WO2013078351A1 - Compositions de film soufflé de polyéthylène modifié possédant une excellente stabilité de bulles - Google Patents

Compositions de film soufflé de polyéthylène modifié possédant une excellente stabilité de bulles Download PDF

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WO2013078351A1
WO2013078351A1 PCT/US2012/066309 US2012066309W WO2013078351A1 WO 2013078351 A1 WO2013078351 A1 WO 2013078351A1 US 2012066309 W US2012066309 W US 2012066309W WO 2013078351 A1 WO2013078351 A1 WO 2013078351A1
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film
modifier
composition
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PCT/US2012/066309
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English (en)
Inventor
Yong Yang
Pradeep P. Shirodkar
Jianya Cheng
Andy H. Tsou
Arnold Lustiger
Johannes M. SOULAGES
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Exxonmobil Chemical Patents Inc.
Exxonmobil Research And Engineering Company
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Priority claimed from US13/302,446 external-priority patent/US8487059B2/en
Priority claimed from US13/584,284 external-priority patent/US8629217B2/en
Application filed by Exxonmobil Chemical Patents Inc., Exxonmobil Research And Engineering Company filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2013078351A1 publication Critical patent/WO2013078351A1/fr

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • 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
    • 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
    • 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
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

  • TITLE MODIFIED POLYETHYLENE BLOWN FILM COMPOSITIONS HAVING EXCELLENT BUBBLE STABILITY
  • the present invention relates to branched modifiers, polyethylene compositions comprising an ethylene based polymer, and a branched modifier and films thereof.
  • melt strength and good optical properties are desirable attributes.
  • a higher melt strength allows fabricators to run their blown film lines at a faster rate. It also allows them to handle thicker films in applications such as geomembranes.
  • Typical metallocene catalyzed polyethylenes are somewhat more difficult to process than low-density polyethylenes (LDPE) made in a high-pressure polymerization process.
  • mPEs which tend to have narrow molecular weight distributions and low levels of branching
  • Typical mPEs also have lower melt strength which, for example, adversely affects bubble stability during blown film extrusion, and they are prone to melt fracture at commercial shear rates.
  • mPEs exhibit superior physical properties as compared to LDPEs.
  • U.S. Patent Application Publication No. 2007/0260016 discloses blends of linear low density polyethylene copolymers with other linear low density polyethylenes or very low density, low density, medium density, high density, and differentiated polyethylenes, as well as articles produced therefrom.
  • U.S. Patent No. 6,300,451 discloses ethylene/butene/l,9-decadiene copolymers, and ethylene hexene vinyl norbornene copolymers (see Tables I and II).
  • the decadiene terpolymers disclosed are designed to be used alone and not in blends for improved processability/property balance.
  • the relatively high MI of the resins suggests that they would not be suitable in blends which exhibit improved extensional strain hardening.
  • Patil, et al, "Rheology of Polyethylenes with Novel Branching Topology Synthesized by Chain Walking Catalyst," Macromolecules, 2005, 38, pp. 10571-10579 discloses dendritic PE produced from chain walking catalyst.
  • the dendritic PE prepared by chain walking catalysts has extensive short and long chain branches with combined branch density of greater than 100 branches per 1000 carbon.
  • the extensive short chain branching leads to amorphous polymers which have limited use in mixtures with semicrystalline polyethylene resins of commercial interest. Additionally, these polymers are prepared at low temperatures and extremely low pressures, both conditions that are not commercially attractive. Additionally, blends are not disclosed in this paper and there is no mention of blown film compositions.
  • US 6,870,010 discloses blown films with improved optical properties produced from blends of linear metallocene PE with high MW HDPE. While the optical properties as measured by haze are improved over unblended film composition, the mechanical properties as measured by Dart Impact suffer a significant deterioration.
  • U.S. Patent Application Publication No. 201 1/01 18420 discloses dendritic hydrocarbon polymer and process for the production thereof.
  • U.S. Patent Application Publication No. 201 1/0118420 also states in the background section, that "...[w]hile LCB technology has been a part of the polyethylene industry since the 1930's, there is still a need to further optimize the type and availability of LCB polyethylenes and other polymers.
  • a useful, inexpensive blend additive in the form of a LCB polymer could significant[ly] impact the processing/performance balance for polyethylenes, particularly the multi-billion dollar market for polyethylene films and molded articles. There could be even greater use in polypropylene, where there is currently little commercially viable technology for incorporating LCB. There is also a need for LCB polymers in the EPDM elastomer market.”
  • branched hydrocarbon modifiers will advantageously improve processability of polyethylene without significantly impacting its mechanical properties. Moreover, addition of these branched hydrocarbon modifiers provides a means to change such properties on a continuous scale, based on real-time needs, which is typically not possible due to the availability of only discrete polyethylene grades. Furthermore, a different set of relationships between processability and properties is obtained, compared to those available from traditional polyethylenes and their blends with conventional LDPE, which allows for new and advantageous properties of the fabricated articles.
  • the present invention relates to polyethylene compositions having improved properties such as melt strength or extensional strain hardening, without substantial loss in blown film, dart impact, MD tear, or other mechanical properties. Additionally, the films produced from these compositions exhibit surprisingly excellent optical properties as measured by lower film haze.
  • this invention relates to polyethylene compositions having improved bubble stability.
  • Previous attempts to remedy the situation by addition of long-chain-branched PEs such as LDPE or other branched PEs (US 6,870,010) have resulted in decreased mechanical properties.
  • Some of the blown films blended with branched PE additives additionally suffered from poor optical properties, e.g., the existence of gel particles.
  • the current invention solves the problem by using a crystalline long-chain-branched hyper branched polyethylene (disclosed in U.S. Patent Application 13/302,446) that is effective in improving processability at very low concentration levels (1%).
  • the films produced from the 1% blend of this crystalline long-chain-branched hyper branched PE with ExceedTM 2018CA PE exhibit the following combination of properties, among other things, which have not been possible in the prior art: a) free of gel and excellent optical properties; b) improved film processability in terms of bubble stability, film gauge variation; and c) enhanced MD/TD tear and no loss in most of the mechanical properties except impact strength.
  • This invention relates to polyethylene compositions comprising one or more ethylene polymers and one or more dendritic hydrocarbon polymer modifiers.
  • This invention further relates to polyethylene blends comprising one or more ethylene polymers and one or more dendritic hydrocarbon polymer modifiers, wherein the modifier has: 1) a g' v j s value less than 0.75; 2) at least 0.6 ppm ester groups as determined by l R NMR; 3) a Tm of 100°C or more; 4) an Mw of 50,000 g/mol or more, as determined by GPC; and 5) an average number of carbon atoms between branch points of 70 or more as determined by l R NMR.
  • Figure 1 depicts an illustrative 3rd generation dendritic structure.
  • FIG. 1 depicts the reaction scheme of Example 1 herein.
  • Figure 3 shows a representative structure of dendritic polymer synthesized and corresponding NMR spectrum for Example 1 herein.
  • Figure 4 depicts linker molecular weight (red) and insertion efficiency T3/T2 (blue) versus catalyst loading (Cyclooctene/Catalyst) for Example 1 herein.
  • Figure 5 depicts the reaction scheme of Example 2 herein.
  • Figure 6 shows NMR spectra of the dendritic polymer of Example 2 herein before hydrogenation (top) and after hydrogenation (bottom) with peak assignments.
  • Figure 7 shows that the neat dendritic PE synthesized exhibits extensional hardening as measured by SER (Sentmanat Extensional Rheometer).
  • Figure 8 shows that extensional strain hardening can be observed in mLLDPE containing 1 wt% and 3 wt% dendritic PE additives as measured by SER (Sentmanat Extensional Rheometer).
  • Figure 9 shows overlaid DSC (Differential Scanning Calorimetry) traces of mLLDPE film, neat dendritic PE, and mLLDPE containing 1 wt% dendritic PE additive.
  • Figure 10 depicts the reaction scheme of Example 3 herein.
  • Figure 11 shows !fi NMR partial spectrum of Example 3 herein before hydrogenation with peak assignments.
  • Figure 12 shows the extensional strain hardening observed in blends of ExceedTM 2018 LLDPE containing 3 wt% Modifier DPEY3 as measured by SER (Sentmanat Extensional Rheometer).
  • Figure 13 is infrared dichroism of neat ExceedTM 2018 Polyethylene blown film and 1 wt% DPEY2 blend blown film.
  • Figure 14 presents illustrations of Cayley tree topology.
  • Figure 15 presents illustrations of Cayley tree layer numbers.
  • an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • olefin including, but not limited to ethylene, hexene, and diene
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that a mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a "polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • copolymer as used herein, includes terpolymers and the like.
  • polymer as used herein, includes copolymers and the like.
  • polyethylene means a polymer or copolymer comprising at least 50 mol% ethylene units (preferably at least 70 mol% ethylene units, more preferably at least 80 mol% ethylene units, even more preferably at least 90 mol% ethylene units, even more preferably at least 95 mol% ethylene units or 100 mol% ethylene units (in the case of a homopolymer)).
  • polyethylene composition means a blend containing one or more polyethylene components.
  • polypropylene As used herein, the terms "polypropylene,” “propylene polymer,” “propylene copolymer,” and “propylene based polymer” mean a polymer or copolymer comprising at least 50 mol% propylene units (preferably at least 70 mol% propylene units, more preferably at least 80 mol% propylene units, even more preferably at least 90 mol% propylene units, even more preferably at least 95 mol% propylene units or 100 mol% propylene units (in the case of a homopolymer)).
  • butene based polymer mean a polymer or copolymer comprising at least 50 mol% butene units (preferably at least 70 mol% butene units, more preferably at least 80 mol% butene units, even more preferably at least 90 mol% butene units, even more preferably at least 95 mol% butene units or 100 mol% butene units (in the case of a homopolymer)).
  • an "EP Rubber” is defined to be a copolymer of ethylene and propylene, and, optionally, diene monomer(s), chemically crosslinked (i.e., cured) or not, where the ethylene content is from 35 wt% to 80 wt%, the diene content is 0 wt% to 15 wt%, and the balance is propylene; and where the copolymer has a Mooney viscosity, ML(l+4) @ 125°C (measured according to ASTM D1646) of 15 to 100.
  • EPDM or "EPDM Rubber” is defined to be an EP Rubber having diene present.
  • an ethylene polymer having a density of 0.86 g/cm 3 or less is referred to as an ethylene elastomer or elastomer; an ethylene polymer having a density of more than 0.86 to less than 0.910 g/cm 3 is referred to as an ethylene plastomer or plastomer; an ethylene polymer having a density of 0.910 to 0.940 g/cm 3 is referred to as a low density polyethylene; and an ethylene polymer having a density of more than 0.940 g/cm 3 is referred to as a high density polyethylene (HDPE).
  • density is determined using the method described under Test Methods below.
  • Polyethylene in an overlapping density range i.e., 0.890 to 0.930 g/cm 3 , typically from 0.915 to 0.930 g/cm 3 , which is linear and does not contain long chain branching is referred to as "linear low density polyethylene” (LLDPE) and can be produced with conventional Ziegler-Natta catalysts, vanadium catalysts, or with metallocene catalysts in gas phase reactors and/or in slurry reactors and/or with any of the disclosed catalysts in solution reactors.
  • LLDPE linear low density polyethylene
  • mLLDPE is an LLDPE made by a metallocene catalyst.
  • Linear means that the polyethylene has no long chain branches; typically referred to as a g' vis of 0.95 or above, preferably 0.97 or above, preferably 0.98 or above.
  • CDBI Composition Distribution Breadth Index
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mz z average molecular weight.
  • MD machine direction.
  • TD transverse direction.
  • This invention relates to polyethylene compositions comprising one or more ethylene polymers (preferably linear ethylene polymers) and one or more dendritic hydrocarbon polymer modifiers (also referred to as the "modifier” or the “branched modifier”).
  • ethylene polymers preferably linear ethylene polymers
  • dendritic hydrocarbon polymer modifiers also referred to as the "modifier” or the “branched modifier”
  • This invention further relates to polyethylene blends comprising one or more ethylene polymers (preferably having a g' v i s of 0.95 or more) and one or more dendritic hydrocarbon polymer modifiers, wherein the modifier has: 1) a g' v j s value or 0.75 or less (preferably 0.70 or less, preferably 0.65 or less, preferably 0.60 or less, preferably 0.55 or less, preferably 0.50 or less, preferably 0.45 or less, preferably 0.40 or less, preferably 0.35 or less, preferably 0.30 or less); 2) at least 0.6 ppm ester groups (preferably 0.75 or more, preferably 1.0 or more, preferably 1.2 or more, preferably 1.50 or more) as determined by NMR; 3) a Tm of 100°C or more (preferably 110°C or more, preferably 120°C or more, preferably 125°C or more) as determined by DSC; 4) an Mw of 50,000 g/mol or more (preferably 100,000 g/mol or more,
  • a density of 0.860 to 0.980 g/cc (preferably from 0.880 to 0.940 g/cc, preferably from 0.900 to 0.935 g/cc, preferably from 0.910 to 0.930 g/cc);
  • an Mw of 20,000 g/mol or more (preferably 20,000 to 2,000,000 g/mol, preferably 30,000 to 1,000,000 g/mol, more preferably 40,000 to 200,000 g/mol, preferably 50,000 to 750,000 g/mol); and
  • a dendritic hydrocarbon polymer modifier(s) wherein the modifier has: 1) a g' vis value less than 0.75 (preferably less than 0.65, preferably less than 0.55, preferably less than 0.45, preferably less than 0.40 ); 2) a Cayley tree topology with a layer number of 2 or more, preferably 3 or more, preferably 4 or more; 3) at least 0.6 ppm (preferably at least 10 ppm, preferably at least 100 ppm, preferably at least 1000 ppm, preferably at least 5000
  • the modifiers described herein contain less than 0.6 ppm silicon, preferably less than 0.3 ppm silicon, preferably less than 0.1 ppm silicon, preferably 0 ppm silicon (as determined by ICPES (Inductively Coupled Plasma Emission Spectrometry)), which is described in J. W. Olesik, "Inductively Coupled Plasma- Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, C. R. Brundle, C. A. Evans, Jr. and S. Wilson, Eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644, is used to determine the amount of an element in a material.
  • ICPES Inductively Coupled Plasma Emission Spectrometry
  • the polyethylene/modifier compositions of this invention comprise less than 5 wt%, (preferably less than 1 wt%, preferably 0 wt%) propylene homopolymer or copolymer, based upon the weight of the composition.
  • the polyethylene/modifier compositions of this invention comprise less than 5 wt%, (preferably less than 1 wt%, preferably 0 wt%) EP Rubber, based upon the weight of the composition.
  • this invention comprises a blend comprising:
  • ethylene polymers having a g' vjs of 0.95 or more, a CDBI of 60% or more and a density of 0.90 g/cc or more, wherein the ethylene polymer has a g' v j s of at least 0.01 units higher than the g' vjs of the branched modifier (preferably at least 0.02, preferably at least 0.03, preferably at least 0.04, preferably at least 0.05, preferably at least 0.1, preferably at least 0.2, preferably at least 0.3, preferably at least 0.4, preferably at least 0.45 units higher).
  • the blends comprising the polyethylene (preferably linear polyethylene) described herein and the branched modifier described herein are gel free.
  • the blend preferably has 5 wt% or less of xylene insoluble material (preferably less than 4 wt%, preferably less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%).
  • the blown film of the compositions described herein are preferably essentially free of defects, e.g., are optically clear.
  • the quality of the films, preferably blown films, comprising the compositions described herein can be characterized by a composite gel count, as described in US 7,393,916 of less than 100 (preferably less than 60, preferably less than 50, preferably less than 40, preferably less than 35.
  • any film, preferably blown films, comprising the compositions described herein may have a FAR ("film appearance rating", visual comparison test to known standards) value of greater than +20 in one embodiment, and greater than +30 in another embodiment, and greater than +40 in yet another embodiment.
  • a FAR value is typically obtained by comparing the extruded film to a set of reference film standards having the same thickness (typically 1.0 mil thickness). For example, one may use the standards available from The Dow Chemical Company (citing Test Method PEG #510 FAR). The FAR test may be conducted as described in US 7,714,072.
  • the blends comprising the polyethylene (preferably linear polyethylene) described herein and the branched modifier described herein have good processability as indicated by strain hardening ratio.
  • the blends comprising the polyethylene (preferably linear polyethylene) described herein and the branched modifier described herein have a strain hardening ratio (SHR) of 1.1 or more, preferably 1.5 or more, preferably 2.0 or more, when the extensional viscosity is measured at a strain rate of 1 sec -1 and at a temperature of 150°C as describe below in the Test Methods.
  • SHR strain hardening ratio
  • the polyethylene compositions comprising one or more ethylene polymers and one or more branched modifiers show characteristics of strain hardening in extensional flow. Strain hardening is observed as a sudden, abrupt upswing of the extensional viscosity in the transient extensional viscosity vs. time plot. This abrupt upswing, away from the behavior of a linear viscoelastic material, was reported in the 1960s for LDPE (reference: J. Meissner, Rheology Acta., Vol. 8, 78, 1969) and was attributed to the presence of long branches in the polymer.
  • the inventive polyethylene compositions have strain-hardening in extensional viscosity.
  • the strain-hardening ratio is preferably 1.2 or more, preferably 1.5 or more, more preferably 2.0 or more, and even more preferably 2.5 or more, when the extensional viscosity is measured at a strain rate of 1 sec -1 and at a temperature of 150°C.
  • the melt strength of the blend is at least 5% higher than the melt strength of ethylene polymer component(s) used in the blend.
  • Rheology of the inventive composition can be different from the rheology of the ethylene polymer component, depending on the properties of the branched modifier polymer.
  • the difference in complex shear viscosity between the inventive composition and ethylene polymer component(s) is less than 10%, preferably less than 5% at all frequencies.
  • the complex shear viscosity of the inventive polyethylene composition is at least 10% higher than the complex viscosity of the ethylene polymer component(s) employed in the blend composition when the complex viscosity is measured at a frequency of 0.1 rad/sec and a temperature of 190°C, and the complex viscosity of the inventive polyethylene composition is the same or less than the complex viscosity of the ethylene polymer component used in the blend composition when the complex viscosity is measured at a frequency of 398 rad/sec and a temperature of 190°C.
  • the complex shear viscosity is measured according to procedure described in the Test Method section below.
  • the shear thinning ratio of the inventive composition is at least 10% higher than the shear thinning ratio of the ethylene polymer component.
  • the blend of the polyethylene and the modifier has a melt index, as measured by ASTM D-1238 at 190°C and 2.16 kg in the range of from 0.01 dg/min to 100 dg/min in one embodiment, from 0.01 dg/min to 50 dg/min in a more particular embodiment, from 0.02 dg/min to 20 dg/min in yet a more particular embodiment, from 0.03 dg/min to 2 dg/min in yet a more particular embodiment, and from 0.002 dg/min to 1 dg/min in yet a more particular embodiment.
  • a melt index as measured by ASTM D-1238 at 190°C and 2.16 kg in the range of from 0.01 dg/min to 100 dg/min in one embodiment, from 0.01 dg/min to 50 dg/min in a more particular embodiment, from 0.02 dg/min to 20 dg/min in yet a more particular embodiment, from 0.03 dg/min to 2 dg/min
  • the HLMI, also referred to as the 121, (ASTM D 1238 190°C, 21.6 kg) of the blend of the polyethylene and the modifier ranges from 0.01 to 800 dg/min in one embodiment, from 0.1 to 500 dg/min in another embodiment, from 0.5 to 300 dg/min in yet a more particular embodiment, and from 1 to 100 dg/min in yet a more particular embodiment wherein a desirable range is any combination of any upper 121 limit with any lower 121 limit.
  • the blend of the polyethylene and the modifier has a melt index ratio
  • the modifiers may have a melt index ratio of from greater than 15 in one embodiment, greater than 20 in a more particular embodiment, greater than 30 in yet a more particular embodiment, greater than 40 in yet a more particular embodiment, and greater than 50 in yet a more particular embodiment.
  • the blend of the polyethylene and the modifier is gel-free. Presence of gel can be detected by dissolving the material in xylene at xylene's boiling temperature. Gel-free product should be dissolved in xylene.
  • the branched modifier has 5 wt% or less (preferably 4 wt% or less, preferably 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0 wt%) of xylene insoluble material.
  • this invention relates to a composition
  • a composition comprising more than 25 wt% (based on the weight of the composition) of one or more ethylene polymers having a g' vjs of 0.95 or more and an M w of 20,000 g/mol or more and at least 0.1 wt% of a dendritic hydrocarbon polymer modifier where the modifier has a g' vjs of less than 0.75, wherein the ethylene polymer has a g' vjs of at least 0.2 units higher than the g' vjs of the branched modifier, preferably at least 0.25 higher, preferably at least 0.30 higher, preferably at least 0.35 higher, preferably at least 0.40 higher.
  • films, preferably blown films, produced from the blend of polyethylene and modifier have an Elmendorf Tear, (reported in grams (g) or grams per mil (g/mil) as determined by ASTM D-1922) of at least 100 g/mil, preferably at least 150 g/mil, preferably at least 200 g/mil, wherein a desirable blend may exhibit any combination of any upper limit with any lower limit.
  • Elmendorf Tear (reported in grams (g) or grams per mil (g/mil) as determined by ASTM D-1922) of at least 100 g/mil, preferably at least 150 g/mil, preferably at least 200 g/mil, wherein a desirable blend may exhibit any combination of any upper limit with any lower limit.
  • films, preferably blown films, produced from the blend of polyethylene and modifier has a haze, (measured according to ASTM D1003) of 25 or less, preferably 15 or less, preferably 10 or less.
  • films, preferably blown films, produced from the blends of polyethylene and modifier described herein has a Dart Drop (determined as described in the Test Methods below and reported as grams per mil) of at least 100 g/mil, preferably at least 150, preferably at least 200 g/mil.
  • films, preferably blown films, produced from the blends of polyethylene and modifier described herein are at least 0.3 mils thick, preferably at least 0.5 mils thick, preferably at least 1.0 mils thick, and preferably the films are less than 5 mils thick, preferably less than 3 mils thick, preferably less than 2 mils thick, wherein a desirable blend may exhibit any combination of any upper limit with any lower limit.
  • the polyethylene compositions of the present invention include a dendritic hydrocarbon polymer modifier (also referred to as a "modifier” or a “branched modifier” or a “branched modifier polymer” or a “dendritic modifier” herein). It will be realized that the classes of materials described herein that are useful as modifiers can be utilized alone or admixed with other modifiers described herein in order to obtain desired properties.
  • Dendritic hydrocarbon polymers useful as modifiers herein are typically produced in a one step process for making a dendritic hydrocarbon polymer by metathesis insertion polymerization and thereafter optionally hydrogenating the polymer.
  • the process comprises polymerizing an amount of one or more cyclic olefins and one or more multi-functional (meth)acrylates in the presence of a metathesis catalyst and under conditions sufficient to produce the dendritic hydrocarbon polymer.
  • the one or more multi-functional (meth)acrylates preferably have a functionality of 3 or higher.
  • the dendritic hydrocarbon polymer is then hydrogenated to form the substantially saturated dendritic hydrocarbon polymer.
  • Dendritic hydrocarbon polymers useful as modifiers herein are typically produced in a one step process by metathesis insertion copolymerization of cyclic olefins and multifunctional (meth)acrylates in the presence of a metathesis catalyst followed by direct hydrogenation in the same reactor. Unlike previously disclosed synthetic methods, this new synthetic method constructs complex dendritic polyolefins in a single step using commercially available monomers and catalysts. A separate hydrogenation step is necessary to deliver fully saturated polyolefins, but it can be done in the same reaction vessel and solvent system, i.e., a one pot method.
  • the cyclic olefins useful in the processes of this disclosure can be any cyclic olefins that are capable of ring opening and polymerization in the presence of a metathesis catalyst.
  • Illustrative cyclic olefins include, for example, cyclooctene and its derivatives, cyclooctadiene, 1,5-dimethylcyclooctadiene, norbornene and its derivatives, cyclic olefins with a suitable ring strain, bicyclic or multicyclic olefins, and the like. Cyclic olefins with sufficient ring strains for ring opening metathesis polymerization are preferred.
  • the method of this disclosure allows the selection of cyclic olefin monomers for designing the dendritic polyolefin backbone composition.
  • the final dendritic and hydrogenated polyolefins can be crystalline or amorphous.
  • the cyclic olefins are conventional materials known in the art and commercially available.
  • the multi-functional (meth)acrylates useful in the processes of this disclosure can be any multi-functional acrylates or methacrylates that are capable of insertion and polymerization with a cyclic olefin.
  • Illustrative multi-functional (meth)acrylates include, for example, trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylate triacrylate, glycerol propoxylate (IPO/OH) triacrylate, l,3,5-triacryloylhexahydro-l,3,5-triazine, tris[2-(acryloyloxy)ethyl] isocyanurate, pentaerythritol tetraacrylate (PETA), di(trimethylolpropane) tetraacrylate, dipentaerythritol hexaacrylate (DPEHA), and the like.
  • TMPTA trimethylolpropane triacrylate
  • IP/OH glyce
  • the functionality of the multi-functional (meth)acrylate is 3 or higher, in order to develop higher generation, greater than second-generation, dendritic polyolefins. Many tri-, terra-, and even higher multi-functional (meth)acrylates are commercially available at reasonable prices. Dendritic generations can be tailored to third or higher with a proper selection of the multi-functional (meth)acrylate and other reaction conditions. Dendritic generation/branching density can also be adjusted by acrylic connector choice.
  • (meth)acrylates used in the process of this disclosure can vary over a wide range and need only be concentrations sufficient to form the dendritic hydrocarbon polymer.
  • the one or more cyclic olefins and one or more multi-functional (meth)acrylates can be present in a molar concentration ratio (cyclic olefin/multi-functional (meth)acrylate) of from 2 and higher, preferably from 3 to 2000, and more preferably from 50 to 200.
  • Dendritic generations can be tailored to third and higher with a proper selection of the cyclic olefin/multi-functional (meth)acrylate molar ratio.
  • (meth)acrylate molar ratio will range from 3 and higher.
  • the cyclic olefin/multi-functional (meth)acrylate molar ratio will range from 2.25 and higher.
  • the cyclic olefin/multi-functional (meth)acrylate molar ratio will range from 2.1 and higher.
  • the cyclic olefin/multi-functional (meth)acrylate molar ratio will range from 2 and higher.
  • the metathesis catalyst can be any catalyst suitable for catalyzing the metathesis polymerization.
  • Illustrative metathesis catalysts useful in the process of this disclosure include, for example, Grubbs 1 st generation catalyst, Grubbs 2 nd generation catalyst, Hoveyda-Grubbs catalysts, ruthenium-based metathesis catalysts, and the like.
  • the catalysts are conventional materials known in the art and commercially available.
  • the metathesis catalyst is one or more of tricyclohexylphosphine[l,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-lH- inden- 1 -ylidene]ruthenium(II) dichloride,
  • the catalyst is l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2- (i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride, and/or tricyclohexylphosphine[3 -phenyl- IH-inden- 1 -ylidene] [ 1 ,3 -bis(2,4,6-trimethylphenyl)- 4,5-dihydroimidazol-2-ylidene]ruthenium(II) dichloride.
  • the metathesis catalyst useful herein may be any of the catalysts described in U.S. Patent Nos. 6,1 11, 121; 5,312,940; 5,342,909; 7,329,758; 5,831, 108; 5,969, 170; 6,759,537; 6,921,735; and U.S. Patent Publication No. 2005-0261451 Al, including, but not limited to:
  • benzy lidene [ 1 , 3 -bis (2 ,4, 6-trimethy lpheny l)-2 imidazolidiny lidene] dichloro (tricyclohexy 1 phosphine) ruthenium;
  • the metathesis catalyst compound comprises one or more of:
  • the concentration of the metathesis catalyst used in the process of this disclosure can vary over a wide range and need only be a concentration sufficient to catalyze the polymerization.
  • the metathesis catalyst can be present in an amount of from 0.00001 M to 1 M, preferably from 0.0001 M to 0.1 M, and more preferably from 0.001 M to 0.01 M.
  • the length between two branching points is tunable, which is controlled by catalyst loading.
  • Dendritic generation/branching density can be adjusted by catalyst loading and/or acrylic connector choice.
  • the average linker length and insertion efficiency can be controlled by the catalyst loading.
  • Linker length increases with the decrease of catalyst loading.
  • a high full insertion ratio can be achieved at a certain catalyst loading.
  • the dendritic polyolefins prepared by the process of this disclosure preferably have a dendritic generation of 2 (e.g., a Cayley tree topology of 2) and higher and have molecular weight between 5,000 to 5,000,000 g/mol, and most preferably between 10,000 and 1,000,000 g/mol.
  • Illustrative dendritic polyolefins prepared by the process described herein are shown in Figure 1.
  • the dendritic structure is a dendritic structure of at least generation 2 (e.g., a Cayley tree topology of at least 2). In another embodiment, the dendritic structure is a dendritic structure of at least generation 3 (e.g., a Cayley tree topology of at least 3).
  • the crystalline dendritic polyolefins of this disclosure can be used as a processability additive in a semi-crystalline polyolefin of similar backbone composition for delivering extensional strain hardening, higher melt strength, and faster blown film processing speed at a concentration of 0.1 wt% to 20 wt%, more preferably 0.25 wt% to 15 wt%, and most preferably 0.5 wt% to 10 wt%.
  • the amorphous dendritic polyolefins of this disclosure can be used as a processability additive in an elastomeric polyolefin of similar backbone composition for delivering extensional hardening and higher melt strength for better compounding processability and cold flow resistance at a concentration of 0.1 wt% to 20 wt%, more preferably 0.25 wt% to 15 wt%, and most preferably 0.5 wt% to 10 wt%.
  • This amorphous dendritic polyolefin can also be used as a viscosity index improver in lubricants due to its temperature invariant solution coil dimension and its shear stability at a concentration of 0.01 wt% to 7.5 wt%, more preferably 0.1 wt% to 5 wt%, and most preferably 0.3 wt% to 3 wt%.
  • Dendritic polyolefins of this disclosure with second and higher generations are unique processability additives in polyolefins for delivering extensional strain hardening, melt strength, and higher blown film processing speed.
  • dendritic polyethylenes of second generation or higher have been prepared by anionic polymerization and anionic condensation followed by hydrogenation. Both anionic polymerization and anionic condensation methods involve more than three synthetic steps including the synthesis of the di-functional initiator and one hydrogenation step. Additionally, anionic methods are sensitive to impurities and reactions can be slow or stopped with accumulation of impurities.
  • a one step synthetic method has been developed for preparing dendritic polyolefins before hydrogenation based on metathesis insertion copolymerization of cyclic olefins and multi-functional (meth)acrylates that have 3 or more functionalities.
  • the dendritic polyolefin backbone composition, the molecular weight of the linker in between branching points, and the dendritic generation can be tailored based on the selection of cyclic olefin monomer, catalyst amount, cyclic olefin to multi-functional (meth)acrylate molar ratio, and the number of functionality on the (meth)acrylate.
  • hydrogenation can be carried out in the same reactor immediately following the polymerization, to furnish fully saturated polyolefins.
  • Various commercial cyclic olefins and multi-functional (meth)acrylates can be directly utilized in the synthesis, to yield dendritic polyolefins of desirable structures.
  • Polymerization conditions for the reaction of the one or more cyclic olefins and one or more multi-functional (meth)acrylates may also vary greatly and any suitable combination of such conditions may be employed herein.
  • the reaction temperature may range between -40°C to 120°C, preferably between 15°C to 100°C, and more preferably between 20°C to 80°C.
  • the reaction is carried out under ambient pressure and the contact time may vary from a matter of seconds or minutes to a few hours or greater.
  • the reactants can be added to the reaction mixture or combined in any order.
  • the stir time employed can range from 3 minutes to 168 hours, preferably from 10 minutes to 72 hours, and more preferably from 30 minutes to 6 hours.
  • substantially saturated as it refers to the dendritic hydrocarbon polymer means that polymer includes on average fewer than 10 double bonds, or fewer than 5 double bonds, or fewer than 3 double bonds, or fewer than 1 double bond per 100 carbons in a hydrocarbon polymer chain.
  • the Rachapudy et al. article discloses a method of preparation of a homogeneous catalyst.
  • the catalyst can be formed by reaction between a metal alkyl and the organic salt of a transition metal.
  • the metal alkyls were n-butyl lithium (in cyclohexane) and triethyl aluminum (in hexane).
  • the metal salts were cobalt and nickel 2-ethyl hexanoates (in hydrocarbon solvents) and platinum and palladium acetyl-acetonates (solids). Hydrogenation was conducted in a 1 -liter heavy -wall glass reactor, fitted with a stainless steel flange top and magnetically stirred.
  • the Rachapudy et al. article also discloses a method of preparation of a heterogeneous catalyst.
  • a 1 -liter high-pressure reactor (Parr Instrument Co.) was used.
  • the catalysts were nickel on kieselguhr (Girdler Co.) and palladium on calcium carbonate (Strem Chemical Co.).
  • the catalysts described herein can be used to hydrogenate hydrocarbons containing unsaturated carbon bonds.
  • the unsaturated carbon bonds which may be hydrogenated include olefinic and acetylenic unsaturated bonds.
  • the process is particularly suitable for the hydrogenation under mild conditions of hydrogenatable organic materials having carbon-to- carbon unsaturation, such as acyclic monoolefins and polyolefins, cyclic monoolefins and polyolefins, and mixtures thereof. These materials may be unsubstituted or substituted with additional non-reactive functional groups such as halogens, ether linkages or cyano groups.
  • Exemplary of the types of carbon-to-carbon compounds useful herein are hydrocarbons of 2 to 30 carbon atoms, e.g., olefinic compounds selected from acyclic and cyclic mono-, di-, and triolefins.
  • the catalysts of this disclosure are also suitable for hydrogenating carbon-to- carbon unsaturation in polymeric materials, for example, in removing unsaturation from butadiene polymers and co-polymers such as styrene-butadiene-styrene.
  • the hydrogenation reaction herein is normally accomplished at a temperature from 40°C to 160°C and preferably from 60°C to 150°C. Different substrates being hydrogenated will require different optimum temperatures, which can be determined by experimentation.
  • the initial hydrogenation pressures may range up to 3,000 psi partial pressure, at least part of which is present due to the hydrogen. Pressures from 1 to 7500 psig are suitable. Preferred pressures are up to 2000 psig, and most preferred pressures are from 100 to 1000 psig are employed.
  • the reactive conditions are determined by the particular choices of reactants and catalysts.
  • the process may be either batch or continuous. In a batch process, reaction times may vary widely, such as between 0.01 second to 10 hours. In a continuous process, reaction times may vary from 0.1 seconds to 120 minutes and preferably from 0.1 second to 10 minutes.
  • the ratio of catalyst to material being hydrogenated is generally not critical and may vary widely within the scope of the disclosure. Molar ratios of catalyst to material being hydrogenated between 1 : 1000 and 10: 1 are found to be satisfactory; higher and lower ratios, however, are possible.
  • the hydrogenation process may be carried out in the presence of an inert diluent, for example, a paraffinic or cycloparaffinic hydrocarbon.
  • an inert diluent for example, a paraffinic or cycloparaffinic hydrocarbon.
  • any of the Group VIII metal compounds known to be useful in the preparation of catalysts for the hydrogenation of ethylenic unsaturation can be used separately or in combination to prepare the catalysts.
  • Suitable compounds include Group VIII metal carboxylates having the formula (RCOO) n M, wherein M is a Group VIII metal, R is a hydrocarbyl radical having from 1 to 50 carbon atoms, preferably from 5 to 30 carbon atoms, and n is a number equal to the valence of the metal M; alkoxides having the formula (RCO) n M, wherein M is again a Group VIII metal, R is a hydrocarbon radical having from 1 to 50 carbon atoms, preferably from 5 to 30 carbon atoms, and n is a number equal to the valence of the metal M; chelates of the metal prepared with beta-ketones, alpha- hydroxycarboxylic acids beta-hydroxycarboxylic acids, beta-hydroxycarbonyl compounds, and the like; salts of sulfur-containing acids
  • the metal carboxylates useful in preparing the catalyst include Group VIII metal salts of hydrocarbon aliphatic acids, hydrocarbon cycloaliphatic acids, and hydrocarbon aromatic acids.
  • hydrocarbon aliphatic acids include hexanoic acid, ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and rhodinic acid.
  • hydrocarbon aromatic acids include benzoic acid and alkyl-substituted aromatic acids in which the alkyl substitution has from 1 to 20 carbon atoms.
  • cycloaliphatic acids include naphthenic acid, cyclohexylcarboxylic acid, and abietic-type resin acids.
  • Suitable chelating agents which may be combined with various Group VIII metal compounds thereby yielding a Group VIII metal chelate compound useful in the preparation of the catalyst include beta-ketones, alpha-hydroxycarboxylic acids, beta-hydroxy carboxylic acids, and beta-hydroxycarbonyl compounds.
  • beta-ketones that may be used include acetylacetone, 1,3-hexanedione, 3,5-nonadione, methylacetoacetate, and ethylacetoacetate.
  • alpha-hydroxycarboxylic acids examples include lactic acid, glycolic acid, alpha-hydroxyphenylacetic acid, alpha-hydroxy-alpha-phenylacetic acid, and alpha- hydroxycyclohexylacetic acid.
  • beta-hydroxycarboxylic acids examples include salicylic acid and alkyl-substituted salicylic acids.
  • beta-hydroxylcarbonyl compounds examples include salicylaldehyde and ⁇ -hydroxyacetophenone.
  • the metal alkoxides useful in preparing the catalysts include Group VIII metal alkoxides of hydrocarbon aliphatic alcohols, hydrocarbon cycloaliphatic alcohols, and hydrocarbon aromatic alcohols.
  • hydrocarbon aliphatic alcohols examples include hexanol, ethylhexanol, heptanol, octanol, nonanol, decanol, and dodecanol.
  • the Group VIII metal salts of sulfur-containing acids and partial esters thereof include Group VIII metal salts of sulfonic acid, sulfuric acid, sulphurous acid, and partial esters thereof.
  • aromatic sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid are particularly useful.
  • any of the alkylalumoxane compounds known to be useful in the preparation of olefin polymerization catalysts may be used in the preparation of the hydrogenation catalyst.
  • Alkylalumoxane compounds useful in preparing the catalyst may, then, be cyclic or linear. Cyclic alkylalumoxanes may be represented by the general formula (R-Al-0) m while linear alkylalumoxanes may be represented by the general formula
  • R will be an alkyl group having from 1 to 8 carbon atoms such as, for example, methyl, ethyl, propyl, butyl, and pentyl; m is an integer from 3 to 40; and n is an integer from 1 to 40. In a preferred embodiment, R will be methyl, m will be a number from 5 to 20, and n will be a number from 10 to 20.
  • alkylalumoxanes may be prepared by reacting an aluminum alkyl with water. Usually the resulting product will be a mixture of both linear and cyclic compounds.
  • the aluminum alkyl may first be dissolved in a suitable solvent such as toluene or an aliphatic hydrocarbon and the solution then contacted with a similar solvent containing relatively minor amounts of moisture.
  • a suitable solvent such as toluene or an aliphatic hydrocarbon
  • an aluminum alkyl may be contacted with a hydrated salt, such as hydrated copper sulfate or ferrous sulfate.
  • a hydrated ferrous sulfate is frequently used.
  • a dilute solution of aluminum alkyl in a suitable solvent such as toluene is contacted with hydrated ferrous sulfate.
  • 1 mole of hydrated ferrous sulfate will be contacted with from 6 to 7 moles of the aluminum trialkyl.
  • aluminum trimethyl is the aluminum alkyl actually used, methane will be evolved as conversion of the aluminum alkyl to an alkylalumoxane occurs.
  • any of the Group la, Ila, or Ilia metal alkyls or hydrides known to be useful in preparing hydrogenation catalysts in the prior art may be used to prepare the catalyst.
  • the Group la, Ila, or Ilia metal alkyls will be peralkyls with each alkyl group being the same or different containing from 1 to 8 carbon atoms and the hydrides will be perhydrides although alkylhydrides should be equally useful.
  • Aluminum, magnesium, and lithium alkyls and hydrides are particularly useful and these compounds are preferred for use in preparing the catalyst.
  • Aluminum trialkyls are most preferred.
  • the one or more alkylalumoxanes and the one or more Group la, Ila, or Ilia metal alkyls or hydrides may be combined and then contacted with the one or more Group VIII metal compounds or the one or more alkylalumoxanes and the one or more Group la, Ila, or Ilia metal alkyls or hydrides may be sequentially contacted with the one or more Group VIII metal compounds with the proviso that when sequential contacting is used, the one or more alkylalumoxanes will be first contacted with the one or more Group VIII metal compounds. Sequential contacting is preferred.
  • the two different reducing agents i.e., the alkylalumoxanes and the alkyls or hydrides
  • the Group VIII metal compound might react with the Group VIII metal compound in such a way as to yield different reaction products.
  • the Group la, Ila, and Ilia metal alkyls and hydrides are a stronger reducing agent than the alkylalumoxanes, and, as a result, if the Group VIII metal is allowed to be completely reduced with a Group la, Ila, or Ilia metal alkyl or hydride, the alkylalumoxanes might make little or no contribution.
  • the reaction product obtained with the alumoxane might be further reduced or otherwise altered by reaction with a Group la, Ila, or Ilia metal alkyl or hydride.
  • the one or more alkylalumoxanes will be combined with the one or more Group VIII metal compounds at a concentration sufficient to provide an aluminum to Group VIII metal atomic ratio within the range from 1.5: 1 to 20: 1 and the one or more Group la, Ila, or Ilia metal alkyls or hydrides will be combined with one or more Group VIII metal compounds at a concentration sufficient to provide a Group la, Ila, or Ilia metal to Group VIII metal atomic ratio within the range from 0.1 : 1 to 20: 1.
  • Contact between the one or more Group VIII compounds and the one or more alkylalumoxanes and the one or more alkyls or hydrides will be accomplished at a temperature within the range from 20°C and 100°C. Contact will typically be continued for a period of time within the range from 1 to 120 minutes. When sequential contacting is used, each of the two contacting steps will be continued for a period of time within this same range.
  • the hydrogenation catalyst will be prepared by combining the one or more Group VIII metal compounds with the one or more alkylalumoxanes and the one or more Group la, Ila, or Ilia metal alkyls or hydrides in a suitable solvent.
  • the solvent used for preparing the catalyst may be anyone of those solvents known in the prior art to be useful as solvents for unsaturated hydrocarbon polymers.
  • Suitable solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; alkyl-substituted cycloaliphatic hydrocarbons such as methylcyclopentane, methylcyclohexane, and methylcyclooctane; aromatic hydrocarbons such as benzene; hydroaromatic hydrocarbons such as decalin and tetralin; alkyl-substituted aromatic hydrocarbons such as toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; and linear and cyclic ethers such as the various dialkyl ethers, polyethers, particularly diethers, and tetrahydrofuran.
  • Suitable hydrogenation catalysts will usually be prepared by combining the catalyst components in a separate vessel prior to feeding the same to the hydrogenation reactor.
  • the modifier has:
  • a g' vis value less than 0.75 (preferably less than 0.70, preferably less than 0.65, preferably less than 0.60, preferably less than 0.55, preferably less than 0.50, preferably less than 0.45, preferably less than 0.40, preferably less than 0.35, preferably less than 0.30); 2) a Cayley tree topology with a layer number of 2 or more, preferably 3 or more, preferably 4 or more; 3) at least 0.6 ppm (preferably at least 10 ppm, preferably at least 100 ppm, preferably at least 1000 ppm, preferably at least 5000 ppm) of ester groups (as determined by l R NMR); 4) optionally, an average Mw between the branch points of 1,000 g/mol or more (preferably 3,000 g/mol or more, preferably 5,000 g/mol or more); 5) optionally, a crystallinity greater than 10% (preferably greater than 15%, preferably greater than 20%, as determined by DSC as described below); and 6) optionally, a heat of
  • the modifier has: 1) a g' vis value or 0.75 or less (preferably 0.70 or less, preferably 0.65 or less, preferably 0.60 or less, preferably 0.55 or less, preferably 0.50 or less, preferably 0.45 or less, preferably 0.40 or less, preferably 0.35 or less, preferably 0.30 or less); 2) at least 0.6 ppm ester groups (preferably 0.75 or more, preferably 1.0 or more, preferably 1.2 or more, preferably 1.50 or more) as determined by NMR; 3) a Tm of 100°C or more (preferably 1 10°C or more, preferably 120°C or more, preferably 125°C or more) as determined by DSC; 4) an Mw of 50,000 g/mol or more (preferably 100,000 g/mol or more, preferably 150,000 g/mol or more, preferably 200,000 g/mol or more, preferably 500,000 or more) as determined by GPC; 5) an average number of carbon atoms between the branch points of 70 or more
  • the average Mw between the branch points is determined by NMR on the unhydrogenated material using the integral ratio of the internal vinylene protons (for example, peak c in Figure 6a) to the double bond proton next to the carbonyl (for example, peak a in Figure 6a).
  • testing on the hydrogenated material uses the integral ratio of the all other alkyl protons (for example, the peak at 1.5 ppm in Figure 6a) to the CH2 proton next to the ester (for example, peak d in figure 6a).
  • Average number of carbon atoms between the branch points is determined by dividing the average Mw between the branch points by 14.
  • the dendritic hydrocarbon polymer modifiers used in this invention are described as having a Cayley tree topology with at least two (preferably at least three, preferably at least four) layers or having at least a second (preferably at least third generation, preferably at least fourth generation) Cayley tree topology as referenced in Van Ruymbeke et al. Macromolecules, Vol. 40, No. 16, 2007 and Blackwell et al, Macromolecules, 2001, 34, 2579-2596.
  • the three armed material on the top left is referred to as having one layer
  • the structure in the top middle is referred to as having two layers
  • the structure on the top right is referred to as having three layers.
  • the structures on the bottom left and right are examples of two and three layer materials, even though each branch point is not symmetric.
  • the layer number affects the relaxation priority and is an important component in affecting the extensional relaxation.
  • the dendritic hydrocarbon polymer modifiers may have a Cayley tree topology with at least four (alternately at least five) layers or having at least a fourth (preferably fifth) generation Cayley tree topology.
  • the layer number is referred to as "n" in Blackwell et al, Macromolecules, 2001, 34, 2579-2596.
  • the layer numbers can be determined based on molecular weight fractionation (for example, where the modifier begins with a tri-armed material, layer 2 will have an Mn roughly equal to the linker Mn times 9 and layer 3 will have an Mn roughly equal to the linker Mn times 21, etc.) and relaxation fractionation (based on Small Amplitude Oscillatory Shear test where two relaxation peaks will be found for layer 2, 3 relaxation peaks will be detected for layer 3, and so on).
  • layer 2 will have a Mn roughly equal to the linker Mn times 16 and layer 3 will have a Mn roughly equal to the linker Mn times 52, etc., and relaxation fractionation (based on Small Amplitude Oscillatory Shear test where two relaxation peaks will be found for layer 2, 3 relaxation peaks will be detected for layer 3, and so on).
  • any dendritic hydrocarbon polymer modifier described herein has an average Mw of 1000 g/mol or more, preferably 3,000 g/mol or more, preferably 5000 g/mol or more between branch points.
  • the dendritic hydrocarbon polymer modifiers have:
  • a g' vis of less than 0.75 (preferably less than 0.70, preferably less than 0.65, preferably less than 0.60, preferably less than 0.55, preferably less than 0.50, preferably less than 0.45, preferably less than 0.40);
  • a density of from about 0.880 to about 0.980 g/cm 3 (preferably from 0.890 to 0.940 g/cc, preferably from 0.900 to 0.935 g/cc, preferably from 0.910 to 0.930 g/cc);
  • Mw/Mn molecular weight distribution
  • xylene insoluble material optionally, less than 5 wt% xylene insoluble material (preferably 4 wt% or less, preferably 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0 wt%).
  • This invention further relates to a dendritic hydrocarbon polymer modifier where the modifier: a) has a g' vis of 0.75 or less (preferably less than 0.70, preferably less than 0.65, preferably less than 0.60, preferably less than 0.55, preferably less than 0.50, preferably less than 0.45, preferably less than 0.40, preferably 0.35 or less, preferably 0.30 or less); b) is essentially gel free (preferably 5 wt% or less of xylene insoluble material, preferably 4 wt% or less, preferably 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0 wt%); c) has a Mw of 10,000 g/mol or more (preferably 25,000 or more, preferably 50,000 or more); d) a Cayley tree topology with 2 or more layers, preferably 3 or more layers, preferably 4 or more layers; e) an average Mw between the branch points that is greater than 1000 g/
  • the modifiers comprise side chain branches that are ethyl, butyl, or hexyl as determined by 13 C NMR as described below.
  • the modifiers are dendritic hydrocarbon polymers, preferably substantially saturated dendritic hydrocarbon polymers, preferably saturated dendritic hydrocarbon polymers as determined by 13 C NMR as described below.
  • the branched structure of the modifiers and the blends containing the modifiers can also be observed by Small Amplitude Oscillatory Shear (SAOS) measurement of the molten polymer performed on a dynamic (oscillatory) rotational rheometer. From the data generated by such a test it is possible to determine the phase or loss angle ⁇ , which is the inverse tangent of the ratio of G" (the loss modulus) to G' (the storage modulus). For a typical linear polymer, the loss angle at low frequencies (or long times) approaches 90 degrees, because the chains can relax in the melt, adsorbing energy, and making the loss modulus much larger than the storage modulus.
  • SAOS Small Amplitude Oscillatory Shear
  • rheological data may be presented by plotting the phase angle versus the absolute value of the complex shear modulus (G * ) to produce a van Gurp-Palmen plot.
  • the plot of conventional polyethylene polymers shows monotonic behavior and a negative slope toward higher G* values.
  • Conventional LLDPE polymers without long chain branches exhibit a negative slope on the van Gurp-Palmen plot.
  • the van Gurp-Palmen plots of some embodiments of the branched modifier polymers described in the present disclosure exhibit two slopes - a positive slope at lower G* values and a negative slope at higher G* values.
  • ⁇ * represents the complex viscosity (Pa.s)
  • ⁇ represents the frequency
  • S is the gel stiffness
  • ⁇ is the gamma function
  • n is the critical relaxation exponent.
  • Modifiers useful herein preferably have a gel stiffness of more than 150 Pa.s, preferably at least 300 Pa.s, and more preferably at least 500 Pa.s. The gel stiffness is determined at the test temperature of 190°C.
  • a preferred critical relaxation exponent n for the modifiers useful herein is less than 1 and more than 0, generally, n will be between 0.1 and 0.92, preferably between 0.2 and 0.85.
  • ⁇ 0.01, 0.1, 1, 10, and 100 seconds.
  • the sum of the r ⁇ 's is equal to the zero shear viscosity, ⁇ 0 .
  • An indication of high levels of branched block products is a high value of ⁇ 5 , corresponding to the relaxation time of 100 s, relative to the zero shear viscosity.
  • the viscosity fraction of the 100 s relaxation time is ⁇ 5 divided by the zero shear viscosity, ⁇
  • the modifiers used herein preferably have good shear thinning.
  • Shear thinning is characterized by the decrease of the complex viscosity with increasing shear rate.
  • One way to quantify the shear thinning is to use a ratio of complex viscosity at a frequency of 0.01 rad/s to the complex viscosity at a frequency of 100 rad/s.
  • the complex viscosity ratio of the modifier is 20 or more, more preferably 50 or more, even more preferably 100 or more when the complex viscosity is measured at 190°C.
  • Shear thinning can be also characterized using a shear thinning index.
  • the term "shear thinning index" is determined using plots of the logarithm (base ten) of the dynamic viscosity versus logarithm (base ten) of the frequency. The slope is the difference in the log (dynamic viscosity) at a frequency of 100 rad/s and the log (dynamic viscosity) at a frequency of 0.01 rad/s divided by 4. These plots are the typical output of small amplitude oscillatory shear (SAOS) experiments.
  • SAOS test temperature is 190°C for ethylene polymers and blends thereof.
  • Polymer viscosity is conveniently measured in Pascal*seconds (Pa*s) at shear rates within a range of from 0.01 to 398 rad/sec and at 190°C under a nitrogen atmosphere using a dynamic mechanical spectrometer such as the Advanced Rheometrics Expansion System (ARES).
  • a dynamic mechanical spectrometer such as the Advanced Rheometrics Expansion System (ARES).
  • ARES Advanced Rheometrics Expansion System
  • a low value of shear thinning index indicates that the polymer is highly shear-thinning and that it is readily processable in high shear processes, for example, by injection molding. The more negative this slope, the faster the dynamic viscosity decreases as the frequency increases.
  • the modifier has a shear thinning index of less than -0.2. These types of modifiers are easily processed in high shear rate fabrication methods, such as injection molding.
  • the branched modifier useful herein also preferably has characteristics of strain hardening in extensional viscosity.
  • An important feature that can be obtained from extensional viscosity measurements is the attribute of strain hardening in the molten state. Strain hardening is observed as a sudden, abrupt upswing of the extensional viscosity in the transient extensional viscosity vs. time plot. This abrupt upswing, away from the behavior of a linear viscoelastic material, was reported in the 1960s for LDPE (reference: J. Meissner, Rheol. Acta., Vol. 8, 78, 1969) and was attributed to the presence of long branches in the polymer.
  • the strain-hardening ratio is defined as the ratio of the maximum transient extensional viscosity over three times the value of the transient zero-shear-rate viscosity at the same strain rate. Strain hardening is present in the material when the ratio is greater than 1.
  • the branched modifiers show strain-hardening in extensional flow.
  • the strain-hardening ratio is 2 or greater, preferably 5 or greater, more preferably 10 or greater, and even more preferably 15 or more, when extensional viscosity is measured at a strain rate of 1 sec -1 and at a temperature of 150°C.
  • the branched modifier also generally exhibits melt strength values greater than that of conventional linear or long chain branched polyethylene of similar melt index.
  • melt strength refers to the force required to draw a molten polymer extrudate at a rate of 12 mm/s 2 at an extrusion temperature of 190°C until breakage of the extrudate whereby the force is applied by take up rollers.
  • the melt strength of the branched modifier polymer is at least 20% higher than that of a linear polyethylene with the same density and MI.
  • the branched modifier has a strain hardening ratio of 5 or more, preferably 10 or more, preferably 20 or more, preferably 30 or more, preferably 40 or more, preferably 50 or more; and/or an Mw of 50,000 g/mol or more, preferably from 50,000 to 2,000,000 g/mol, alternately from 100,000 to 1,000,000 g/mol, alternately from 150,000 to 750,000 g/mol.
  • the modifier has a melt index as measured by ASTM D-1238 at 190°C and
  • the HLMI (ASTM D 1238 190°C, 21.6 kg) of the modifier ranges from
  • a desirable range is any combination of any upper 121 limit with any lower 121 limit.
  • the modifiers useful herein preferably have a melt index ratio (MIR, or 121/12) of from 10 to 500 in one embodiment, from 15 to 300 in a more particular embodiment, and from 20 to 200 in yet a more particular embodiment.
  • MIR melt index ratio
  • the modifiers may have a melt index ratio of from greater than 15 in one embodiment, greater than 20 in a more particular embodiment, greater than 30 in yet a more particular embodiment, greater than 40 in yet a more particular embodiment, and greater than 50 in yet a more particular embodiment.
  • the branched modifier is gel-free. Presence of gel can be detected by dissolving the material in xylene at xylene's boiling temperature. Gel-free product should be dissolved in xylene.
  • the branched modifier has 5 wt% or less (preferably 4 wt% or less, preferably 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0 wt%) of xylene insoluble material.
  • the branched modifier preferably has an M w of 10,000 to 2,000,000 g/mol, preferably
  • M w /M n of 2 to 40, preferably 2.5 to 30, more preferably 3 to 20, more preferably 3 to 25 as measured by size exclusion chromatography; and/or a M z /M w of 2 to 50, preferably 2.5 to 30, more preferably 3 to 20, more preferably 3 to 25.
  • the branched modifier preferably has a density of 0.85 to 0.97 g/cm 3 , preferably 0.86 to 0.965 g/cm 3 , preferably 0.88 to 0.96 g/cm 3 , alternatively between 0.860 and 0.910 g/cm 3 , alternatively between 0.910 and 0.940 g/cm 3 , or alternatively between 0.94 to 0.965 g/cm 3 (determined according to ASTM D 1505 using a density-gradient column on a compression- molded specimen that has been slowly cooled to room temperature (i.e., over a period of 10 minutes or more) and allowed to age for a sufficient time that the density is constant within +/- 0.001 g/cm 3 ).
  • any branched modifier described herein has a g' Z ave ) of 0.90 or less, preferably 0.85 or less, preferably 0.80 or less, preferably 0.75 or less, preferably 0.70 or less, preferably 0.65 or less, preferably 0.60 or less.
  • Z average branching index (g'(2 ave )) is determined using data generated using the
  • the modifier has a shear thinning ratio of complex viscosity at a frequency of 0.01 rad/sec to the complex viscosity at a frequency of 398 rad/sec greater than 53.9* ⁇ 2(-° ⁇ 74 ), where 12 is the melt index according to ASTM 1238 D, 190°C, 2.16 kg.
  • the modifiers described herein are blended with at least one ethylene polymer to prepare the compositions of this invention.
  • the ethylene polymer is selected from ethylene homopolymer, ethylene copolymers, and blends thereof.
  • Useful copolymers comprise one or more comonomers in addition to ethylene and can be a random copolymer, a statistical copolymer, a block copolymer, and/or blends thereof.
  • the ethylene polymer blends described herein may be physical blends or in situ blends of more than one type of ethylene polymer or blends of ethylene polymers with polymers other than ethylene polymers where the ethylene polymer component is the majority component (e.g., greater than 50 wt%).
  • the method of making the polyethylene is not critical, as it can be made by slurry, solution, gas phase, high pressure, or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylenes, such as Ziegler-Natta-type catalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems, or combinations thereof, or by free-radical polymerization.
  • the ethylene polymers are made by the catalysts, activators and processes described in U.S. Patent Nos. 6,342,566; 6,384, 142; 5,741,563; PCT publications WO 03/040201 ; and WO 97/19991.
  • Such catalysts are well known in the art, and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mulhaupt and Hans H. Brintzinger, eds., Springer- Verlag 1995); Resconi et al; and I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).
  • Preferred ethylene polymers and copolymers that are useful in this invention include those sold by ExxonMobil Chemical Company in Houston Texas, including those sold as ExxonMobil HDPE, ExxonMobil LLDPE, and ExxonMobil LDPE; and those sold under the ENABLETM , EXACTTM, EXCEEDTM, ESCORENETM, EXXCOTM, ESCORTM, PAXONTM, and OPTEMATM tradenames.
  • the polyethylene copolymers preferably have a composition distribution breadth index (CDBI) of 60% or more, preferably 60% to 80%, preferably 65% to 80%.
  • CDBI composition distribution breadth index
  • the ethylene copolymer has a density of 0.910 to 0.950 g/cm 3 (preferably 0.915 to 0.940 g/cm 3 , preferably 0.918 to 0.925 g/cm 3 ) and a CDBI of 60% to 80%, preferably between 65% and 80%.
  • these polymers are metallocene polyethylenes (mPEs).
  • the ethylene copolymer comprises one or more mPEs described in U.S. Patent Application Publication No. 2007/0260016 and U.S. Patent No. 6,476, 171, e.g., copolymers of an ethylene and at least one alpha olefin having at least 5 carbon atoms obtainable by a continuous gas phase polymerization using supported catalyst of an activated molecularly discrete catalyst in the substantial absence of an aluminum alkyl based scavenger (e.g., triethylaluminum, trimethylaluminum, tri-isobutyl aluminum, tri-n- hexylaluminum, and the like), which polymer has a Melt Index of from 0.1 to 15 (ASTM D 1238, condition E); a CDBI of at least 70%, a density of from 0.910 to 0.930 g/cc; a Haze (ASTM D 1003) value of less than 20; a Melt Index ratio (121/12, ASTMD 123
  • Patent No. 6,255,426) of from 20,000 to 60,000 psi (13790 to 41369 N/cm 2 ) and a relation between M and the Dart Impact Strength (26 inch, ASTM D 1709) in g/mil (DIS) complying with the formula:
  • the ethylene polymer comprises a Ziegler-Natta polyethylene, e.g., CDBI less than 50, preferably having a density of 0.910 to 0.950 g/cm 3 (preferably 0.915 to 0.940 g/cm 3 , preferably 0.918 to 0.925 g/cm 3 ).
  • the ethylene polymer comprises olefin block copolymers as described in EP 1 716 190.
  • the ethylene polymer is produced using chrome based catalysts, such as, for example, in U.S. Patent No. 7,491,776 including that fluorocarbon does not have to be used in the production.
  • chrome based catalysts such as, for example, in U.S. Patent No. 7,491,776 including that fluorocarbon does not have to be used in the production.
  • Commercial examples of polymers produced by chromium include the PaxonTM grades of polyethylene produced by ExxonMobil Chemical Company, Houston Texas.
  • the ethylene polymer comprises ethylene and an optional comonomer of propylene, butene, pentene, hexene, octene nonene or decene, and said polymer has a density of more than 0.86 to less than 0.910 g/cm 3 , an Mw of 20,000 g/mol or more (preferably 50,000 g/mol or more), and a CDBI of 90% or more.
  • the ethylene polymer comprises substantially linear ethylene polymers (SLEPs).
  • SEPs substantially linear ethylene polymers
  • Substantially linear ethylene polymers and linear ethylene polymers, and their method of preparation are fully described in U.S. Patent Nos. 5,272,236; 5,278,272; 3,645,992; 4,937,299; 4,701,432; 4,937,301; 4,935,397; 5,055,438; and EP 129,368; EP 260,999; and WO 90/07526, which are fully incorporated herein by reference.
  • a linear or substantially linear ethylene polymer means a homopolymer of ethylene or a copolymer of ethylene and one or more alpha-olefin comonomers having a linear backbone (i.e., no cross linking), a specific and limited amount of long-chain branching or no long-chain branching, a narrow molecular weight distribution, a narrow composition distribution (e.g., for alpha-olefin copolymers), or a combination thereof. More explanation of such polymers is discussed in U.S. Patent No. 6,403,692, which is incorporated herein by reference for all purposes.
  • Preferred ethylene homopolymers and copolymers useful in this invention typically have:
  • T m of 30°C to 150°C, preferably 30°C to 140°C, preferably 50°C to 140°C, more preferably 60°C to 135°C, as determined by the DSC method described below in the Test Methods section;
  • the polyethylene may have a crystallinity of at least 30%, preferably at least 40%, alternatively at least 50%), where crystallinity is determined by the DSC method described below in the Test Methods section; and/or
  • Tc crystallization temperature
  • a heat deflection temperature of 30°C to 120°C, preferably 40°C to 100°C, more preferably 50°C to 80°C, as measured according to ASTM D648 on injection molded flexure bars, at 66 psi load (455kPa); and/or
  • a density of 0.860 to 0.980 g/cc (preferably from 0.880 to 0.940 g/cc, preferably from 0.900 to 0.935 g/cc, preferably from 0.910 to 0.930 g/cc) (alternately from 0.85 to 0.97 g/cm 3 , preferably 0.86 to 0.965 g/cm 3 , preferably 0.88 to 0.96 g/cm 3 , alternatively between 0.860 and 0.910 g/cm 3 , alternatively between 0.910 and 0.940 g/cm 3 , or alternatively between 0.94 to 0.965 g/cm 3 ) (determined according to ASTM D 1505 using a density-gradient column on a compression-molded specimen that has been slowly cooled to room temperature (i.e., over a period of 10 minutes or more) and allowed to age for a sufficient time that the density is constant within +/- 0.001 g/cm 3 ).
  • the polyethylene may be an ethylene homopolymer, such as HDPE.
  • the ethylene homopolymer has a molecular weight distribution (M w /M n ) of up to 40, preferably ranging from 1.5 to 20, from 1.8 to 10 in another embodiment, from 1.9 to 5 in yet another embodiment, and from 2.0 to 4 in yet another embodiment.
  • the 1% secant modulus (determined according to ASTM D 882) of the ethylene polymer falls in a range of 200 to 1000 MPa, and from 300 to 800 MPa in another embodiment, and from 400 to 750 MPa in yet another embodiment, wherein a desirable polymer may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit.
  • the melt index (MI) of preferred ethylene homopolymers range from 0.05 to 800 dg/min in one embodiment, and from 0.1 to 100 dg/min in another embodiment, as measured according to ASTM D1238 (190°C, 2.16 kg).
  • the polyethylene comprises less than 20 mol% propylene units (preferably less than 15 mol%, preferably less than 10 mol%, preferably less than 5 mol%, preferably 0 mol% propylene units).
  • the ethylene polymer is an ethylene copolymer, either random, or block, of ethylene and one or more comonomers selected from C3 to C20 a-olefins, typically from C3 to C JQ a-olefins in another embodiment.
  • the comonomers are present from 0.1 wt% to 50 wt% of the copolymer in one embodiment, from 0.5 wt% to 30 wt% in another embodiment, from 1 wt% to 15 wt% in yet another embodiment, and from 0.1 wt% to 5 wt% in yet another embodiment, wherein a desirable copolymer comprises ethylene and C3 to C20 a-olefin derived units in any combination of any upper wt% limit with any lower wt% limit described herein.
  • the ethylene copolymer will have a weight average molecular weight of from greater than 8,000 g/mol in one embodiment, greater than 10,000 g/mol in another embodiment, greater than 12,000 g/mol in yet another embodiment, greater than 20,000 g/mol in yet another embodiment, less than 1,000,000 g/mol in yet another embodiment, and less than 800,000 g/mol in yet another embodiment, wherein a desirable copolymer may comprise any upper molecular weight limit with any lower molecular weight limit described herein.
  • the ethylene copolymer comprises ethylene and one or more other monomers selected from the group consisting of C3 to C20 linear, branched or cyclic monomers, and in some embodiments is a C3 to (3 ⁇ 4 linear or branched alpha-olefin, preferably butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl- pentene-1, 3-methyl pentene-1, 3,5,5-trimethyl-hexene- l, and the like.
  • the monomers may be present at up to 50 wt%, preferably from 0 wt% to 40 wt%, more preferably from 0.5 wt% to 30 wt%, more preferably from 2 wt% to 30 wt%, more preferably from 5 wt% to 20 wt%.
  • Preferred linear alpha-olefins useful as comonomers for the ethylene copolymers useful in this invention include C3 to Cg alpha-olefins, more preferably 1-butene, 1-hexene, and 1-octene, even more preferably 1-hexene.
  • Preferred branched alpha-olefins include 4- methyl-l-pentene, 3 -methyl- 1-pentene, and 3,5,5-trimethyl-l-hexene, 5-ethyl-l-nonene.
  • Preferred aromatic-group-containing monomers contain up to 30 carbon atoms. Suitable aromatic-group-containing monomers comprise at least one aromatic structure, preferably from one to three, more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety. The aromatic-group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone.
  • the aromatic-group containing monomer may further be substituted with one or more hydrocarbyl groups including, but not limited to, C j to CJQ alkyl groups. Additionally, two adjacent substitutions may be joined to form a ring structure.
  • Preferred aromatic-group- containing monomers contain at least one aromatic structure appended to a polymerizable olefinic moiety. Particularly, preferred aromatic monomers include styrene, alpha- methylstyrene, para-alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene, paramethyl styrene, 4-phenyl- 1-butene, and allyl benzene.
  • Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C 4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms.
  • Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1 ,6-heptadiene, 1,7 -octadiene, 1,8- nonadiene, 1,9-deca
  • Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, or higher ring containing diolefins with or without substituents at various ring positions.
  • the ethylene polymer used herein is a plastomer having a density of 0.91 g/cm 3 or less, as determined by ASTM D1505, and a melt index (MI) between 0.1 and 50 dg/min, as determined by ASTM D1238 (190°C, 2.16 kg).
  • the useful plastomer is a copolymer of ethylene and at least one C3 to C12 a-olefin, preferably C 4 to Cg a-olefins.
  • the amount of C3 to C12 a-olefin present in the plastomer ranges from 2 wt% to 35 wt% in one embodiment, from 5 wt% to 30 wt% in another embodiment, from 15 wt% to 25 wt% in yet another embodiment, and from 20 wt% to 30 wt% in yet another embodiment.
  • Preferred plastomers useful in the invention have a melt index of between 0.1 and 40 dg/min in one embodiment, from 0.2 to 20 dg/min in another embodiment, and from 0.5 to 10 dg/min in yet another embodiment.
  • the average molecular weight of preferred plastomers ranges from 10,000 to 800,000 g/mole in one embodiment, and from 20,000 to 700,000 g/mole in another embodiment.
  • the 1% secant modulus (ASTM D 882) of preferred plastomers ranges from 5 MPa to 100 MPa in one embodiment and from 10 MPa to 50 MPa in another embodiment.
  • preferred plastomers that are useful in compositions of the present invention have a melting temperature (T m ) of from 30°C to 100°C in one embodiment, and from 40°C to 80°C in another embodiment.
  • T m melting temperature
  • the degree of crystallinity of preferred plastomers is between 3% and 30%.
  • preferred plastomers useful in the present invention are synthesized using a single-site catalyst, such as a metallocene catalyst, and comprise copolymers of ethylene and higher a-olefins, such as propylene, 1-butene, 1-hexene and 1-octene, and which contain enough of one or more of these comonomer units to yield a density between 0.86 and 0.91 g/cm 3 in one embodiment.
  • the molecular weight distribution (M w /M n ) of desirable plastomers ranges from 1.5 to 5 in one embodiment and from 2.0 to 4 in another embodiment.
  • Examples of commercially available plastomers are EXACTTM 4150, a copolymer of ethylene and 1-hexene, the 1-hexene derived units making up from 18 wt% to 22 wt% of the plastomer and having a density of 0.895 g/cm 3 and MI of 3.5 dg/min (ExxonMobil Chemical Company, Houston, TX); and EXACTTM 8201, a copolymer of ethylene and 1-octene, the 1- octene derived units making up from 26 wt% to 30 wt% of the plastomer, and having a density of 0.882 g/cm 3 and MI of 1.0 dg/min (ExxonMobil Chemical Company, Houston, TX).
  • the melt index (MI) of preferred ethylene polymers ranges from 0.02 dg/min to 800 dg/min in one embodiment, from 0.05 to 500 dg/min in another embodiment, and from 0.1 to 100 dg/min in another embodiment.
  • the polyethylene has a MI of 20 dg/min or less, 7 dg/min or less, 5 dg/min or less, 2 dg/min or less, or less than 2 dg/min.
  • the polymer has a Mooney viscosity, ML(l+4) @ 125°C (measured according to ASTM D1646) of 100 or less, 75 or less, 60 or less, or 30 or less.
  • the 1% secant modulus of preferred ethylene polymers ranges from 5 MPa to 1000 MPa, from 10 MPa to 800 MPa in another embodiment, and from 5 MPa to 200 MPa in yet another embodiment, wherein a desirable polymer may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit.
  • the crystallinity of the polymer may also be expressed in terms of crystallinity percent.
  • the thermal energy for the highest order of polyethylene is estimated at 290 J/g. That is, 100% crystallinity is equal to 290 J/g.
  • the polymer has a crystallinity (as determined by DSC as described in the Test methods section below) within the range having an upper limit of 80%, 60%, 40%, 30%, or 20%, and a lower limit of 1%, 3%, 5%, 8%, or 10%.
  • the polymer has a crystallinity of 5% to 80%, preferably 10% to 70, more preferably 20% to 60%.
  • the polyethylene may have a crystallinity of at least 30%, preferably at least 40%, alternatively at least 50%, where crystallinity is determined.
  • the ethylene polymer has a single melting point.
  • a sample of ethylene copolymer will show secondary melting peaks adjacent to the principal peak, which is considered together as a single melting point. The highest of these peaks is considered the melting point.
  • the polymer preferably has a melting point (as determined by DSC as described in the Test methods section below) ranging from an upper limit of 150°C, 130°C, or 100°C to a lower limit of 0°C, 30°C, 35°C, 40°C, or 45°C.
  • Preferred ethylene copolymers useful herein are preferably a copolymer comprising at least 50 wt% ethylene and having up to 50 wt%, preferably 1 wt% to 35 wt%, even more preferably 1 wt% to 6 wt%, of a C3 to C20 comonomer (preferably hexene or octene), based upon the weight of the copolymer.
  • the polyethylene copolymers preferably have a composition distribution breadth index (CDBI) of 60% or more, preferably 60% to 80%, preferably 65% to 80%.
  • the ethylene copolymer has a density of 0.910 to 0.950 g/cm 3 (preferably 0.915 to 0.940 g/cm 3 , preferably 0.918 to 0.925 g/cm 3 ) and a CDBI of 60% to 80%, preferably between 65% and 80%.
  • these polymers are metallocene polyethylenes (mPEs). Further useful mPEs include those described in U.S. Patent Application Publication No. 2007/0260016 and U.S. Patent No.
  • 6,476,171 e.g., copolymers of an ethylene and at least one alpha olefin having at least 5 carbon atoms obtainable by a continuous gas phase polymerization using supported catalyst of an activated molecularly discrete catalyst in the substantial absence of an aluminum alkyl based scavenger (e.g., triethylaluminum, trimethylaluminum, tri-isobutyl aluminum, tri-n-hexylaluminum, and the like), which the polymer has a Melt Index of from 0.1 to 15 (ASTM D 1238, condition E); a CDBI of at least 70%; a density of from 0.910 to 0.930 g/cc; a Haze (ASTM D1003) value of less than 20; a Melt Index ratio (121/11, ASTMD 1238) of from 35 to 80; an averaged Modulus (M) (as defined in U.S.
  • M averaged Modulus
  • Patent No. 6,255,426) of from 20,000 to 60,000 psi (13790 to 41369 N/cm 2 ); and a relation between M and the Dart Impact Strength (26 inch, ASTM D 1709) in g/mil (DIS) complying with the formula:
  • Useful mPE homopolymers or copolymers may be produced using mono- or bis- cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure, or gas phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings may be substituted or unsubstituted.
  • Several commercial products produced with such catalyst/activator combinations are commercially available from ExxonMobil Chemical Company in Baytown, Texas under the tradename EXCEEDTM Polyethylene or ENABLETM Polyethylene.
  • the polyethylene compositions of the present invention may also contain other additives.
  • additives include antioxidants; nucleating agents; acid scavengers; stabilizers; anticorrosion agents; plasticizers; blowing agents; cavitating agents; surfactants; adjuvants; block; antiblock; UV absorbers, such as, chain-breaking antioxidants, oils, etc.; quenchers; antistatic agents; slip agents; processing aids; UV stabilizers; neutralizers; lubricants; waxes; color masterbatches; pigments; dyes and fillers; and cure agents, such as, peroxide.
  • the additives may each individually present at 0.01 wt% to 50 wt% in one embodiment, from 0.01 wt% to 10 wt% in another embodiment, and from 0.1 wt% to 6 wt% in another embodiment, based upon the weight of the composition.
  • dyes and other colorants common in the industry may be present from 0.01 wt% to 10 wt% in one embodiment and from 0.1 wt% to 6 wt% in another embodiment, based upon the weight of the composition.
  • Preferred fillers, cavitating agents, and/or nucleating agents include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay, and the like.
  • antioxidants and stabilizers such as, organic phosphites, hindered amines, and phenolic antioxidants, may be present in the polyethylene compositions of the invention from 0.001 wt% to 2 wt%, based upon the weight of the composition, in one embodiment; from 0.01 wt% to 0.8 wt% in another embodiment; and from 0.02 wt% to 0.5 wt% in yet another embodiment.
  • Non-limiting examples of organic phosphites that are suitable are tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) and di(2,4-di-tert- butylphenyl)pentaerithritol diphosphite (ULTRANOX 626).
  • Non-limiting examples of hindered amines include poly[2-N,N'-di(2,2,6,6-tetramethyl-4-piperidinyl)-hexanediamine-4- (l-amino-l, l,3,3-tetramethylbutane)sym-triazine] (CHIMASORB 944) and bis(l,2,2,6,6- pentamethyl-4-piperidyl)sebacate (TINUVIN 770).
  • Non-limiting examples of phenolic antioxidants include pentaerythrityl tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010) and l,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 31 14).
  • Fillers may be present from 0.001 wt% to 50 wt% in one embodiment, from 0.01 wt% to 25 wt%, based upon the weight of the composition, in another embodiment, and from 0.2 wt% to 10 wt% in yet another embodiment.
  • Desirable fillers include, but are not limited to, titanium dioxide; silicon carbide; silica (and other oxides of silica, precipitated or not); antimony oxide; lead carbonate; zinc white; lithopone; zircon; corundum; spinel; apatite;
  • Barytes powder barium sulfate; magnesiter; carbon black; dolomite; calcium carbonate; talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr, or Fe and CO3, and/or
  • fillers may particularly include any other fillers and porous fillers and supports known in the art, and may have the modifier of the invention pre-contacted or pre- absorbed into the filler prior to addition to the ethylene polymer in one embodiment.
  • Metal salts of fatty acids may also be present in the polyethylene compositions of the present invention. Such salts may be present from 0.001 wt% to 1 wt% of the composition in one embodiment and from 0.01 wt% to 0.8 wt% in another embodiment.
  • fatty acids include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid, or any monocarboxylic aliphatic saturated or unsaturated acid having a chain length of 7 to 22 carbon atoms.
  • Suitable metals include Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, and so forth.
  • metal salts of fatty acids are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.
  • slip additives may be present in the compositions of this invention.
  • the slip additives are present at 0.001 wt% to 1 wt% (10 ppm to 10,000 ppm), more preferably 0.01 wt% to 0.5 wt% (100 ppm to 5000 ppm), more preferably 0.1 wt% to 0.3 wt% (1000 ppm to 3000 ppm), based upon the weight of the composition.
  • Desirable slip additives include, but are not limited to, saturated fatty acid amides (such as palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, palmityl pamitamide, and stearyl arachidamide); saturated ethylene-bis-amides (such as stearamido- ethyl-stearamide, stearamido-ethyl-palmitamide, and palmitamido-ethyl-stearamide); unsaturated fatty acid amides (such as oleamide, erucamide, and linoleamide); unsaturated ethylene-bis-amides (such as ethylene-bis-stearamide, ethylene-bis-oleamide, stearyl- erucamide, erucamido-ethyl-erucamide, oleamido-ethyl-oleamide, erucamido-ethyl-oleamide, oleamido-ethyl
  • Preferred slip additives are unsaturated fatty acid amides, which are commercially available from Crompton (KekamideTM grades), Croda Universal (CrodamideTM grades), and Akzo Nobel Amides Co. Ltd. (ARMOSLIPTM grades).
  • Particularly, preferred slip agents include unsaturated fatty acid amides having the chemical structure:
  • Preferred versions include: 1) Erucamide, where x is 11, also referred to as cis-13-docosenoamide (commercially available as ARMOSLIP E); 2) Oleylamide, where x is 8; and 3) Oleamide, where x is 7, also referred to as N-9-octadecenyl-hexadecanamide.
  • stearamide is also useful in this invention.
  • Other preferred slip additives include those described in WO 2004/005601A1.
  • the polyethylene compositions produced by this invention may be blended with one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s).
  • thermoplastic polymer(s) is meant a polymer that can be melted by heat and then cooled without appreciable change in solid-state properties before and after heating.
  • Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene- styrene resins, polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more of the above.
  • Preferred polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40 olefins, preferably polymers comprising ethylene copolymerized with one or more C3 to C40 olefins, preferably a C3 to C20 alpha olefin, more preferably C3 to C ⁇ Q alpha-olefins.
  • a particularly preferred example is polybutene.
  • the most preferred polyolefin is polypropylene.
  • polystyrene resins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C3 to C40 olefin, preferably a C3 to C20 alpha olefin, more preferably propylene, butene, hexene, and/or octene.
  • elastomers all natural and synthetic rubbers, including those defined in ASTM D1566.
  • the blend comprising the modifier may further be combined with one or more polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), and polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.
  • polymers polymerizable by a high-pressure free radical process polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), and polymers
  • Tackifiers may be blended with the ethylene compositions of this invention.
  • useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.
  • the tackifier is hydrogenated. In other embodiments the tackifier is non-polar. (Non-polar is meant that the tackifier is substantially free of monomers having polar groups. Preferably, the polar groups are not present; however, if they are, preferably they are present at not more than 5 wt%, preferably at not more than 2 wt%, and even more preferably at not more than 0.5 wt%, based upon the weight of the tackifier.) In some embodiments, the tackifier has a softening point (Ring and Ball, as measured by ASTM E-28) of 80°C to 140°C, preferably 100°C to 130°C.
  • a softening point Ring and Ball, as measured by ASTM E-28
  • the tackifier if present, is typically present at about 1 wt% to about 50 wt%, based upon the weight of the blend, more preferably 10 wt% to 40 wt%, and even more preferably 20 wt% to 40 wt%. Preferably, however, tackifier is not present, or if present, is present at less than 10 wt%, preferably less than 5 wt%, and more preferably at less than 1 wt%.
  • compositions and blends described herein may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin- screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process.
  • additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired.
  • additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOXTM 1010 or
  • IRGANOXTM 1076 available from Ciba-Geigy
  • phosphites e.g., IRGAFOSTM 168 available from Ciba-Geigy
  • anti-cling additives such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins
  • UV stabilizers heat stabilizers
  • antiblocking agents release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.
  • the polymers suitable for use in the present invention can be in any physical form when used to blend with the modifier of the invention.
  • reactor granules defined as the granules of polymer that are isolated from the polymerization reactor prior to any processing procedures, are used to blend with the modifier of the invention.
  • the reactor granules typically have an average diameter of from 50 ⁇ to 10 mm in one embodiment and from 10 ⁇ to 5 mm in another embodiment.
  • the polymer is in the form of pellets, such as, for example, having an average diameter of from 1 mm to 10 mm that are formed from melt extrusion of the reactor granules.
  • the components of the present invention can be blended by any suitable means, and are typically blended to yield an intimately mixed composition which may be a homogeneous, single phase mixture.
  • they may be blended in a static mixer, batch mixer, extruder, or a combination thereof, that is sufficient to achieve an adequate dispersion of modifier in the polymer.
  • the mixing step may involve first dry blending using, for example, a tumble blender, where the polymer and modifier are brought into contact first, without intimate mixing, which may then be followed by melt blending in an extruder.
  • Another method of blending the components is to melt blend the polymer pellets with the modifier directly in an extruder or batch mixer. It may also involve a "master batch” approach, where the final modifier concentration is achieved by combining neat polymer with an appropriate amount of modified polymer that had been previously prepared at a higher modifier concentration.
  • the mixing step may take place as part of a processing method used to fabricate articles, such as in the extruder on an injection molding machine or blown-film line or fiber line.
  • the ethylene polymer and modifier are "melt blended" in an apparatus such as an extruder (single or twin screw) or batch mixer.
  • the ethylene polymer may also be "dry blended” with the modifier using a tumbler, double-cone blender, ribbon blender, or other suitable blender.
  • the ethylene polymer and modifier are blended by a combination of approaches, for example, a tumbler followed by an extruder.
  • a preferred method of blending is to include the final stage of blending as part of an article fabrication step, such as in the extruder used to melt and convey the composition for a molding step like injection molding or blow molding. This could include direct injection of the modifier into the extruder, either before or after the polyethylene is fully melted.
  • Extrusion technology for polyethylene is described in more detail in, for example, PLASTICS EXTRUSION TECHNOLOGY 26-37 (Friedhelm Hensen, ed. Hanser Publishers 1988).
  • the polyethylene composition may be blended in solution by any suitable means, by using a solvent that dissolves both components to a significant extent.
  • the blending may occur at any temperature or pressure where the modifier and the ethylene polymer remain in solution.
  • Preferred conditions include blending at high temperatures, such as 10°C or more, preferably 20°C or more over the melting point of the ethylene polymer.
  • Such solution blending would be particularly useful in processes where the ethylene polymer is made by solution process and the modifier is added directly to the finishing train, rather than added to the dry polymer in another blending step altogether.
  • Such solution blending would also be particularly useful in processes where the ethylene polymer is made in a bulk or high pressure process where both the polymer and the modifier were soluble in the monomer. As with the solution process the modifier is added directly to the finishing train, rather than added to the dry polymer in another blending step altogether.
  • any means of combining the polyethylene and modifier to achieve the desired composition serve equally well as fully formulated pre- blended pellets, since the forming process includes a re-melting and mixing of the raw material; example combinations include simple blends of neat polymer pellets and modifier, of neat polymer granules and modifier, of neat polymer pellets and pre-blended pellets, and of neat polymer granules and pre-blended pellets.
  • pre-blended pellets means pellets of a polyethylene composition comprising ethylene polymer and modifier at some concentration.
  • the enhanced properties of the polyethylene compositions described herein are useful in a wide variety of applications, including transparent articles, such as cook and storage ware, and in other articles, such as furniture, automotive components, toys, sportswear, medical devices, sterilizable medical devices and sterilization containers, nonwoven fibers and fabrics and articles therefrom, such as drapes, gowns, filters, hygiene products, diapers, and films, oriented films, sheets, tubes, pipes and other items where softness, high impact strength, and impact strength below freezing is important.
  • compositions of the invention include films, sheets, fibers, woven and nonwoven fabrics, automotive components, furniture, sporting equipment, food storage containers, transparent and semi- transparent articles, toys, tubing and pipes, sheets, packaging, bags, sacks, coatings, caps, closures, crates, pallets, cups, non-food containers, pails, insulation, and medical devices.
  • Further examples include automotive components, wire and cable jacketing, pipes, agricultural films, geomembranes, toys, sporting equipment, medical devices, casting and blowing of packaging films, extrusion of tubing, pipes and profiles, sporting equipment, outdoor furniture (e.g., garden furniture) and playground equipment, boat and water craft components, and other such articles.
  • compositions are suitable for automotive components such as bumpers, grills, trim parts, dashboards and instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, trucks, boats, and other vehicles.
  • automotive components such as bumpers, grills, trim parts, dashboards and instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, trucks, boats, and other vehicles.
  • Other useful articles and goods may be formed economically by the practice of our invention including: crates, containers, packaging, labware, such as roller bottles for culture growth and media bottles, office floor mats, instrumentation sample holders and sample windows; liquid storage containers such as bags, pouches, and bottles for storage and IV infusion of blood or solutions; packaging material including those for any medical device or drugs including unit-dose or other blister or bubble pack, as well as for wrapping or containing food preserved by irradiation.
  • Other useful items include medical tubing and valves for any medical device including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices or food which is irradiated including trays, as well as stored liquid, particularly water, milk, or juice, containers including unit servings and bulk storage containers, as well as transfer means such as tubing, pipes, and such.
  • Fabrication of these articles may be accomplished by injection molding, extrusion, thermoforming, blow molding, rotational molding (rotomolding), fiber spinning, spin bonding or melt blown bonding such as for non-woven fabrics, film blowing, stretching for oriented films, casting such as for films (including use of chill rolls), profile deformation, coating (film, wire, and cable), compression molding, calendering, foaming, laminating, transfer molding, cast molding, pultrusion, protrusion, draw reduction, and other common processing methods, or combinations thereof, such as is known in the art and described in, for example, PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986).
  • Use of at least thermoforming or film applications allows for the possibility of and derivation of benefits from uniaxial or biaxial orientation. Sufficient mixing should take place to assure that an intimately mixed, preferably uniform, blend will be produced prior to conversion into a finished product.
  • the polymers of this invention or blends thereof can be used as adhesives, either alone or combined with tackifiers.
  • Preferred tackifiers are described above.
  • the tackifier is typically present at about 1 wt% to about 50 wt%, based upon the weight of the blend, more preferably 10 wt% to 40 wt%, even more preferably 20 wt% to 40 wt%.
  • Other additives, as described above, may be added also.
  • the adhesives of this invention can be used in any adhesive application including, but not limited to, disposables, packaging, laminates, pressure sensitive adhesives, tapes labels, wood binding, paper binding, non-wovens, road marking, reflective coatings, and the like.
  • the adhesives of this invention can be used for disposable diaper and napkin chassis construction, elastic attachment in disposable goods converting, packaging, labeling, bookbinding, woodworking, and other assembly applications.
  • preferred applications include: baby diaper leg elastic, diaper frontal tape, diaper standing leg cuff, diaper chassis construction, diaper core stabilization, diaper liquid transfer layer, diaper outer cover lamination, diaper elastic cuff lamination, feminine napkin core stabilization, feminine napkin adhesive strip, industrial filtration bonding, industrial filter material lamination, filter mask lamination, surgical gown lamination, surgical drape lamination, and perishable products packaging.
  • compositions described above and the blends thereof may be formed into monolayer or multilayer films.
  • These films may be formed by any of the conventional techniques known in the art including extrusion, co-extrusion, extrusion coating, lamination, blowing, and casting.
  • the film may be obtained by the flat film or tubular process which may be followed by orientation in a uniaxial direction or in two mutually perpendicular directions in the plane of the film.
  • One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents. This orientation may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, preferably 7 to 9.
  • MD Machine Direction
  • TD Transverse Direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the other layer(s) may be any layer typically included in multilayer film structures.
  • the other layer or layers may be:
  • Polyolefins include homopolymers or copolymers of C2 to C40 olefins, preferably C2 to C20 olefins, preferably a copolymer of an alpha-olefin and another olefin or alpha-olefin (ethylene is defined to be an alpha-olefin for purposes of this invention).
  • ethylene is defined to be an alpha-olefin for purposes of this invention.
  • thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, elastomers such as ethylene propylene rubber, ethylene propylene diene monomer rubber, neoprene, and blends of thermoplastic polymers and elastomers, such as, for example, thermoplastic elastomers and rubber toughened plastics.
  • thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random cop
  • Polar polymers include homopolymers and copolymers of esters, amides, acetates, anhydrides, copolymers of a C2 to C20 olefin, such as ethylene, and/or propylene, and/or butene with one or more polar monomers such as acetates, anhydrides, esters, alcohol, and/or acrylics.
  • Preferred examples include polyesters, polyamides, ethylene vinyl acetate copolymers, and polyvinyl chloride.
  • Cationic polymers include polymers or copolymers of geminally disubstituted olefins, alpha-heteroatom olefins, and/or styrenic monomers.
  • Preferred geminally disubstituted olefins include isobutylene, isopentene, isoheptene, isohexane, isooctene, isodecene, and isododecene.
  • Preferred alpha-heteroatom olefins include vinyl ether and vinyl carbazole
  • preferred styrenic monomers include styrene, alkyl styrene, para-alkyl styrene, alpha-methyl styrene, chloro-styrene, and bromo-para- methyl styrene.
  • Preferred examples of cationic polymers include butyl rubber, isobutylene copolymerized with para methyl styrene, polystyrene, and poly-alpha-methyl styrene. 4. Miscellaneous.
  • Other preferred layers can be paper, wood, cardboard, metal, metal foils (such as aluminum foil and tin foil), metallized surfaces, glass (including silicon oxide (SiO x ) coatings applied by evaporating silicon oxide onto a film surface), fabric, spunbonded fibers, and non-wovens (particularly, polypropylene spun bonded fibers or non-wovens), and substrates coated with inks, dyes, pigments, and the like.
  • metal such as aluminum foil and tin foil
  • metallized surfaces glass (including silicon oxide (SiO x ) coatings applied by evaporating silicon oxide onto a film surface), fabric, spunbonded fibers, and non-wovens (particularly, polypropylene spun bonded fibers or non-wovens), and substrates coated with inks, dyes, pigments, and the like.
  • the films may vary in thickness depending on the intended application; however, films of a thickness from 1 ⁇ to 250 ⁇ are usually suitable. Films intended for packaging are usually from 10 to 60 micron thick.
  • the thickness of the sealing layer is typically 0.2 ⁇ to 50 ⁇ .
  • Additives such as block, antiblock, antioxidants, pigments, fillers, processing aids, UV stabilizers, neutralizers, lubricants, surfactants, and/or nucleating agents may also be present in one or more than one layer in the films.
  • Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium sterate, carbon black, low molecular weight resins, and glass beads, preferably, these additives are present at from 0.1 ppm to 1000 ppm.
  • one more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, or microwave irradiation.
  • one or both of the surface layers is modified by corona treatment.
  • the films described herein may also comprise from 5 wt% to 60 wt%, based upon the weight of the polymer and the resin, of a hydrocarbon resin.
  • the resin may be combined with the polymer of the seal layer(s) or may be combined with the polymer in the core layer(s).
  • the resin preferably has a softening point above 100°C, even more preferably from 130°C to 180°C.
  • Preferred hydrocarbon resins include those described above.
  • the films comprising a hydrocarbon resin may be oriented in uniaxial or biaxial directions to the same or different degrees. For more information on blends of tackifiers and modifiers useful herein, see USSN 60/617,594, filed October 8, 2004.
  • the films described above may be used as stretch and/or cling films.
  • Stretch/cling films are used in various bundling, packaging, and palletizing operations.
  • tackifying additives include polybutenes, terpene resins, alkali metal stearates and hydrogenated rosins, and rosin esters.
  • the cling properties of a film can also be modified by the well-known physical process referred to as corona discharge. Some polymers (such as ethylene methyl acrylate copolymers) do not need cling additives and can be used as cling layers without tackifiers.
  • Stretch/clings films may comprise a slip layer comprising any suitable polyolefin or combination of polyolefins such as polyethylene, polypropylene, copolymers of ethylene and propylene, and polymers obtained from ethylene and/or propylene copolymerized with minor amounts of other olefins, particularly C 4 to (3 ⁇ 4 olefins. Particularly, preferred is linear low density polyethylene (LLDPE).
  • the slip layer may include one or more anticling (slip and/or antiblock) additives which may be added during the production of the polyolefin or subsequently blended in to improve the slip properties of this layer.
  • additives are well- known in the art and include, for example, silicas, silicates, diatomaceous earths, talcs, and various lubricants. These additives are preferably utilized in amounts ranging from about 100 ppm to about 20,000 ppm, more preferably between about 500 ppm to about 10,000 ppm, by weight based upon the weight of the slip layer.
  • the slip layer may, if desired, also include one or more other additives as described above.
  • films comprising blends described herein have a gauge variation that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a dart impact strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • films comprising blends described herein have a gauge variation that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a MD Tear strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • films comprising blends described herein have a haze that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a dart impact strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • films comprising blends described herein have a haze that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a MD Tear strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • films comprising blends described herein have a haze of 10% or less.
  • films comprising blends described herein have a haze that is at least 10% less than the haze measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have a dart impact strength that is greater than or within 30% less than the dart impact strength measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have an MD Tear strength that is greater than or within 30% less than the MD Tear strength measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions, and the film has a Dart Drop, in g/mil, that is within 30% of the Dart Drop measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions, and the film has an MD Tear strength that is greater than or within 30% less than the MD Tear strength measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have a strain hardening ratio that is at least 10% greater than the strain hardening ratio measured on a composition, absent the dendritic hydrocarbon polymer modifier, and the film has a Dart Drop, in g/mil, that is within 30% of the Dart Drop measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films comprising blends described herein have a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions, and the film has a haze that is at least 10% less than haze measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • films prepared from the compositions described herein have improved bubble stability compared to the ethylene copolymers of the compositions alone as determined by reduced gauge variation, e.g., a gauge variation of 10% or less, preferably 8% or less, preferably 5% or less.
  • films prepared from the compositions described herein have excellent optical properties, such as a haze (ASTM D1003) of 20 or less, preferably 15 or less, preferably 10 or less.
  • films, preferably blown films, prepared from the blends described herein have one or more of the following properties:
  • TD Tensile Strength
  • Elmendorf Tear of at least 300g/mil, preferably at least 325 g/mil; and/or
  • Elmendorf Tear of at least 400 g/mil, preferably at least 410 g/mil; and/or
  • the films described herein, preferably the blown films have at least two of the above properties in any combination whatsoever, preferably at least three of the above properties in any combination whatsoever, preferably at least four of the above properties in any combination whatsoever, preferably at least five of the above properties in any combination whatsoever, preferably at least six of the above properties in any combination whatsoever, preferably at least seven of the above properties in any combination whatsoever, preferably at least eight of the above properties in any combination whatsoever, preferably at least nine of the above properties in any combination whatsoever, preferably at least ten of the above properties in any combination whatsoever, preferably at least eleven of the above properties in any combination whatsoever, preferably at least twelve of the above properties in any combination whatsoever, preferably at least thirteen of the above properties in any combination whatsoever, preferably at least fourteen of the above properties in any combination whatsoever, preferably at least fifteen of the above properties in any combination whatsoever, preferably at least sixteen of the above properties in any combination whatsoever, preferably at least seventeen of the above properties in any combination whatsoever, preferably at least eighteen of the above properties in
  • the blown film has a total haze of 10% or less, a 1% (MD) Secant Modulus of 25,000 psi or more, an MD Tear of 300 g or more, and a Dart Drop of 200 or more g/mil, and TD 1% Secant Modulus of 25,000 psi or more.
  • the blown film has a total haze of 10% or less, a Gauge COV of less than 12%, a 1% (MD) Secant Modulus of 25,000 psi or more, an MD Tear of 300 g or more, and a Dart Drop of 200 or more g/mil.
  • the polyethylene composition described above may also be used to prepare molded products in any molding process including, but not limited to, injection molding, gas-assisted injection molding, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrusion, and profile extrusion.
  • injection molding gas-assisted injection molding
  • extrusion blow molding injection blow molding
  • injection stretch blow molding injection stretch blow molding
  • compression molding rotational molding
  • foam molding thermoforming, sheet extrusion, and profile extrusion.
  • compositions described herein may be shaped into desirable end use articles by any suitable means known in the art.
  • Thermoforming, vacuum forming, blow molding, rotational molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, injection molding, spray techniques, profile co- extrusion, or combinations thereof are typically used methods.
  • Thermoforming is a process of forming at least one pliable plastic sheet into a desired shape.
  • An embodiment of a thermoforming sequence is described; however, this should not be construed as limiting the thermoforming methods useful with the compositions of this invention.
  • First, an extrudate film of the composition of this invention (and any other layers or materials) is placed on a shuttle rack to hold it during heating.
  • the shuttle rack indexes into the oven which pre-heats the film before forming. Once the film is heated, the shuttle rack indexes back to the forming tool.
  • the film is then vacuumed onto the forming tool to hold it in place and the forming tool is closed.
  • the forming tool can be either "male” or "female” type tools.
  • thermoforming is accomplished by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and variations of these, once the sheet of material reaches thermoforming temperatures, typically of from 140°C to 185°C or higher.
  • a pre-stretched bubble step is used, especially on large parts, to improve material distribution.
  • an articulating rack lifts the heated laminate towards a male forming tool, assisted by the application of a vacuum from orifices in the male forming tool. Once the laminate is firmly formed about the male forming tool, the thermoformed shaped laminate is then cooled, typically by blowers. Plug-assisted forming is generally used for small, deep drawn parts.
  • Plug material, design, and timing can be critical to optimization of the process. Plugs made from insulating foam avoid premature quenching of the plastic.
  • the plug shape is usually similar to the mold cavity, but smaller and without part detail. A round plug bottom will usually promote even material distribution and uniform side-wall thickness. For a semicrystalline polymer, fast plug speeds generally provide the best material distribution in the part.
  • the shaped laminate is then cooled in the mold. Sufficient cooling to maintain a mold temperature of 30°C to 65°C is desirable. The part is below 90°C to 100°C before ejection in one embodiment. The shaped laminate is then trimmed of excess laminate material.
  • Blow molding is another suitable forming means, which includes injection blow molding, multi-layer blow molding, extrusion blow molding, and stretch blow molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers.
  • Blow molding is described in more detail in, for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).
  • profile co-extrusion can be used.
  • the profile co-extrusion process parameters are as above for the blow molding process, except the die temperatures (dual zone top and bottom) range from 150°C to 235°C, the feed blocks are from 90°C to 250°C, and the water cooling tank temperatures are from 10°C to 40°C.
  • the shaped laminate is placed into the injection molding tool.
  • the mold is closed and the substrate material is injected into the mold.
  • the substrate material has a melt temperature between 180°C and 300°C in one embodiment, from 200°C and 250°C in another embodiment, and is injected into the mold at an injection speed of between 2 and 10 seconds.
  • the material is packed or held at a predetermined time and pressure to make the part dimensionally and aesthetically correct. Typical time periods are from 5 to 25 seconds and pressures from 1,000 kPa to 15,000 kPa.
  • the mold is cooled between 10°C and 70°C to cool the substrate. The temperature will depend on the desired gloss and appearance desired. Typical cooling time is from 10 to 30 seconds, depending on part on the thickness.
  • the mold is opened and the shaped composite article ejected.
  • molded articles may be fabricated by injecting molten polymer blend into a mold that shapes and solidifies the molten polymer into desirable geometry and thickness of molded articles.
  • a sheet may be made either by extruding a substantially flat profile from a die, onto a chill roll, or alternatively by calendering. Sheets will generally be considered to have a thickness of from 10 mils to 100 mils (254 ⁇ to 2540 ⁇ ), although sheets may be substantially thicker.
  • Tubing or pipe may be obtained by profile extrusion for uses in medical, potable water, land drainage applications, or the like. The profile extrusion process involves the extrusion of molten polymer through a die.
  • the extruded tubing or pipe is then solidified by chill water or cooling air into a continuous extruded articles.
  • the tubing will generally be in the range of from 0.31 cm to 2.54 cm in outside diameter and have a wall thickness of in the range of from 254 ⁇ to 0.5 cm.
  • the pipe will generally be in the range of from 2.54 cm to 254 cm in outside diameter and have a wall thickness of in the range of from 0.5 cm to 15 cm.
  • Sheets made from the products of an embodiment of a version of the present invention may be used to form containers. Such containers may be formed by thermoforming, solid phase pressure forming, stamping, and other shaping techniques. Sheets may also be formed to cover floors or walls or other surfaces.
  • the oven temperature is between 160°C and 195°C, the time in the oven between 10 and 20 seconds, and the die temperature, typically a male die, between 10°C and 71°C.
  • the final thickness of the cooled (room temperature), shaped laminate is from 10 ⁇ to 6000 ⁇ in one embodiment, from 200 ⁇ to 6000 ⁇ in another embodiment, from 250 ⁇ to 3000 ⁇ in yet another embodiment, and from 500 ⁇ to 1550 ⁇ in yet another embodiment, a desirable range being any combination of any upper thickness limit with any lower thickness limit.
  • the melt temperature of the substrate material is between 190°C and 255°C in one embodiment and between 210°C and 250°C in another embodiment; the fill time from 2 to 10 seconds in one embodiment and from 2 to 8 seconds in another embodiment; and a tool temperature of from 25°C to 65°C in one embodiment and from 27°C and 60°C in another embodiment.
  • the substrate material is at a temperature that is hot enough to melt any tie- layer material or backing layer to achieve adhesion between the layers.
  • compositions of this invention may be secured to a substrate material using a blow molding operation.
  • Blow molding is particularly useful in such applications as for making closed articles such as fuel tanks and other fluid containers, playground equipment, outdoor furniture, and small enclosed structures.
  • the steps outlined above may be varied, depending upon the desired result.
  • the extruded sheet of the compositions of this invention may be directly thermoformed or blow molded without cooling, thus skipping a cooling step.
  • Other parameters may be varied as well in order to achieve a finished composite article having desirable features.
  • this invention relates to:
  • a polyethylene blend comprising one or more ethylene polymers and one or more dendritic hydrocarbon polymer modifiers, wherein the modifier has: 1) a g' vjs value less than
  • composition of paragraph 1 wherein the modifier has 5 wt% or less of xylene insoluble material.
  • composition of paragraph 1 or 2 wherein the modifier has a weight average molecular weight between the branch points of 1,000 g/mol or more.
  • a polyethylene film comprising the blend of any of paragraphs 1 to 8, said film having a gauge variation that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a dart impact strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • a polyethylene film comprising the blend of any of paragraphs 1 to 9, said film having a gauge variation that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a MD Tear strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • a polyethylene film comprising the blend of any of paragraphs 1 to 10, said film having a haze that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a dart impact strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • a polyethylene film comprising the blend of any of paragraphs 1 to 1 1, said film having a haze that is at least 10% lower than that of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions and a MD Tear strength that is within 20% of a film of the same thickness and of the same composition, absent the modifier, prepared under the same conditions.
  • a film comprising the composition of any of paragraphs 1 to 12, said film having a haze of 10% or less.
  • a film comprising the composition of any of paragraphs 1 to 13, wherein the film has a haze that is at least 10% less than the haze measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the composition of any of paragraphs 1 to 14, wherein the film has a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the composition of any of paragraphs 1 to 15, wherein the film has a dart impact strength that is greater than or within 30% less than the dart impact strength measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the composition of any of paragraphs 1 to 16, wherein the film has an MD Tear strength that is greater than or within 30% less than the MD Tear strength measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the blend of any of paragraphs 1 to 17, wherein the film has a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions, and the film has a Dart Drop, in g/mil, that within 30% of the Dart Drop measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the blend of any of paragraphs 1 to 18, wherein the film has a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions, and the film has an MD Tear strength that is greater than or within 30% less than the MD Tear strength measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the blend of any of paragraphs 1 to 19, wherein the blend composition has a strain hardening ratio that is at least 10% greater than the strain hardening ratio measured on a composition, absent the dendritic hydrocarbon polymer modifier, and the film has a Dart Drop, in g/mil, that within 30% of the Dart Drop measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • a film comprising the blend of any of paragraphs 1 to 20, wherein the film has a gauge variation that is at least 10% less than the gauge variation measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions, and the film has a haze that is at least 10% less than haze measured on a film of the same thickness and of the same composition, absent the dendritic hydrocarbon polymer modifier, prepared under the same conditions.
  • composition of any of paragraphs 1 to 21 comprising more than 25 wt% (based on the weight of the composition) of one or more ethylene polymers having a g' vjs of 0.95 or more and an M w of 20,000 g/mol or more and at least 0.1 wt% of a dendritic hydrocarbon polymer modifier where the modifier has a g' vjs of less than 0.75, wherein the ethylene polymer has a g' vjs of at least 0.25 units higher than the g' vjs of the branched modifier.
  • MI Melt Index
  • the units for MI are g/10 min or dg/min.
  • High Load Melt Index (HLMI, also referred to as 121) is the melt flow rate measured according to ASTM D-1238 at 190°C, under a load of 21.6 kg.
  • the units for HLMI are g/10 min or dg/min.
  • Melt Index Ratio is the ratio of the high load melt index to the melt index
  • Density is measured by density-gradient column, as described in ASTM D1505, on a compression-molded specimen that has been slowly cooled to room temperature (i.e., over a period of 10 minutes or more) and allowed to age for a sufficient time that the density is constant within +/- 0.001 g/cm 3 .
  • the units for density are g/cm 3 .
  • Gauge reported in mils, was measured using a Measuretech Series 200 instrument. The instrument measures film thickness using a capacitance gauge. For each film sample, ten film thickness data points were measured per inch of film as the film was passed through the gauge in a transverse direction. From these measurements, an average gauge measurement was determined and reported. Coefficient of variation (Gauge COV) is used to measure the variation of film thickness in the transverse direction. The Gauge COV is defined as a ratio of the standard deviation to the mean of film thickness.
  • Elmendorf Tear reported in grams (g) or grams per mil (g/mil), was measured as specified by ASTM D- 1922.
  • Haze reported as a percentage (%), was measured as specified by ASTM D-1003. Internal Haze, reported as a percentage (%), is the haze excluding any film surface contribution.
  • the film surfaces are coated with ASTM approved inert liquids to eliminate any haze contribution from the film surface topology.
  • the internal haze measurement procedure is per ASTM D 1003. Unless otherwise indicated the haze value reported is total haze.
  • Gloss a dimensionless number, was measured as specified by ASTM D-2457 at 45 degrees.
  • DIS Dart Drop Impact or Dart Drop Impact Strength
  • Melt strength is defined as the force required to draw a molten polymer extrudate at a rate of 12mm/s 2 and at an extrusion temperature of 190°C until breakage of the extrudate whereby the force is applied by take up rollers.
  • the polymer is extruded at a velocity of 0.33 mm/s through an annular die of 2 mm diameter and 30 mm length.
  • Melt strength values reported herein are determined using a Gottfert Rheotens tester and are reported in centi- Newtons (cN). Additional experimental parameters for determining the melt strength are listed in Table 1. For the measurements of melt strength, the resins were stabilized with 500 ppm of Irganox 1076 and 1500 ppm of Irgafos 168.
  • the rheometer was thermally stable at 190°C for at least 30 minutes before inserting compression-molded sample of resin onto the parallel plates.
  • frequency sweeps in the range from 0.01 to 385 rad/s were carried out at 190°C under constant strain. Depending on the molecular weight and temperature, strains of 10% and 15% were used and linearity of the response was verified.
  • a nitrogen stream was circulated through the sample oven to minimize chain extension or cross-linking during the experiments.
  • the shear thinning slope was measured using plots of the logarithm (base ten) of the dynamic viscosity versus logarithm (base ten) of the frequency.
  • the slope is the difference in the log(dynamic viscosity) at a frequency of 100 s _1 and the log(dynamic viscosity) at a frequency of 0.01 s _1 divided by 4.
  • the three parameters in this model are: r)o, the zero-shear viscosity; ⁇ , the average relaxation time; and n, the power-law exponent.
  • the zero-shear viscosity is the value at a plateau in the Newtonian region of the flow curve at a low frequency, where the dynamic viscosity is independent of frequency.
  • the average relaxation time corresponds to the inverse of the frequency at which shear-thinning starts.
  • the power-law exponent describes the extent of shear-thinning, in that the magnitude of the slope of the flow curve at high frequencies approaches ⁇ -n on a log(r)*)-log(co) plot.
  • n 1 and the dynamic complex viscosity is independent of frequency.
  • n 1, so that enhanced shear-thinning behavior is indicated by a decrease in n (increase in ⁇ -n).
  • the transient uniaxial extensional viscosity was measured using a SER-2-A Testing Platform available from Xpansion Instruments LLC, Tallmadge, OH, USA.
  • the SER Testing Platform was used on a Rheometrics ARES-LS (RSA3) strain-controlled rotational rheometer available from TA Instruments Inc., New Castle, DE, USA.
  • the SER Testing Platform is described in U.S. Patent Nos. 6,578,413 and 6,691,569, which are incorporated herein for reference.
  • a general description of transient uniaxial extensional viscosity measurements is provided, for example, in "Strain hardening of various polyolefins in uniaxial elongational flow," The Society of Rheology, Inc., J. Rheol.
  • a strain hardening ratio (SHR) is used to characterize the upswing in extensional viscosity and is defined as the ratio of the maximum transient extensional viscosity over three times the value of the transient zero- shear-rate viscosity at the same strain. Strain hardening is present in the material when the ratio is greater than 1.
  • Comonomer content (such as for butene, hexene, and octene) was determined via FTIR measurements according to ASTM D3900 (calibrated versus 13 C NMR). A thin homogeneous film of polymer, pressed at a temperature of about 150°C, was mounted on a Perkin Elmer Spectrum 2000 infrared spectrophotometer. The weight percent of copolymer is determined via measurement of the methyl deformation band at ⁇ 1375 cm-1. The peak height of this band is normalized by the combination and overtone band at ⁇ 4321 cm-1, which corrects for path length differences.
  • Peak melting point, Tm also referred to as melting point
  • peak crystallization temperature, Tc also referred to as crystallization temperature
  • glass transition temperature (Tg) glass transition temperature (Tg)
  • heat of fusion (AHf or Hf) heat of fusion
  • percent crystallinity were determined using the following DSC procedure according to ASTM D3418-03.
  • Differential scanning calorimetric (DSC) data were obtained using a TA Instruments model Q200 machine. Samples weighing approximately 5-10 mg were sealed in an aluminum hermetic sample pan. The DSC data were recorded by first gradually heating the sample to 200°C at a rate of 10°C/minute.
  • the sample was kept at 200°C for 2 minutes and then cooled to -90°C at a rate of 10°C/minute, followed by an isothermal for 2 minutes and heating to 200°C at 10°C/minute. Both the first and second cycle thermal events were recorded. Areas under the endothermic peaks were measured and used to determine the heat of fusion and the percent of crystallinity. The percent crystallinity is calculated using the formula, [area under the melting peak
  • polymer molecular weight (weight-average molecular weight, Mw, number-average molecular weight, Mn, and Z-averaged molecular weight, Mz) and molecular weight distribution (M w /M n ) are determined using Size-Exclusion Chromatography.
  • Equipment consists of a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), with a differential refractive index detector (DRI), an online light scattering detector, and a viscometer. Three Polymer Laboratories PLgel 10mm Mixed-B columns are used. The nominal flow rate is 0.5 cm 3 /min and the nominal injection volume is 300 ⁇ ⁇ .
  • Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ glass pre-filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
  • TCB reagent grade 1,2,4 trichlorobenzene
  • Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for about 2 hours. All quantities are measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 135°C.
  • the injection concentration can range from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and the injector Prior to running each sample, the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI allowed to stabilize for 8 to 9 hours before injecting the first sample. The LS laser is turned on 1 to 1.5 hours before running samples.
  • the concentration, c, at each point in the chromatogram is calculated from the DRI signal after subtracting the prevailing baseline, using the following equation:
  • K DR[ is a constant determined by calibrating the DRI
  • (dn/dc) is the same as described below for the LS analysis.
  • the processes of subtracting the prevailing baseline (i.e., background signal) and setting integration limits that define the starting and ending points of the chromatogram are well known to those familiar with SEC analysis. Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm 3 , molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.
  • the light scattering detector is a Wyatt Technology High Temperature mini-DAW .
  • the polymer molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
  • AR(9) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • A2 is the second virial coefficient
  • ⁇ ( ⁇ ) is the form factor for a monodisperse random coil (described in the above reference), and K 0 is the optical constant for the system:
  • a 2 0.0015
  • a high temperature Viscotek Corporation viscometer is used, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity for the solution flowing through the viscometer at each point in the chromatogram, (r ⁇ s , is calculated from the ratio of their outputs.
  • the intrinsic viscosity at each point in the chromatogram, [r ⁇ , is calculated by solving the following equation (for the positive root) at each point i:
  • the branching index (g' v i s ) is calculated using the output of the SEC-DRI-LS-VIS method (described above) as follows.
  • ] aV g, of the sample is calculated by:
  • the branching index g' is defined as:
  • the hydrogenated polybutadiene based modifier can be represented as a butane copolymer for these calculations with 12% butene.
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • the polymer sample is dissolved in 1 , 1 ,2,2-tetrachloroethane-d2 (TCE-d2) and transferred into a 5 mm glass NMR tube.
  • samples are prepared by adding about 0.3 g sample to approximately 3 g of tetrachloroethane-d2 in a 10 mm NMR tube.
  • the samples are dissolved and homogenized by heating the tube and its contents to 150°C.
  • the data are collected using a Varian spectrometer, with corresponding lH frequencies of either 400 or 700 MHz (in event of conflict, 700 MHz shall be used).
  • the data are acquired using nominally 4000 transients per data file with a about a 10 second pulse repetition delay.
  • multiple data files may be added together.
  • the spectral width was adjusted to include all the NMR resonances of interest and FIDs were collected containing a minimum of 32K data points.
  • the samples are analyzed at 120°C in a 10 mm broad band probe.
  • TMPTA trimethylolpropane triacrylate
  • COE cyclooctene
  • DCM dichloromethane
  • the solution was stirred by a magnetic stirrer.
  • a small volume of Grubbs 2nd generation catalyst solution in DCM (1 milliliter) was prepared and injected into the stirred monomer solution.
  • the reaction mixture was stirred at 40°C under slow nitrogen flow for 16 hours before it was quenched by several drops of ethyl vinyl ether. Silica gel was then added and the mixture was stirred overnight at room temperature.
  • T3/T2 means more fully inserted connectors and thus more completed dendritic structures. This is a conservative estimation because less Tl (a Tl moiety has 2 unreacted acrylic double bonds) is needed to account for the same amount of terminal acrylic double bonds than T2 (a T2 moiety has only 1 unreacted acrylic double bond). If the insertion efficiency is calculated as T3/(T2+T1), the value will be higher than T3/T2.
  • linker length increases along with the decrease of catalyst loading.
  • a reaction flask was charged with 60 mmol cyclooctene (COE), 0.363 mmol pentaerythritol tetraacrylate (PETA), and 20 milliliters of toluene.
  • COE cyclooctene
  • PETA pentaerythritol tetraacrylate
  • a small volume of 85 milligrams of Grubbs 2nd generation catalyst solution in toluene (1 milliliter) was prepared and injected into the stirred monomer solution.
  • reaction mixture was stirred at 60°C under slow nitrogen flow for 16-48 hours before it was quenched by several drops of ethyl vinyl ether. During the synthesis, no gels were formed. A small amount of reaction mixture was taken out by syringe and dried for NMR and GPC analyses. To the same reaction flask, excess p-toluenesulfonhydrazide (TSH, normally 3 equivalents to olefins), 10-40 milligrams butylated hydroxy toluene (BHT), and
  • the branching index g' of DPEY was found to be 0.42 by GPC-3D, suggesting a highly branched structure.
  • the mass recovery of GPC was nearly quantitative, indicating no gel presence in the synthesis.
  • Differential Scanning Calorimetry (DSC) showed the melting point of the DPEY was 128°C and its crystallinity was 66%. This synthesis can be scaled up to kilogram scale by utilizing large reaction vessel and mechanical stirrer.
  • the same reaction performed by utilizing a mechanical stirrer yielded a dendritic PE with the same chemical composition but higher molecular weight and lower branching index.
  • the fully hydrogenated dendritic polyethylene, DPEY2 synthesized by mechanical stirring had Mw of 327,000 g/mol (light scattering detector with reference to linear polyethylene standards). Its branching index g' was determined to be 0.31 by GPC-3D, indicating an even higher branched structure. DSC showed the melting point of DPEY2 is 127°C and its crystallinity is 67%.
  • the dendritic PEs demonstrated excellent thermal stability confirmed by both Thermal Gravimetric Analysis (TGA) and rheology. As shown in the Figure 7, DPEY2 exhibits extensional hardening with a large strain hardening ratio (SHR) of 30.
  • TGA Thermal Gravimetric Analysis
  • SHR strain hardening ratio
  • a reaction flask was charged with 12 mmol cyclooctene (COE), 48 mmol 1,5-dimethylcyclooctadiene (DMCOD), 0.363 mmol tetraacrylate PETA, and 17 milliliters of toluene.
  • the solution was stirred by a magnetic stirrer.
  • a small volume of 85 milligrams of Grubbs 2nd generation catalyst solution in toluene (1 milliliter) was prepared and injected into the stirred monomer solution.
  • the reaction mixture was stirred at 60°C under slow nitrogen flow for 16-48 hours before it was quenched by several drops of ethyl vinyl ether. Silica gel was then added and the mixture was stirred overnight at room temperature.
  • the reaction mixture was filtered and the filtrate was concentrated followed by precipitation to methanol.
  • the reaction scheme is shown in Figure 10.
  • the polymer product was received after filtration and drying as an off-white gummy solid with high yields.
  • the structure of the polymer was determined by lH NMR as shown in Figure 11.
  • GPC analysis showed the unsaturated polymer had Mw of 116 kDa and PDI of 7.6 (refractive index detector with reference to polyisobutylene standards).
  • DSC showed no obvious melting point.
  • NMR confirmed almost all the PETA connectors were fully inserted into the copolymer of COE and DMCOD.
  • an amorphous 50/50 (wt/wt) dendritic EP copolymer is expected and can be used as a viscosity index improver in lubricant oils.
  • the synthesis can be scaled up to kilogram scale by utilizing large reaction vessel and mechanical stirrer.
  • cyclic olefins other than DMCOD such as norbornene or its derivatives, can be employed.
  • ExceedTM 2018 Polyethylene a linear m-LLDPE, ExxonMobil Chemical Company, Houston Texas, 0.918 g/cc, MI of 2 dg/min (190°C, 2.16 kg), Mw of about 94,000 g/mol, an Mw
  • the minor component and matrix polyethylene were compounded in a 1 " Haake twin screw extruder.
  • the Haake twin screw extruder was set at 50 rpm and the melt temperature was targeted at 190°C.
  • the blown film experiments were conducted on a Haake blown film line containing a 1 " single screw extruder and a 1 " monolayer blown film die.
  • the single screw has a Maddock mixing session.
  • the pure resin or the blends were fed into the 1 " single screw extruder to be melted and homogenized.
  • the molten polymer was pressurized and fed into a 1" tubular die.
  • the annular die forms an annular shape with the molten polymer melt with even flow distribution around its circumference.
  • BUR blowup ratio
  • D is the die diameter and L is the film bubble lay flat width.
  • the BUR is the same and is set at 2.8.
  • the film gauge is 1.5 mil. (The film had a lay flat of 4.4 inches (11.2 cm), an extruder speed of 33 rpm, and extrusion temperatures in zones 1, 2, 3, and 5 (die) were 190°C, 195°C, 190°C, and 185°C, respectively.)
  • the nip rollers are driven by a motor with varied speeds.
  • the film was solidified prior to reach the up-nip rollers.
  • the film was collected after passing through the up-nip rollers.
  • the thickness of the film is controlled by speed of the nip rollers.
  • Blend C A comparative blend/film of ExceedTM 2018 PE combined with 5 wt% LDPE (ExxonMobil Chemical Company, Houston, Texas LD071.LRTM PE, 0.924 g/cc, 0.70 dg/min, 190°C, 2.16 kg) and 0.1 wt% BHT was also prepared under the conditions described above (referred to as Blend C).
  • the blend compositions and film properties are listed in Table 1.
  • the 1% modifier blends produce gel-free films with the excellent optics.
  • the haze value is reduced from 43.2% for ExceedTM 2018 PE to 5.9% for the blend.
  • One of the blown film processability measurements is the film gauge variation as measured by the coefficient of variation (COV).
  • Blend B shows lower gauge COV compared to Blend A.
  • Blend B also retains most of the mechanical properties except dart impact strength, which is lower than Blend A but higher than the ExceedTM 2018 PE blend with 5% LDPE. Although the 5% LDPE blend improved the gauge COV and optical properties, the dart impact strength was reduced significantly.
  • the 1% modifier (DPEY2) blend exhibited improved MD/TD tear properties. Both MD tear and TD tear were improved by 5 ⁇ 9% in comparison to neat ExceedTM 2018 PE film, while the MD tear of 5% LDPE blend was reduced by 23% in comparison to neat ExceedTM 2018 PE film.
  • compositions, an element or a group of elements are preceded with the transitional phrase "comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

La présente invention concerne des compositions de polyéthylène qui comprennent un ou plusieurs polymères d'éthylène et un ou plusieurs modificateurs polymères hydrocarbonés dendritiques. La présente invention concerne également, en particulier, des mélanges de polyéthylène comprenant un ou plusieurs polymères d'éthylène et un ou plusieurs modificateurs polymères hydrocarbonés dendritiques. Le modificateur possède : 1) une valeur g'vis inférieure à 0,75 ; 2) au moins 0,6 ppm de groupes ester déterminés par RMN 1H ; 3) une Tm supérieure ou égale à 100 °C ; 4) un Mp supérieur ou égal à 50 000 g/mol, comme déterminé par chromatographie par perméation de gel ; 5) un nombre moyen d'atomes de carbone entre les points de ramification supérieur ou égal à 70, tel que déterminé par RMN 1H.
PCT/US2012/066309 2011-11-22 2012-11-21 Compositions de film soufflé de polyéthylène modifié possédant une excellente stabilité de bulles WO2013078351A1 (fr)

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US13/302,446 2011-11-22
US13/302,446 US8487059B2 (en) 2011-11-22 2011-11-22 Synthesis of dendritic polyolefins by metathesis insertion polymerization
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US13/584,284 US8629217B2 (en) 2011-11-22 2012-08-13 Modified polyethylene blown film compositions having excellent bubble stability
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