent of monomer with 0.01-30, preferably 3-30 and most preferably 5-20, 5-10 mole percent comonomer.
- metallocene is defined to contain one or more cyclopentadienyl moiety in combination with a transition metal of the Periodic Table of Elements.
- metallocene catalysts includes alumoxane as the cocatalyst.
- alumoxane as the cocatalyst.
- metallocenes such as trialkylaluminum compounds; or ionizing ionic activators or compounds such as, tri (n-butyl) ammonium tetra (pentaflurophenyl) boron, which ionize the neutral metallocene compound.
- ionizing compounds may contain an active proton, or some other cation associated with but not coordinated or only loosely coordinated to the remaining ion of the ionizing ionic compound.
- Such compounds are described in EP-A-0 277 003 and
- the metallocene catalyst component can be a monocyclopentadienyl heteroatom containing compound. This heteroatom is activated by either an alumoxane or an ionic activator to form an active polymerization catalyst system to produce polymers useful in this present invention.
- catalyst systems are described in, for example, PCT International Publications WO 92/00333 published January 9, 1992, U.S. Patent Nos. 5,096,867 and 5,055,438, EP-A-0420436 and WO 91/ 04257 all of which are fully inco ⁇ orated herein by reference.
- the metallocene catalysts useful in this invention can include non-cyclopentadienyl catalyst components, or ancillary ligands such as boroles or carbollides in combination with a transition metal.
- the catalysts and catalyst systems may be those described in U.S. Patent No. 5,064,802 and PCT pubUcations WO 93/08221 and WO 93/08199 pubUshed April 29, 1993 aU of which are herein inco ⁇ orated by reference.
- the catalyst systems described above may be, optionally, prepolymerized or used in conjunction with an additive or scavenging component to enhance catalytic productivity.
- the catalyst particles in a gas phase process may be supported on a suitable paniculate material such as polymeric supports or inorganic oxide such as silica, alumina or both.
- a suitable paniculate material such as polymeric supports or inorganic oxide such as silica, alumina or both.
- a key characteristic of the resins of the present invention is their composition distribution.
- the composition distribution of a copolymer relates to the uniformity of distribution of comonomer among the molecules of the copolymer.
- Metallocene catalysts are known to inco ⁇ orate comonomer very evenly among the polymer molecules they produce.
- copolymers produced from a catalyst system having a single metallocene component have a very narrow composition distribution - most of the polymer molecules wiU have roughly the same comonomer content, and within each molecule the comonomer wiU be randomly distributed.
- Ziegler-Natta catalysts on the other hand generally yield copolymers having a considerably broader composition distribution. Comonomer inclusion will vary widely among the polymer molecules.
- CDBI Composition Distribution Breadth Index
- a solubility distribution curve is first generated for the copolymer. This may be accompUshed using data acquired from the TREF technique described above. This solubihty distribution curve is a plot of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted to a weight fraction versus composition distribution curve. For the pu ⁇ ose of simplifying the correlation of composition with elution temperature the weight fractions less than 15,000 are ignored. These low weight fractions generally represent a trivial portion of the resin of the present invention. The remainder of this description and the appended claims maintain this convention of ignoring weight fractions below 15,000 in the CDBI measurement.
- the CDBI is determined by estabUshing what weight percent of the sample has a comonomer content within 25% each side of the median comonomer content. Further details of determining the CDBI of a copolymer are known to those skiUed in the art. See, for example, PCT Patent Application WO 93/03093, pubUshed February 18, 1993.
- the resins of the present invention have CDBI's generally in the range of
- the films of this invention are also distinguishable from known films made from Ziegler-Natta based resins on the basis of their molecular weight distribution
- the MWD of the present resins is materially narrower than that of resins produced using traditional Ziegler-Natta catalysts.
- the polydispersity index (M w Mn) of our resins is typically in the range of 1.5-3, compared to a range of 3 and above for most known Ziegler catalyzed resins.
- the present resins are very different from many commercially available resins produced using Ziegler-Natta catalysts.
- the tails of the molecular weight distribution curve for the present resin are considerably smaUer than those of known Ziegler- Natta LLDPEs.
- the melt index of the resins of the invention are generaUy in the range of 0.1 to 1000 dg/min, preferably 0.1 to 100 dg/min, more preferably 0.1 to 20 dg/min and even more preferably 0.1 to 10 dg/min and most preferably 0.1 to 5 dg/min. Properties of films produced from the resins
- a state-of-the-art die system was used, including a 6" multi-ported low pressure spiral mandrel die with a 1/2" die land. Mandrel extensions for 60 mU die gaps were used, all with parallel die lands.
- the air ring was a duel orifice air ring employing a forming cone of 6" height and 11" top diameter.
- the resins of this invention have lower WVTR than traditional Ziegler- Natta produced materials at the same or similar density. This can best be seen in Figure 1 which plots WVTR as a function of density.
- WVTR tests were performed on a MOCON permatron developed by Modern Controls, Inc. using ASTMF 372-73 at 100°F (378°C) and 100% relative humidity.
- the WVTR's of the films of the invention are generally in the range of 0.5 g mil/100 in 2 /day to 3.0 g mil/100 in 2 /day.
- film having a WVTR in the range of 0.5 g mil/100 in 2 /day to 2.5 g mil 100 in 2 /day and more preferably in the range of 0.55 g mil/100 in /day to 2.0 g mil/100 in 2 /day.
- This particular attribute is most pronounced in films having a density less than 0.940 g/cm 3 , preferably less than or equal to 0.935 g/cm 3 and a density greater than 0.860 g/cm 3 , preferably greater than 0.88 g/cm 3 .
- films having densities in the range of 0.865 g/cm 3 to 0.940 g/cm 3 , preferably 0.87 g/cm 3 to 0.935 g/cm 3 , most preferably 0.88 g/cm 3 to less than 0.935 g/cm 3 , most preferably 0.900 g/cm 3 to 0.930 g/cm 3 and even most preferably .900 g/cm 3 to 0.915 g/cm 3 .
- the resin of the invention is characterized in that at a density of 0.90 g/cm 3 said film has a WVTR less than 2.25 gmil 100 in 2 /day, preferably the WVTR is less than 2.0 g mil/100 in 2 /day, more preferably less than 1.75 g mil 100 in 2 /day and most preferably less than 1.5 g mil/100 in 2 /day.
- the resin is characterized in that at a density of
- said film has a WVTR less than 1.5 g mil/100 in 2 /day, most preferably less than 1.4 g mil/100 in /day.
- the resin is characterized in that at a density of 0.912 g/cm 3 said film has a WVTR is less than 1.55 g mil/100 in 2 /day preferably less than 1.5 g mil 100 in 2 /day.
- the WVTR for the films of this invention are represented by the following general empirical formula derived from Figure 1 :
- WVTR 314.43 - (650.45 X D) + (336.5 X D 2 ) where D is the density.
- WVTR wiU be less than WVTR 1 .
- a particular attribute of the present resins is their very low level of extractable components.
- the extractables level for most grades of resins are in the range of between 5.5% to below 0.1%, preferably below 2.6%, more preferably below 1.0%, even more preferably below 0.8% and most preferably below 0.5%.
- the extractables level of our resins generally increases with decreasing molecular weight and decreasing density. At any given molecular weight and density (or side chain branching) our resins have an extractables level significantly below that of the coutite ⁇ art Ziegler-Natta grade. For the pu ⁇ oses of this specification and the appended claims, the extractables level is measured by exposing film produced from the resin to n-hexane at 50°C for 2 hours.
- the exceUent tensile strength, impact strength and puncture properties of the present resins permit resin density to be raised as required to achieve the desired film stiffness and/or yield strength without reducing toughness below acceptable levels for most appUcations.
- This superior toughness/stiffness balance has significant benefit by permitting simplified film formulations for applications requiring yield strength as weU as exceUent water vapor transmission rates.
- Dart impact strengths above 1000 g/mil may be easily obtained. Indeed, many grades have dart impact strengths above 1500 g/mU.
- Dart impact strengths for the films of this invention are in the range of about 100 g/mU to greater than 1500 g/mil, preferably greater than 400 g/mU to more preferably greater than 900 g/mil and most preferably greater than 1000 g/mU. It is not beyond the scope of the invention to blend the resins of the films of the invention with other materials such as LLDPE, LDPE, HDPE, PP, PB, EVA, SBS and the Uke.
- the films of the invention include blown or cast films in mono- layer or multUayer construction formed by coextrusion or lamination.
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Abstract
La présente invention concerne certaines classes de polymères à base d'hydrocarbures non polaires, leur production et leur utilisation. Les polymères de la présente invention sont particulièrement adaptés pour être utilisés dans la production de films présentant des combinaisons uniques de propriétés, en particulier une faible vitesse de transmission de la vapeur d'eau (WVTR).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US9350193A | 1993-07-16 | 1993-07-16 | |
US08/093,501 | 1993-07-16 |
Publications (1)
Publication Number | Publication Date |
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WO1995002630A1 true WO1995002630A1 (fr) | 1995-01-26 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/007553 WO1995002630A1 (fr) | 1993-07-16 | 1994-07-06 | Films polymeres a faibles vitesses de transmission de vapeur d'eau |
Country Status (1)
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WO (1) | WO1995002630A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996019527A2 (fr) * | 1994-12-22 | 1996-06-27 | Exxon Chemical Patents Inc. | Articles en polyethylene a resistance amelioree a la transmission de la vapeur d'eau |
WO1997011116A1 (fr) * | 1995-09-18 | 1997-03-27 | Exxon Chemical Patents Inc. | Compositions de polypropylene hautement impermeables et leur utilisation comme emballages |
WO1998005502A1 (fr) * | 1996-08-01 | 1998-02-12 | Exxon Chemical Patents Inc. | Films stratifies de nwf respirants tres permeables a la vapeur d'eau et prepares a partir de films precurseurs de polyolefine/charge moules a chaud |
WO1998005501A1 (fr) * | 1996-07-31 | 1998-02-12 | Exxon Chemical Patents Inc. | Feuils charges en polyolefine presentant une vitesse accrue de transmission de vapeur d'eau et leur procede de fabrication |
US6159612A (en) * | 1997-08-25 | 2000-12-12 | Mobil Oil Corporation | Multi-layer films with syndiotactic barrier layer containing a wax |
US7652113B2 (en) | 1998-10-27 | 2010-01-26 | Westlake Longview Corporation | Polyethylene copolymers having low n-hexane extractable |
EP3705503A4 (fr) * | 2017-12-26 | 2020-12-30 | Lg Chem, Ltd. | Polymère à base d'oléfine |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992014784A2 (fr) * | 1991-02-22 | 1992-09-03 | Exxon Chemical Patents Inc. | Melange thermoscellable d'un plastomere ou d'un polyethylene tres basse densite avec des polymeres a base de polypropylene et film thermoscellable et articles fabriques avec ce melange |
-
1994
- 1994-07-06 WO PCT/US1994/007553 patent/WO1995002630A1/fr active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992014784A2 (fr) * | 1991-02-22 | 1992-09-03 | Exxon Chemical Patents Inc. | Melange thermoscellable d'un plastomere ou d'un polyethylene tres basse densite avec des polymeres a base de polypropylene et film thermoscellable et articles fabriques avec ce melange |
Non-Patent Citations (3)
Title |
---|
"Packaging resins based on new "single site" catalysis", MODERN PLASTICS INTERNATIONAL, vol. 23, no. 10, October 1993 (1993-10-01), LAUSANNE, pages 99 * |
MAPLESTON P.: "New versions of LLDPE may take share of LDPE market", MODERN PLASTICS INTERNATIONAL, vol. 23, no. 12, December 1993 (1993-12-01), LAUSANNE, pages 16 - 17 * |
MARTINO R.: "New polyolefin resin emerge: "Branched linear" copolymers", MODERN PLASTICS INTERNATIONAL, vol. 22, no. 11, November 1992 (1992-11-01), LAUSANNE, pages 16 - 18 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996019527A3 (fr) * | 1994-12-22 | 1996-08-22 | Exxon Chemical Patents Inc | Articles en polyethylene a resistance amelioree a la transmission de la vapeur d'eau |
WO1996019527A2 (fr) * | 1994-12-22 | 1996-06-27 | Exxon Chemical Patents Inc. | Articles en polyethylene a resistance amelioree a la transmission de la vapeur d'eau |
US6419966B1 (en) | 1994-12-22 | 2002-07-16 | Exxonmobil Chemical Patents Inc. | Polyethylene articles with improved resistance to water vapor transmission |
WO1997011116A1 (fr) * | 1995-09-18 | 1997-03-27 | Exxon Chemical Patents Inc. | Compositions de polypropylene hautement impermeables et leur utilisation comme emballages |
US5795946A (en) * | 1995-09-18 | 1998-08-18 | Exxon Chemical Patents Inc. | High barrier propylene compositions and their use in packaging applications |
USH1955H1 (en) | 1996-07-31 | 2001-04-03 | Exxon Chemical Patents Inc. | Polyolefin/filler films having increased WVTR and method for making |
WO1998005501A1 (fr) * | 1996-07-31 | 1998-02-12 | Exxon Chemical Patents Inc. | Feuils charges en polyolefine presentant une vitesse accrue de transmission de vapeur d'eau et leur procede de fabrication |
WO1998005502A1 (fr) * | 1996-08-01 | 1998-02-12 | Exxon Chemical Patents Inc. | Films stratifies de nwf respirants tres permeables a la vapeur d'eau et prepares a partir de films precurseurs de polyolefine/charge moules a chaud |
USH2000H1 (en) | 1996-08-01 | 2001-11-06 | Exxon Chemical Patents, Inc. | Method for making polyolefin/filler films having increased WVTR |
US6159612A (en) * | 1997-08-25 | 2000-12-12 | Mobil Oil Corporation | Multi-layer films with syndiotactic barrier layer containing a wax |
US7652113B2 (en) | 1998-10-27 | 2010-01-26 | Westlake Longview Corporation | Polyethylene copolymers having low n-hexane extractable |
US7893180B2 (en) | 1998-10-27 | 2011-02-22 | Westlake Longview Corp. | Process for the polymerization of olefins; novel polyethylenes, and films and articles produced therefrom |
EP3705503A4 (fr) * | 2017-12-26 | 2020-12-30 | Lg Chem, Ltd. | Polymère à base d'oléfine |
US11440984B2 (en) | 2017-12-26 | 2022-09-13 | Lg Chem, Ltd. | Olefin-based polymer |
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