Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
  • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/06—Metallocene or single site catalysts

Definitions

• the present invention relates to high clarity films and articles made from such films.
• the invention relates to a blend of metallocene produced polyethylenes (mPE), one of which has a narrow molecular weight distribution and narrow composition distribution, the other has a broader molecular weight distribution and a more narrow composition distribution.
• mPE metallocene produced polyethylenes
• polymers are used to form films; such films may then be used to form packages or bags.
• Polymers or blends of polymers used to make films are selected for use because they provide good physical properties, good processability, good clarity or a combination of these attributes.
• Blends of high pressure process produced polyethylenes (HP-LDPE) with either mPE and Z-N PE can generally improve the optics of the resulting film over that of either mPE or Z-N PE by themselves. This optics improvement however generally results in a reduction in other physical properties; most notably Elmendorf Tear (generally in the machine direction (MD)) and dart drop impact resistance. Such blends also improve the processing compared to Z-N PE or mPE by themselves.
• Component A and a conventional Ziegler-Natta catalyzed polymer, Component B.
• Component A is said to have a narrow molecular weight distribution and narrow composition distribution
• Component B is said to have a broad molecular weight distribution and a broad composition distribution Therefore, there is a commercial need for a polyethylene or polyethylene blend that has both good physical properties and excellent clarity and haze.
• the blend of polymers of embodiments of this invention generally include at least a first polymer, Component A, which has a narrow molecular weight distribution and a narrow composition distribution and at least a second polymer, Component B, which has a broader molecular weight distribution than Component A and an extremely narrow composition distribution.
• Component A and Component B is produced by a metallocene catalyst.
• Component A comprises between 10 to 90 weight percent of the total weight percent polymer blend and Component B comprises between 90 to 10 weight percent of the total weight percent polymer blend of the invention.
• the molecular weight distribution or MWD (also Mw/Mn) of Component A is in the range of from 1.5 to 3.0 and the composition distribution breadth index (CDBI) in the range of from 50 to 70%.
• the relaxation spectrum index (RSI), normalized for melt index of Component A of the blend, will be in the range of from 1.8 to 2.5.
• the branching factor will be in the range of from 0.95 to 1.0.
• the MWD of Component B will be in the range of from 3.5 to 15, and the CDBI in the range of from 75 to 90%.
• the relaxation spectrum index (RSI), normalized for melt index of Component B of the blend, will be in the range of from 8 to 11.
• the branching factor will be in the range of from 0.7 to 0.8.
• the haze of the blend will be in the range of from 3 to 10%, preferably 4 to 9%, more preferably 5 to 9%, most preferably 5 to 8%, while the gloss (45 degree) will be in the range of from 50 to 80, preferably 55 to 75, more preferably 60 to 75.
• the polymer blend of the invention is useful in or as a film or part of a multilayer film in an article of manufacture.
• Figure 1 illustrates the haze of both 100% Component A and 100% Component B and several blends of the two.
• the line drawn from the haze of 100% Component A to the haze of 100% of Component B represents the linear, expected haze of the blend spectrum.
• Figure 2 illustrates the gloss (45 degree) of both 100% Component A and 100% Component B and several blends of the two.
• the line drawn from the gloss of 100% Component A to the gloss of 100% of Component B represents the linear, expected gloss of the blend spectrum.
• Embodiments of this invention concern a blend of preferably at least two metallocene catalyzed polymers, Component A and a Component B, their production and applications for their use.
• the polymer blends of embodiments of this invention have unique properties which make the blend particularly well suited for use in polymeric films. These films are very useful in applications requiring good physical properties combined with excellent clarity.
• a characteristic of the polymers of Component A and Component B of the present invention is their composition distribution (CD).
• CD 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 incorporate comonomer very evenly among the polymer molecules they produce.
• copolymers produced from a catalyst system having a single metallocene component have a na ⁇ ow composition distribution, most of the polymer molecules will have roughly the same comonomer content, and within each molecule the comonomer will 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 accomplished using data acquired from the TREF technique described above. This solubility 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 purpose 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, maintains this convention of ignoring weight fractions below 15,000 in the CDBI measurement.
• the CDBI of Component A of the present invention is in the range of from 50 to 80%), preferably in the range of from 55 to 75%, more preferably in the range of from 50 to 70%.
• the CDBI of Component B of the present invention is in the range of from 75 to 95%), preferably in the range of from 75 to 90%, more preferably in the range of from 80 to 90%.
• MWD or polydispersity
• MWD is a well known characteristic of polymers.
• MWD is generally described as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
• Mw/Mn can be measured directly by gel permeation chromatography techniques as are well known in the art.
• Permeation Chromatograph equipped with Ultrastyrogel columns and a refractive index detector.
• the operating temperature of the instrument was set at 145°C
• the eluting solvent was trichlorobenzene
• the calibration standards included sixteen polystyrenes of precisely known molecular weight, ranging from a molecular weight of 500 to a molecular weight of 5.2 million, and a polyethylene standard, NBS 1475.
• Narrow MWD means a Mw/Mn less than 3, preferably in the range of from 1.5 to 3.0, more preferably in the range of 2.5 to 3.0.
• the MWD of the polymer Component B of this invention are termed "relatively broad" relative that is to the above, Component A MWD.
• the MWD of the B Component is in the range of from 3.5 to 15, preferably in the range of from 3.5 to 10, preferably in the range of 3.5 to 7.5, more preferably in the range of from 3.5 to 5.0.
• the RSI (normalized for melt index) of the polymer Component A of embodiments of my invention will be in the range of from 1.0 to 4.0, preferably 1.5 to 3.0, more preferably in the range of from 2.0 to 3.0, most preferably in the range of from 2.5 to 3.0.
• the RSI (normalized for melt index) of the polymer Component B of embodiments of my invention will be in the range of from 6.0 to 14.0, preferably 7.0 to 12.0, more preferably in the range of from 8.0 to 11.0.
• the G-Factor A plot of log melt index (MI), ASTM D- 1238 measured at 190°C vs. intrinsic viscosity, [ ⁇ ], measured in Decalin at 135°C for a wide range of linear polyethylenes versus that representing a series of HP-LDPE having substantial LCB content provides a further manner of looking at branching.
• MI log melt index
• G G-factor
• [ ⁇ ] is the experimentally measured intrinsic viscosity of a sample of melt index MI.
• G v the intrinsic viscosity and melt index for a sample, then compute, for the measured MI, what the linear [ ⁇ ] would be.
• the G-factor reflects LCBs (that matter to resin processability and is relatively insensitive to molecular weight distribution, as reflected by Mw/Mn).
• the branching factor for Component A is in the range of from 0.95 to 1.0.
• the branching factor for Component B is in the range of from 0.7 to 0.8, and preferably in the range from 0.72 to 0.78.
• the Melt Index (MI) of the polymers of the invention are generally in the range of from 0.1 dg/min to 1000 dg/min, preferably 0.2 dg/min to 300 dg/min, more preferably 0.3 to 200 dg/min and most preferably 0.5 dg/min to 100 dg/min.
• MI (I 2 ) is measured according to ASTM D-1238, Condition E, at 190°C, I 21 is measured according to ASTM D-1238, Condition F, at 190°C)and the melt flow ratio (MFR) is I 21 /I 2 .
• Contemplated densities of Component A and/or Component B of the invention are in the range of from 0.86 to 0.97 g/cm 3 , preferably from 0.88 to 0.96 g/cm 3 , more preferably from 0.90 to 0.95 g/cm 3 , more preferably from 0.90 to 0.93 g/cm 3 , and most preferably from 0.910 to 0.925 g/cm 3 .
• Component A may consist of a blend of Component A polymers, which can be prepared by blending the desired components in the desired proportion using conventional blending techniques and apparatus, such as, for example, screw-type extruders, Banbury mixers, and the like.
• the blends may be made by direct polymerization, without isolation of the blend components, using, for example, two or more catalysts in one reactor, or by using a single catalyst and two or more reactors in series or parallel.
• the B Component of the polymer blend of the invention may consist of a blend of different polymers, each differing in one or more of: molecular weight, MWD, comonomer type and content, density, MI and CD as long as the overall blend making up the B Component has the MWD and CD as discussed above.
• the polymer blend of embodiments of the invention herein refe ⁇ ed to as, the "A-B blend” may be used to form articles with particularly desirable optical properties.
• the A-B blend may be used to form films which are in turn formed into bags or pouches by heat sealing techniques known in the art.
• the articles described herein are formed from the A-B blend of the invention.
• the A-B blend of polymers may be formed into films by methods well known in the art. For example, the polymers may be extruded in a molten state through a flat die and then cooled.
• the polymers may be extruded in a molten state through an annular die and then blown and cooled to form a tubular film.
• the tubular film may be axially slit and unfolded to form a flat film.
• the films of the invention may be unoriented, uniaxially oriented or biaxially oriented.
• the optical properties referred to in the present description are those of blown films.
• the films of the invention may be single layer or multiple layer films.
• the multiple layer films may comprise one or more layers formed from the A- B polymer blend.
• the films may also have one or more additional layers formed from other materials such as other polymers, polypropylene, polyester, low density polyethylene, high density polyethylene, ethylene vinyl acetate, ethylene vinyl alcohol and the like.
• Multiple layer films may be formed by methods well known in the art. If all layers are polymers, the polymers may be coextruded through a coextrasion feedblock and die assembly to yield a film with two or more layers adhered together but differing in composition. Multiple layer films may also be formed by extrusion coating whereby a substrate material is contacted with the hot molten polymer as the polymer exits the die. Blend Proportions
• the polymer blend of the invention contains 10 to 90 weight percent of polymer Component A, preferably 40 to 85 percent, more preferably 50 to 80 weight percent, even more preferably 50 to 75 weight percent. In one embodiment of the invention the polymer blend contains 90 to 10 weight percent of polymer Component B, preferably 15 to 60 weight percent, more preferably 50 to 20 weight percent, even more preferably 50 to 25 weight percent. All weight percentages of the A-B blends refer to a total of 100 percent of the total polyethylene content.
• the blend may also be compounded with various conventional additives known in the art such as, for example, antioxidants, UN stabilizers, pigments, fillers, slip additives, block additives, and the like.
• additives known in the art such as, for example, antioxidants, UN stabilizers, pigments, fillers, slip additives, block additives, and the like.
• Component A is an mPE produced in a gas phase polymerization reaction utilizing the metallocene catalyst bis(l,3-methyl-n-butyl cyclopentadienyl) zirconium dichloride
• Component B is an mPE produced in a gas phase polymerization reaction utilizing the metallocene catalyst dimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride.
• Typical gas phase polymerization processes and the preparation of both bis(l,3-methyl-n-butyl cyclopentadienyl) zirconium dichloride and dimethylsilyl-bis(tetrahydroindenyl) zirconium dichloride are as described in PCT Publication No. W0 00/02930, published January 20,2000, herein incorporated by reference.
• Blends of granular Component B, a nominal 1.0 melt index (MI), 0.920 g/cm 3 density polyethylene (mPE) and Component A, a nominal 1.0 MI, 0.917 g/cm 3 density polyethylene are used in this example. Blends are made at 30/70, 50/50 and 70/30, weight percent Component B/Component, respectively, where the weight percent of each component is based upon total weight polyethylene content.
• Each of the blends and the unblended Component A and Component B are formulated with 1500 ppm each of Irganox ®1076 and Irgafos ®168, both from Ciba-Geigy, Tarrytown, New York, and 1000 ppm of Dynamar® FX-9613, a product of Dyneon Corp, Oakdale, Minnesota.
• the films were made on a 3.5 inch (8.89 cm) Gloucester blown film line with a 6 inch die with a 90 mil die gap and a Polycool® air ring. Processing conditions and film properties are shown on table 1.
• Non-linear, therefore surprising and unexpected properties, are tear, haze and gloss.
• the Elmendorf tear (MD) (g/mil) for the 70/30 blends of Component B/Component A, is nearly 10% greater than an arithmetic average of the individual components, such average being that value which would be predicted by those of skill in the art.
• the haze of the same blend is also 10% below (better) than that expected , whilele the haze of a 50/50 blend is 42% less than expected and a 30/70 blend where the haze is 32% better (lower) than expected.
• EXAMPLE III Blends that follow are made using the following polyethylenes HS-7028 (described above), DYNH-1 available from Union Carbide Corp., (a HP-LDPE, 1.8 MI, 0.920 g/cm 3 density, typically higher than 75% CDBI, 27.3 RSI, and 6 ⁇ 15% MWD) Component A and Component B. Films are made on a 1 Vi inch Sterling extruder with a 3 inch (7.62 cm) die and 90 mil die gap and a dual lip Addex® air ring. Nominal 1.0 mil films are made at a 2.0 blow up ratio (BUR) and an output rate of 3 lb./hr/die inch. The processability and film properties are shown in Table 3.

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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2000
  • 2000-02-16 US US09/505,648 patent/US6359072B1/en not_active Expired - Lifetime
• 2001
  • 2001-01-31 AU AU3471101A patent/AU3471101A/xx active Pending
  • 2001-01-31 EP EP01906851A patent/EP1265958A1/en not_active Withdrawn
  • 2001-01-31 JP JP2001560285A patent/JP4034965B2/ja not_active Expired - Fee Related
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